Impact of BaTiO(3) nanoparticles on pretransitional effects in liquid crystalline dodecylcyanobiphenyl.

The pretransitional behavior of dodecylcyanobiphenyl (12CB) (isotropic-smectic-A-solid mesomorphism) with d=50nmBaTiO(3) nanoparticles (NPs) linked to the cubic phase was monitored via temperature studies of dielectric constant. Tests were carried out in the isotropic, liquid crystal mesomorphic, and solid phases. For each phase transition the same value of the critical exponent α∼0.5 was obtained, including nanocolloids. All phase transitions show the weakly discontinuous nature. The temperature metric of the discontinuity ΔT notably decreases when adding nanoparticles. The addition of nanoparticles first decreases the dielectric constant by approximately 50% in comparison with pure 12CB, but already for a concentration ∼x=0.4% NP an increase over 50% takes place. It is notable that for the latter concentration unique hallmarks of the pretransitional effect emerge also for the solid-mesophase transition. All these indicate the important impact of nanoparticles on multimolecular mesoscale fluctuations.

Fractional Debye-Stokes-Einstein behaviour in an ultraviscous nanocolloid: glycerol and silver nanoparticles.

One of the major features of glass forming ultraviscous liquids is the decoupling between translational and orientational dynamics. This paper presents studies of this phenomenon in glycerol, an accepted molecular glass former, concentrating on the impact of two exogenic factors: high pressures (P) up to the extreme 1.5 GPa and silver (Ag) nanoparticles (NPs). The analysis is focused on the fractional Debye-Stokes-Einstein (FDSE) relationship: σ(T,P)(τ(T,P))(S) = const, linking DC electric conductivity (σ) and primary (alpha, structural) relaxation time (τα). In glycerol and its nanocolloid (glycerol + Ag NPs) at atmospheric pressure only negligible decoupling (S ∼ 1) was detected. However, in the compressed nanocolloid, a well-defined transformation (at P = 1.2 GPa) from S ∼ 1 to the very strongly decoupled dynamics (S ∼ 0.5) occurred. For comparison, in pressurized 'pure' glycerol the stretched shift from S ∼ 1 to S ∼ 0.7 took place. This paper also presents the general discussion of FDSE behavior in ultraviscous liquids, including the new link between the FDSE exponent, fragility and the apparent activation enthalpy and volume.

Scaling the dynamics of orientationally disordered mixed crystals.

The evolution of the primary relaxation time of orientationally disordered (OD) mixed crystals [(CH(3))(2)C(CH(2)OH)(2)](1-X)[(CH(3))C(CH(2)OH)(3)](X), with 0 < X < or = 0.5, on approaching the glass temperature (T(g)) is discussed. The application of the distortion-sensitive, derivative-based procedure revealed a limited adequacy of the Vogel-Fulcher-Tammann parametrization and a superiority of the critical-like description tau proportional to (T - T(C))(-phi(') ), phi(') = 9-11.5, and T(C) approximately T(g) - 10 K. Basing on these results as well as that of Drozd-Rzoska et al. [J. Chem. Phys. 129, 184509 (2008)] the question arises whether such behavior may be suggested as the optimal universal pattern for dynamics in vitrifying OD crystals (plastic crystals). The obtained behavior is in fair agreement with the dynamic scaling model (DSM) [R. H. Colby, Phys. Rev. E 61, 1783 (2000)], originally proposed for vitrifying molecular liquids and polymers. The application of DSM made it possible to estimate the size of the cooperatively rearranging regions ("heterogeneities") in OD phases near T(g).

On the glass temperature under extreme pressures.

The application of a modified Simon-Glatzel-type relation [Z. Anorg. Allg. Chem. 178, 309 (1929)] for the pressure evolution of the glass temperature is presented, namely, Tg(P)=Tg0[1+DeltaP/(pi+Pg0)]1/bexp[-(DeltaP/c)], where (Tg0,Pg0) are the reference temperature and pressure, DeltaP=P-Pg0, -pi is the negative pressure asymptote, b is the power exponent, and c is the damping pressure coefficient. The discussion is based on the experimental Tg(P) data for magmatic silicate melt albite, polymeric liquid crystal P8, and glycerol. The latter data are taken from Cook et al. [J. Chem. Phys. 100, 5178 (1994)] and from the authors' dielectric relaxation time (tau(P)) measurements, which employs the novel pressure counterpart of the Vogel-Fulcher-Tammann equation: tau(P)=tau0P exp[DPDeltaP/(P0-P)], where DeltaP=P-PSL (PSL is the stability limit hidden under negative pressure), P0 is the estimation of the ideal glass pressure, and D(P) is the isothermal fragility strength coefficient. Results obtained suggest the hypothetical maximum of the Tg(P) curve, which can be estimated due to the application of the supporting derivative-based analysis. A hypothetical common description of glass formers characterized by dTg/dP>0 and dTg/dP<0 coefficients is suggested. Finally, the hypothetical link between molecular and colloidal glass formers is recalled.

Complex dielectric relaxation in supercooling and superpressing liquid-crystalline chiral isopentylcyanobiphenyl.

Results of broadband dielectric studies in glass-forming liquid crystalline chiral isopentylcyanobiphenyl (5(*)CB) are presented. Tests conducted as a function of temperature and pressure revealed the coexistence of glassy and critical properties. The latter are associated with the isotropic-cholesteric phase transition at T(I-Ch) approximately 250 K under atmospheric pressure. Dielectric loss curves in the isotropic liquid and in the cholesteric phase are clearly broadened on cooling and pressuring towards the glass transition. Although in the isotropic phase there is a single stretched loss curve, in the mesophase an additional relaxation process can be distinguished. The evolution of relaxation times is non-Arrhenius and can be portrayed by the Vogel-Fulcher-Tamman relation or its pressure counterpart. The glassy dynamics coexists with the critical-like behavior for the static dielectric permittivity and for the maxima of the dielectric loss curves. Their temperature and pressure dependences are associated with the critical exponent phi=1-alpha approximately 1/2, where alpha approximately 1/2 is the specific heat critical exponent. This behavior is associated with the continuous phase transition placed at DeltaT approximately 1.5 K below the clearing temperature for P=0.1 MPa. It has been found that 5(*)CB shows a unique pressure-temperature phase diagram. Pressure and temperature changes which begin in the isotropic liquid below at ca. T approximately 265 K always result in the transition to the cholesteric phase which can be supercooled or superpressed. For T>265 K the phase transition to another phase, presumably a solid one, always occurs. However, a cholesteric-solid phase border seems to exist only in isothermal pressure tests. It does not appear in the temperature studies.

Complex dynamics of isotropic 4-cyano-4-n-pentylbiphenyl (5CB) in linear and nonlinear dielectric relaxation studies.

A comprehensive presentation of the temperature evolution of "linear" and "nonlinear" dielectric relaxation in the isotropic phase of nematic liquid crystalline compound 5CB (4-cyano-4-n-pentylbiphenyl) is given. The "nonlinear" relaxation is related to the strong pretransitional rise in the lifetime of prenematic fluctuations. The "linear" relaxation has a clear non-Debye and non-Arrhenius form. In the immediate vicinity of the nematic clearing point it shows a weak pretransitional anomaly. Results obtained coincide with the complex liquid relaxation pattern found in transient grating optical Kerr effect studies [A. Sengupta and M. D. Fayer, J. Chem. Phys. 102, 4193 (1995); R. Torre et al., Philos. Mag. A 77, 645 (1997)]. The striking similarity to the behavior found in critical, binary mixtures suggests the extension of the "fluidlike" hypothesis for the isotropic-nematic transition to dynamic phenomena in the isotropic phase [P. K. Mukherjee. J. Phys.: Condens. Matter 10, 9191 (1998)]. The presence of both glassy and fluidlike features in isotropic 5CB coincides with the recent results of simulation analysis for the system of hard ellipsoids by Latz et al. [Phys. Rev. E 62, 5173 (2000)] and with the novel general picture for liquid-liquid transitions proposed by Tanaka [Phys. Rev. E 62, 6968 (2000)].

Critical behavior in broad-band dielectric relaxation on approaching the critical consolute point in ethanol-dodecane mixture.

We present a quantitative experimental evidence for the influence of critical fluctuations on the high frequency dielectric relaxation in a binary critical mixture. The analysis clearly shows the presence of critical anomaly both for the maxima (epsilon(")(p)) and frequencies (f(p)) of loss curves peaks. For the temperature evolution of epsilon(")(p) similar relation as for the static dielectric permittivity was obtained. The temperature dependence of relaxation times can be portrayed by using the Eyring-type equation remote from the critical consolute point and shows the unusual precritical speeding up. The obtained behavior resembles that found recently in the isotropic phase of nematic liquid crystals [A. Drozd-Rzoska and S. J. Rzoska, Phys. Rev. E 65, 041701 (2002)]. Results presented agree also with the recent theoretical suggestion [S. Goodyear and S. C. Tucker, J. Chem. Phys. 111, 9673 (1999)] that relaxation in supercritical fluids may exhibit glasslike features.

Glassy and fluidlike behavior of the isotropic phase of n-cyanobiphenyls in broad-band dielectric relaxation studies.

It is shown that the temperature behavior of peaks f p, of dielectric loss curves in the isotropic phase of n-cyanobiphenyls n = 8, 9, 10 with isotropic-nematic and isotropic-smectic A transitions exhibits features characterisic for both supercooled, glass-forming liquids and critical, binary mixtures. The behavior of f p T can be portrayed by the Vogel-Fulcher-Tamman relation and the "critical-like", mode-coupling theory (MCT) equation. The latter is supported by the novel analysis of electric conductivity σ T . The obtained f p T and σT dependencies can be related by using the fractional Debye-Einstein-Stokes law. For all tested mesogens the static dielectric permittivities ɛ(') T and T are described by dependencies resembling those applied in the homogeneous phase of critical mixturesbut with specific-heat critical exponent α≈ 0.5. This behavior agrees with the novel fluidlike description for the isotropic-nematic transition (P.K. Mukherjee, Phys. Rev. E 51, 5745 (1995); A. Drozd-Rzoska, Phys. Rev. E 59, 5556 (1999)). The obtained glassy features of dielectric relaxation support the recent simulation analysis carried out by M. Letz et al.Phys. Rev. E 62, 5173 (2000)).

Pretransitional behavior of dielectric permittivity on approaching a clearing point in a mixture of nematogens with antagonistic configurations of dipoles.

The results of studies of static dielectric permittivity epsilon(T) in the isotropic phase of 4-cyano-4-pentylalkylbiphenyl and n-p-methoxybenzylidene-p'-butylaniline (5CB-MBBA) mixtures are presented. 5CB and MBBA are nematogens with antagonistic permanent dipole moments configurations. An increase in MBBA concentration strongly decreases the pretransitional effect. However, a derivative analysis detected the existence of a pretransitional anomaly even if its weakness made a straightforward epsilon(T) fit impossible. The obtained anomalies can be well portrayed by fluidlike equations, isomorphic to that applied in critical binary mixtures. Every time the same value of the specific heat critical exponent alpha approximately 0.5 was obtained. A preliminary discussion of the influence of the permanent dipole configuration on the pretransitional behavior of dielectric permittivity was also possible.

Critical anomaly of dielectric permittivity for the temperature and pressure paths on approaching the critical consolute point.

The experimental results of isothermal pressure dielectric permittivity epsilon studies in a critical mixture characterized by a negative shift of critical temperature induced by pressure (dT(C)/dP<0) are presented. The critical effect is portrayed by the same relation as in previous epsilon(T) and epsilon(P) studies, with the critical exponent alpha=0.12+/-0.03. The advantage of pressure studies is the negligible influence of the correction-to-scaling term and the low-frequency Maxwell-Wagner effect. This conclusion is supported by the distortion-sensitive derivative analysis of the experimental data. In contrast to previous epsilon(P) studies, carried out in mixtures with dT(C)/dP>0, the critical effect manifests by the bending-up behavior near the critical point. It is suggested that signs of the critical amplitudes of epsilon(P) and epsilon(T) anomalies may be related to the excess volume V(E) and the excess enthalpy H(E), respectively.

Quasicritical behavior of the low-frequency dielectric permittivity in the isotropic phase of liquid crystalline materials.

Results presented give evidence of the existence of quasicritical, fluidlike behavior in the isotropic phase of 4-cyano-4-pentyl-biphenyl (5CB) for frequencies ranging from the static to the ionic-dominated [low-frequency (LF)] region. Despite the boost of dielectric permittivity on lowering the frequency below 1 kHz, values of the isotropic-nematic transition discontinuity (approximately 1.1 K) and the critical exponent alpha (approximately 0.5) remain constant. It is shown that the contribution from residual ionic impurities is a linear function of temperature in the critical, prenematic fluctuation-dominated region. The validity of the fluidlike and critical behavior for LF dielectric permittivity confirmed results of a derivative analysis of the experimental data: d(epsilon)/dT proportional to (T-T*)(-alpha), originally proposed for critical mixtures. Results of a preliminary test in the isotropic phase of 4-decyl-4'-isothiocyanatobiphenyl (10BT), on approaching the smectic-E phase, may indicate a general validity of results obtained.

Quasicritical behavior of dielectric permittivity in the isotropic phase of smectogenic n-cyanobiphenyls

Results are presented of temperature and pressure studies of static dielectric permittivity (epsilon) and the nonlinear dielectric effect (NDE) in the isotropic phase of smectogenic n-cyanobiphenyls: 9CB, 10CB, and 12CB (4-cyano-4'-n-alkylbiphenyl, n = 9, 10, and 12). For the mentioned properties, pretransitional effects can be well portrayed by applying the relations used for the isotropic phase of nematogens, where evidence of the quasicritical, fluidlike behavior with exponents alpha approximately 0.5 and gamma = 1 exists. This kind of behavior one can also observe on approaching the isotropic-smectic A transition. NDE studies in 10CB and 12CB made it possible to determine the pressure evolution of the discontinuity (delta T) of the I-SmA transition. It was found that pressure first decreases the discontinuity of the transition, and that next a gradual rise appears. This behavior is unlike the one observed for the isotropic-nematic transition, where only an increase of delta T with rising pressure was observed.

Phase transitions from the isotropic liquid to liquid crystalline mesophases studied by linear and nonlinear static dielectric permittivity

Results of studies of static dielectric permittivity (epsilon) and nonlinear dielectric effect (NDE) in the isotropic phase of 4-n-4'-isothiocyanatobiphenyl (nBT) homologous series from n = 2 to n = 10 exhibiting the isotropic-smectic E (I-SmE) transition, are presented. They are compared with results of similar studies in 4-cyano-4-n-alkylbiphenyls (nCB) from n = 4 to n = 12. In this homologous series isotropic-nematic (I-N) and isotropic-smectic-A (I-Sm-A) transitions take place. Despite significant differences between N, Sm-A, and Sm-E phases the same pretransitional behavior of epsilon and NDE in the isotropic phase, described by critical exponents gamma = 1 and alpha = 0.5, was found. It has been shown that when the length of the alkyl chain of a compound increases the discontinuity of the transition drops in nBT and rises in nCB. The influence of pressure on the discontinuity is also discussed.

Dynamics of critical fluctuations in a binary mixture of limited miscibility under a strong electric field

Experimental investigations of relaxation after switching off the strong electric field in a nitrobenzene-dodecane mixture are presented. Studies were conducted for mixtures of critical and noncritical concentrations using the time-resolved nonlinear dielectric effect. The decays obtained can be portrayed by means of the stretched exponential function with the value of the exponent in agreement with the dynamic droplet model predictions. It has been shown that experimental decays exhibit a universal scaling behavior. The relaxation time (scaling factor) shows a power behavior with the exponent y approximately 1.2 for the critical mixture and y-->1 for the noncritical one. These values are much smaller than theoretically predicted y=1.8-1.9. Based on the assumption that a strong electric field induces in the mixture a quasinematic structure with semiclassical critical properties, a quantitative explanation of this difference is proposed.

Shear viscosity studies above and below the critical consolute point in a nitrobenzene-decane mixture

The shear viscosity has been studied in a nitrobenzene-decane critical mixture above the critical consolute temperature T(C), in the homogeneous phase, and below T(C), in coexisting phases. The form of background viscosity for coexisting phases has been postulated. The same value of the critical exponent straight phi has been obtained in the lower (L), upper (U), and homogeneous (H) phases. The pretransitional amplitudes (A(L,U)) in coexisting phases are approximately the same, whereas A(L,U)/A(H) approximately 0.965. In the homogeneous phase the possibility of the appearance of the quasinematic, field-induced structure of critical fluctuations has been discussed.

Quasicritical behavior of dielectric permittivity in the isotropic phase of n-hexyl-cyanobiphenyl in a large range of temperatures and pressures.

Results of studies of the dielectric permittivity and nonlinear dielectric effect (NDE) in the isotropic phase of n-hexyl-cyanobiphenyl are presented. The data reported cover both pressure and temperature dependence. Measurements under atmospheric pressure were carried out in a wide range, up to 100 K from the clearing temperature. The application of a weak measurement frequency (f=67 kHz) resulted in a negligible influence of relaxation processes on NDE results. For both temperature and pressure paths, the dielectric permittivity and the NDE exhibited strong pretransitional effects, described by "critical" exponents phi =1-alpha approximately 0.5 and gamma=1, respectively. Scaling expressions for the pretransitional behavior of the NDE and of the dielectric permittivity have been proposed. The relationship between pretransitional effects in the isotropic phase of nematogens and in critical solutions has also been discussed.