Specific heat of around the glass transition

Dynamic calorimetric measurements are performed for the quaternary metallic glass Zr₆₅Al_7.5Cu_17.5Ni₁₀ in order to analyse the dependence on different heating rates for the glass transition temperature T_g. We compare two different temperature programs used for sample relaxation, to estimate the influence of the thermal history on T_g. A lower limit for the glass transition temperature T_g was calculated according to two different models based on the fact, that width and temperature of the glass transition depend on the experimental time scale set by the heating rate: One model assumes a Vogel-Fulcher-Tammann type behaviour, as used to describe more or less “fragile” glass formers and the other assumes an Arrhenius-like behaviour, which is related to “strong” glass formers. The values obtained from both models differ by about 80K. From additional absolute specific heat capacity measurements we calculate the Kauzmann temperature T_K, as a lower limit for the temperature of the glass transition from thermodynamic aspects. Comparing T_K with the temperature values obtained from the two evaluation models we can classify the quaternary metallic glass Zr₆₅Al_7.5Cu_17.5Ni₁₀, to behave more like a “strong” glass former. Received: 23 January 1998 / Received in final form and Accepted: 31 August 1998     

Cellular solid behaviour of liquid crystal colloids 2. Mechanical properties

This paper presents the results of a rheological study of thermotropic nematic colloids aggregated into cellular structures. Small sterically stabilised PMMA particles dispersed in a liquid crystal matrix densely pack on cell interfaces, but reversibly mix with the matrix when the system is heated above . We obtain a remarkably high elastic modulus, , which is a nearly linear function of particle concentration. A characteristic yield stress is required to disrupt the continuity of cellular structure and liquify the response. The colloid aggregation in a “poor nematic” MBBA has the same cellular morphology as in the “good nematic” 5CB, but the elastic strength is at least an order of magnitude lower. These findings are supported by theoretical arguments based on the high surface tension interfaces of a foam-like cellular system, taking into account the local melting of nematic liquid and the depletion locking of packed particles on interfaces. Received 13 March 2000 and Received in final form 6 June 2000     

A small-angle X-ray scattering study of the isotropic and nematic phases of V2O5 suspensions

We report small-angle X-ray scattering experiments performed in both the isotropic and nematic phases of aqueous V₂O₅ suspensions. We show that the scattering in the isotropic phase can be well described in the whole accessible q-range by only considering the form factor of non-interacting ribbons. We investigate the influence of concentration and pH on the dimensions of V₂O₅ ribbons and show that these parameters do not have any significant effect, as long as the system stays well within the chemical stability domain of the ribbons. We then show that nematic single domains display an anisotropic small-angle scattering pattern, even at scattering vectors small compared to that at which a characteristic correlation peak is observed. This feature is expected for a nematic phase, but was rarely observed. We finally try to describe this scattering within the framework of theories developed for the structure factor of a nematic polymer, and we reach the conclusion that chain ends are certainly important to understand this pattern. Received 21 July 1999 and Received in final form 17 December 1999     

Smectic-A edge dislocations in a very thin cell

We study stable “bookshelf” smectic-A structures within a very thin plane-parallel cell of thickness L in which the mismatch between surface preferred (d _s) and intrinsic (d₀) smectic layer thicknesses occurs. The Landau-Ginzburg approach based on a complex smectic order parameter is used. For a weak enough smectic positional anchoring strength W smectic layers adopt the modified bookshelf profile. In a thick enough cell with increasing W a lattice of edge dislocations is continuously formed at the confining surfaces and then depinned from them. The structure with dislocations is formed when the condition d ₀/( d ₀/d _s - 1) ∼ 2 is fulfilled, where is the positional surface anchoring extrapolation length. If the cell is thin enough the dislocations formed at opposite cell plates annihilate and consequently the smectic layers adopt a locked bookshelf structure. This transition is discontinuous and takes place when d ₀/(L d ₀/d _s - 1) ∼ 5 is realized. To observe these transitions in a cell of thickness L∼ 1μm the conditions W∼ 10^-6 J/m ² and d ₀/d _s - 1∼ 5 ^. 10^-4 have to be fulfilled. All the three qualitatively different structures coexist at the triple point. Received 21 February 2002     

Elastic neutron scattering and dielectric behaviour of 4% brominated betaine calcium chloride dihydrate (BCCD)

We report a combined experimental study by means of elastic neutron scattering and dielectric measurements of a partially deuterated and brominated BCCD (Betaine Calcium Chloride Dihydrate) crystal. The lowest-temperature phase is one-dimensional modulated and characterized by the coexistence of different commensurate domains (with = 1/4, 4/17, 2/9 and 1/5 on cooling), but with a clear predominance of the five-fold phase. A huge global thermal hysteresis of the wave-vector of the modulation, attaining values of about 9 K in the incommensurate phase and up to 15 K in the “harmless” low temperature part of the phase diagram, is observed up to . The role of lattice defects on this phenomenon is discussed. Similarly to the behaviour of the pure compound, the structural modulation evolves on cooling towards a soliton regime (growth of third and fifth-order satellite peaks), probably with respect to a non-stabilized non-modulated ferroelectric phase. The critical temperatures deduced from dielectric constant and pyroelectric current measurements are in very good agreement with those obtained from neutron scattering. The dielectric anomaly observed in at K, and known as the “-anomaly”, could not be related with any special feature detected in the neutron data, and in particular no correlation between this anomaly and the appearance of the soliton regime can be established. Received 26 October 1998     

Lattice model for translational and rotational motions based on generalised diffusion equations: I. General formalism

A simple lattice model based on generalised diffusion equations and Gaussian statistics, aimed at describing diffusive translational and rotational motions, is presented. It is shown that it allows the generation of correlation functions relevant to spectroscopic techniques that are very similar to those experimentally observed in a large variety of complex systems. For some ranges of values of the model parameters, these functions, which can be expressed in closed mathematical forms, can be approximately represented by the sum of two exponentials or by “stretched" exponentials. Received 17 September 1999 and Received in final form 10 February 2000     

The commensurate and incommensurate TGBC^* liquid crystal phases

We propose complements to the Renn model of the liquid crystal TGBC^* phase. We argue that the rotation angle per helislab is spontaneously in the radian range, not too small to limit the energy cost of the twist grain boundaries between the helislabs, not too large to preserve the double twisting efficiency. Taking the elastic interactions between the helislabs into account, we show that the structure may undergo two different lock-ins, provided that the uncontrolled interactions at the sample surfaces are small enough. First, for appropriate values of the elastic constants, an angular lock-in may fix the rotation angle per helislab at values exactly commensurate to π. Three characteristic lengths of the TGBC^* phase, the TGB period and the thicknesses of both the smectic blocks and of the helislabs are then commensurate to one another, with moreover, integer ratios at the most efficient commensurabilities. The TGBC^* phase could thus exist in several versions, incommensurate and commensurate, according to the steps of a restricted Devil's staircase. A second elastic lock-in should then arise in the commensurate TGBC^* phases, to set the arrays of disclination lines between the helislabs in simple rectangular lattices, arranged in a helical manner. Being placed right behind one another, the disclination lines then coincide when observed along the TGB axis. This could explain the typical textures with square or hexagonal grids, observed in oriented samples. The commensurability of the TGBC^* phases could be analyzed with X-ray scattering experiments in the same manner as already reported for the TGBC phase. Received 30 November 1999 and Received in final form 5 May 2000     

Switching of banana liquid crystal mesophases under field

Taking advantage of the great number of bent-core or “banana" compounds synthesized and studied in the laboratory, we describe their behaviour under the application of an external electric field. If the field were a static one, we would work within the frame of an equilibrium phase diagram in a (field E, temperature T) space where some phases would be simple dielectrics and others ferroelectric ones with a macroscopic polarization, either spontaneous or induced by the field. In this paper, we deal with the basic responses of “banana” liquid crystals under the application of a low frequency (1 to 100 Hz) AC field. Firstly square-wave voltages allow us to locate the phase boundary between dielectric (at lower field) and ferroelectric phases (higher field) at a given temperature and field threshold. Then we apply slowly varying AC voltages with shapes like triangle or “triple-plateau” to check out the stability of the induced ferroelectric phase versus field removal. Three behaviours are encountered, the unstable one (short lifetime of the high-field ferroelectric phase) where the macroscopic polarization is destroyed and then rebuilt in the opposite direction during each half period and usually called “antiferroelectric”; the stable one (long lifetime) with a polarization that rotates at constant modulus which is labeled as “ferroelectric” and a new one where the macroscopic polarization is proportional to the applied fied, we named this behaviour as “superparaelectric”. Let us stress that these observations apply to the ferroelectric phases of the (E, T) phase diagram not to the zero field (0,T) phases observed in the usual phase characterization experiments except for an eventual spontaneous ferroelectric phase. Received 18 April 2002 and Received in final form 17 January 2003 Published online: 16 April 2003 RID="a" ID="a"e-mail: marcerou@crpp.u-bordeaux.fr RID="b" ID="b"URL: http://www.crpp-bordeaux.cnrs.fr     

Griffiths phase manifestation in disordered dielectrics

We predict the existence of a Griffiths phase in dielectrics with a concentrational crossover between dipole glass (electric analog of spin glass) and ferroelectricity. Particular representatives of the above substances are KTaO₃:Li, Nb, Na, or relaxor ferroelectrics like Pb_1–xLa_xZr_0.65Ti_0.35O₃. Since this phase exists above the ferroelectric phase-transition temperature (but below that temperature for ordered substances), we call it a “para-glass phase”. We assert that the difference between paraelectric and para-glass phases in the above substances is the existence of clusters (inherent to the “ordinary” Griffiths phase of Ising magnets) of correlated dipoles. We show that randomness plays a decisive role in the Griffiths (para-glass) phase formation: this phase does not exist in a mean field approximation. To investigate the Griffiths phase properties, we calculate the density of Yang-Lee (YL) zeros in the partition function and find that it has “tails” inherent to the Griffiths phase in the above temperature interval. We perform calculations on the basis of our self-consistent equation for the long-range order parameter in an external electric field. This equation has been derived in the framework of the random field theory. The latter automatically incorporates both short-range (due to indirect interaction via transverse optical phonons of the host lattice) and long-range (ordinary dipole-dipole) interactions between impurity dipoles, so that the problem of long-range interaction considerations does not appear in it. Received 17 May 2000     

Phases hexagonales colonnaires thermotrope et lyotrope : défauts observés par cryofracture et caractère anomal du thermotrope

Electron microscopy observations of replicas of freeze-fractured samples of two columnar hexagonal phases of different nature (a lyotropic one, the inverse AOT in water; a thermotropic one, ) yield very different results: most defects at microscopic scales are screw dislocations in the lyotropic phase, longitudinal edge dislocations in the thermotropic phase. A possible way to interpret these differences is as follows: in the lyotropic the Lamé coefficients and μ and the bend modulus K₃ would not display any anomaly compared to expected values; in the thermotropic the shear modulus μ would be ten times smaller than the compressibility modulus , while K₃ would still be comparable to (but larger than) the bend modulus of a small molecules liquid crystal. We present an elementary theoretical model of the latter case which could explain the anomalous measurements of K₃ and of the longitudinal compressibility (Ref. [#!ref10!#]) without contradicting more recent measurements of (Refs. [#!ref17!#,#!ref22!#]). Essentially, the hexagonal phase would be a phase with defects (longitudinal dislocations) akin to an hexatic phase but with some differences. Re?u : 26 mai 1997 / Révisé : 20 Janvier 1998 / Accepté : 27 avril 1998     

Evolution of charge ordering in manganites

Charge ordering phenomena in the manganites Ca_1-xSm_xMnO₃ have been studied for , using electron diffraction and lattice imaging, completed by magnetic and transport measurements. Three domains can be distinguished, depending on the nature of the structural transitions with temperature. For , the structural transition from a pseudo-tetragonal to a monoclinic form, with decreasing temperature, coincides with the competition between ferromagnetism and antiferromagnetism that is characterized by the temperature T_peak on the M ( T ) curves; short-range charge ordering is observed for manganites. For the second domain, , a structural transition from an orthorhombic to a long-range charge ordered state is clearly observed with decreasing temperature. The corresponding temperature T_CO coincides with the temperature T_peak deduced from magnetic measurements. This long range charge ordering, which appears along a, is either commensurate or incommensurate depending on the x value, with a modulation vector, q being close to x. These modulated superstructures correspond to a stacking of single Mn³⁺ stripes with multiple Mn⁴⁺ stripes along a, either in a commensurate or in an incommensurate manner. The third domain , is characterized by a transition to a charge ordered state with commensurate superstructure at low temperature. The latter can be described as a “partially” charge ordered state in which single “Mn³⁺” stripes alternate with mixed “Mn³⁺/Mn⁴⁺” stripes. Received 17 June 1998     

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     

Spinodal dewetting of thin liquid films at soft interfaces

We study theoretically the behavior of nanoscopic liquid films L (thickness e) intercalated between a solid S and a rubber R (elastic modulus μ). Thickness modulations involve a healing length , which results from a competition between elastic and disjoining pressure. With van der Waals interactions, , where a is a molecular size and h₀ the rubber capillary length ( , interfacial tension). If the Hamaker constant of the intercalated liquid is negative, the film dewets by amplification of peristaltic fluctuations (“spinodal dewetting”). The typical size of the contacts is predicted to scale like for films of thicknesses . The rise time of the fastest mode, predicted to scale like , should be very sensitive to the film thickness. Received 11 February 2000 and Received in final form 22 May 2000     

Localization and dephasing driven by magnetic fluctuations in low carrier density colossal magnetoresistance materials

Localization and dephasing of conduction electrons in a low carrier density ferromagnet due to scattering on magnetic fluctuations is considered. We claim the existence of the “mobility edge”, which separates the states with fast diffusion and the states with slow diffusion; the latter is determined by the dephasing time. When the “mobility edge” crosses the Fermi energy a large and sharp change of conductivity is observed. The theory provides an explanation for the observed temperature dependence of conductivity in ferromagnetic semiconductors and manganite pyrochlores. Received 17 January 1999 and Received in final form 12 March 1999     

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     

Elastic Green's function of icosahedral quasicrystals

The elastic theory of quasicrystals considers, in addition to the “normal” displacement field, three “phason” degrees of freedom. We present an approximative solution for the elastic Green's function of icosahedral quasicrystals, assuming that the coupling between the phonons and phasons is small. Received: 18 December 1997 / Accepted: 6 March 1998     

Lyotropic bicontinuous cubic phase single crystals investigated using high-resolved X-ray scattering

Single crystals of an Ia d bicontinuous direct cubic phase formed by a non-ionic surfactant in water are investigated using high-resolved X-ray diffraction. The shape of the Bragg peaks confirms the existence of a 3D long-range order inside the cubic phase. A weak diffuse scattered intensity signal is measured very near the Bragg peaks. We attribute this signal to thermal diffuse scattering (TDS) and we give an estimation of the contribution of elastic waves to this TDS. Received 4 May 2000     

Droplet suction on porous media

We study the forced aspiration of small ( mm) and large ( cm) liquid drops, deposited on prewetted porous membranes, and pumped mechanically with a constant current J. Two kinds of membranes are used where the pores are i) disconnected, cylindrical and calibrated or ii) interconnected “sponge-like”. Whatever the size of the drops and the intensity J of the current, two suction regimes are observed versus time: 1) a “locked” regime, when the drop is pinned, with a dynamic contact angle decreasing from advancing () to finite receding () contact angle; 2) an “unlocked” regime, where the contour line recedes with a constant contact angle closed to . In both regimes, the shape of the drop remains quasistatic, during the suction process, i.e. a spherical cap for small drops and a flat “gravity pancake” for large ones. Received 19 January 2000     

Thermal conductivity of pressure polymerized C60

60 polymerization in the temperature interval at pressures below by measurements of the time dependence of the thermal conductivity. It has been found at that the polymerization process at is slower than the reverse transformation from “polymeric” to “monomeric” phase at . The thermal conductivity of polymerized C₆₀ was measured in the temperature range and found to increase with increasing temperature, which reflects strong phonon scattering. Both the presence of non-bonded C₆₀ molecules and a high degree of structural disorder in the crystalline lattice of the polymeric phase might be responsible for the behaviour of . The results for are qualitatively similar to those reported previously for C₆₀ polymerized at higher , but an order of magnitude smaller. Received: 20 September 1996/Accepted: 11 November 1996