Calorimetric evidence for the existence of an intermediate phase between the ferroelectric nematic phase and the nematic phase in the liquid crystal RM734.

The idea that rodlike molecules possessing an electric dipole moment could exhibit a ferroelectric nematic phase was suggested more than a century ago. However, only recently such a phase has been reported for two quite different liquid crystals: RM734 [4-[(4-nitrophenoxy)carbonyl)]phenyl 2,4-dimethoxybenzoate] and DIO [2.3',4',5'-tetrafluoro[1,1'-biphenyl]-4-yl 2.6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate]. For RM734 a direct ferroelectric nematic (N_{F}) to classical nematic N transition was reported, whereas for DIO an intermediate phase N_{x} was discovered between the N_{F} and the N phases. Here we present high-resolution calorimetric evidence that an intermediate N_{x} phase also exists in RM734 along a narrow temperature range between the N_{F} and the N phases.

Phase transitions study of the liquid crystal DIO with a ferroelectric nematic, a nematic, and an intermediate phase and of mixtures with the ferroelectric nematic compound RM734 by adiabatic scanning calorimetry.

High-resolution calorimetry has played a significant role in providing detailed information on phase transitions in liquid crystals. In particular, adiabatic scanning calorimetry (ASC), capable of providing simultaneous information on the temperature dependence of the specific enthalpy h(T) and on the specific heat capacity c_{p}(T), has proven to be an important tool to determine the order of transitions and render high-resolution information on pretransitional thermal behavior. Here we report on ASC results on the compound 2,3',4',5'-tetrafluoro[1,1'-biphenyl]-4-yl 2,6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate (DIO) and on mixtures with 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). Both compounds exhibit a low-temperature ferroelectric nematic phase (N_{F}) and a high-temperature paraelectric nematic phase (N). However, in DIO these two phases are separated by an intermediate phase (N_{x}). From the detailed data of h(T) and c_{p}(T), we found that the intermediate phase was present in all the mixtures over the complete composition range, albeit with strongly decreasing temperature width for that phase with decreasing mole fraction of DIO (x_{DIO}). The x_{DIO} dependence on the transition temperatures for both transitions could be well described by a quadratic function. Both these transitions were weakly first order. The true latent heat of the N_{x}-N transition of DIO was as low as L=0.0075±0.0005J/g and L=0.23±0.03J/g for the N_{F}-N_{x} transition, which is about twice the previously reported value of 0.115 J/g for the N_{F}-N transition in RM734. In the mixtures both transition latent heats decrease gradually with decreasing x_{DIO}. At all the N_{x}-N transitions pretransition fluctuation effects are absent and these transitions are purely but very weakly first order. As in RM734 the transition from the N_{F} to the higher-temperature phase exhibits substantial pretransitional behavior, in particular, in the high-temperature phase. Power-law analysis of c_{p}(T) resulted in an effective critical exponent α=0.88±0.1 for DIO and this value decreased in the mixtures with decreasing x_{DIO} toward α=0.50±0.05 reported for RM734. Ideal mixture analysis of the phase diagram was consistent with ideal mixture behavior provided the total transition enthalpy change was used in the analysis.

Convincing evidence for the Halperin-Lubensky-Ma effect at the N-SmA transition in alkyloxycyanobiphenyl binary mixtures via a high-resolution birefringence study.

We present new high-resolution experimental data for the temperature behavior of optical birefringence for a series of mixture of the liquid crystals octyloxycyanobiphenyl (8OCB) and nonyloxycyanobiphenyl (9OCB) by using a rotating analyzer technique. The birefringence data have been used to probe the temperature dependence of the nematic order parameter [Formula: see text]. We have then arrived at values for possible entropy discontinuities at the nematic-smectic A transition temperature [Formula: see text] from the detailed inspection of [Formula: see text] data in the immediate vicinity of [Formula: see text]. The 9OCB mole fraction dependence of the obtained reduced entropy discontinuities has been shown to be well fitted with a crossover function which is itself consistent with the mean-field free energy expression with a non-zero cubic term arising from the Halperin-Lubensky-Ma (HLM) coupling. The obtained results are in good accordance with existing results from adiabatic scanning calorimetry (ASC). Our birefringence results and determined entropy discontinuities (consistent with calorimetry results) are in striking contrast with the recent birefringence results of Barman et al. (Phase Transit. 91, 58 (2018) published online 16 Aug. 2017) claiming second-order nematic-to-smectic A transitions for all mixtures. In this paper we present a possible explanation for this discrepancy. We have also extracted the effective critical exponent values [Formula: see text] characterizing the critical fluctuations near the N-SmA transition for all compositions by using the fact that the temperature derivative of the order parameter [Formula: see text] near [Formula: see text] exhibits the same power-law divergence as the specific heat capacity. Measurable latent heat values were extracted from optical birefringence data for mole fractions of 9OCB where the [Formula: see text] values are as low as 0.2, which is substantially lower than the tricritical value [Formula: see text]. This is qualitatively different from what has been observed so far in other liquid-crystal systems. Together with ASC data, these pecuilarities of the 8OCB+9OCB system render further convincing evidence for the presence of the HLM coupling effect at the N-SmA transition phase transition line.

High-resolution birefringence investigation of octylcyanobiphenyl (8CB): an upper bound on the discontinuity at the smectic-A to nematic phase transition.

We report optical birefringence data by two different methods with high temperature resolution for octylcyanobiphenyl (8CB) near the smectic-A to nematic (Sm-A-N) phase transition temperature T(AN). Within the resolution of our experiments, we find that the Sm-A-N phase transition is continuous. For a possible discontinuity in the orientational order parameter S(T) at T(AN), we arrive at an upper limit of 0.0002, which is substantially smaller than other estimates in literature, but consistent with the value of 0.00008 derived from the upper limit of the latent heat from high-resolution adiabatic scanning calorimetry (ASC), which is itself consistent with the Halperin-Lubensky-Ma theory. The temperature derivative of the order parameter exhibits a power law divergence with a critical exponent that is consistent with the value α = 0.31 ± 0.03 for the specific heat capacity obtained by ASC.

Evidence from adiabatic scanning calorimetry for the Halperin-Lubensky-Ma effect at the N-SmA phase transitions in mixtures of 7OCB+heptane with an injected SmA phase.

The high-resolution adiabatic scanning calorimetric technique has been used to investigate the nematic-smectic A transition (N-SmA in binary mixtures of the non-smectogenic liquid crystal heptyloxycyanobiphenyl (7OCB) and heptane, exhibiting a so-called injected smectic A phase. With the exception of a mixture with the lowest heptane mole fraction for which only an upper limit of 0.2 ± 0.2 J kg(-1) for a possible latent heat could be obtained, for all other mixtures finite latent heats were obtained. The mole fraction dependence of the latent heat could be well fitted with a crossover function consistent with a mean-field free energy expression with a non-zero cubic term arising from the Halperin-Lubensky-Ma (HLM) coupling between the SmA order parameter and the orientational director fluctuations. The mole fraction dependence of the heat capacity effective critical exponents is similar to that observed in mixtures of the two liquid crystals octyloxycyanobiphenyl (8OCB) and nonylcyanobiphenyl (9OCB). The thermal behavior observed along the N-SmA phase transition line yields further strong evidence for the HLM coupling effect.

A line-of-sight electron cyclotron emission receiver for electron cyclotron resonance heating feedback control of tearing modes.

An electron cyclotron emission (ECE) receiver inside the electron cyclotron resonance heating (ECRH) transmission line has been brought into operation. The ECE is extracted by placing a quartz plate acting as a Fabry-Perot interferometer under an angle inside the electron cyclotron wave (ECW) beam. ECE measurements are obtained during high power ECRH operation. This demonstrates the successful operation of the diagnostic and, in particular, a sufficient suppression of the gyrotron component preventing it from interfering with ECE measurements. When integrated into a feedback system for the control of plasma instabilities this line-of-sight ECE diagnostic removes the need to localize the instabilities in absolute coordinates.

Contrast-enhanced dynamic magnetic resonance imaging of finger joints in osteoarthritis and rheumatoid arthritis: an analysis based on pharmacokinetic modeling.

PURPOSE: To investigate a two-compartment kinetic model applied to the dynamic time course of contrast enhancement as a method to differentiate between finger-joint synovitis in established osteoarthritis (OA) and rheumatoid arthritis (RA). MATERIAL AND METHODS: Dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) of one hand in 19 patients and six healthy volunteers was undertaken. Eight patients had OA of the hand and eleven patients had RA. From the signal intensity curves, the three parameters Kps (endothelial transfer constant), Kep (elimination rate constant from extracellular space back to plasma) and Kel (elimination rate constant from plasma by renal excretion) were calculated. RESULTS: The rate constant Kps showed the best separation between the groups with significantly higher values in the RA group compared to the OA group (P<0.005) and in the OA group compared to the control group (P<0.005). Significantly higher values of Kep were also found in the RA group compared with the OA group (P<0.005). CONCLUSION: DCE-MRI may provide useful information that can help differentiate synovitis in OA from synovitis in RA.

Weakly first-order character of the nematic-isotropic phase transition in liquid crystals.

The classification of phase transitions in first-order and second-order (or continuous) ones is widely used. The nematic-to-isotropic (NI) transition in liquid crystals is a weakly first-order transition, with only small discontinuities in enthalpy and specific volume at the transition which are not always easy to measure. On the other hand, fluctuation effects near the transition, typical for a continuous transition, are present because of the only weakly first-order character. In a recent paper [Phys. Rev. E 69, 022701 (2004)], it was concluded from the static dielectric permittivity in the isotropic phase near the NI transition that less polar mesogens (with little or no pretransitional effects) are characteristic for a first-order NI phase transition, whereas in the case of strongly polar ones (with large pretransitional effects) the NI transition is close to second order. In this paper, we address the question whether it is, indeed, possible to use these fluctuation effects in the isotropic phase to quantify the "strength" of a weakly first-order transition, i.e., how far it is from second order. Therefore, we measured the temperature dependence of the enthalpy near the NI transition of seven liquid crystals with adiabatic scanning calorimetry and compared the measured values of the latent heat with pretransitional effects in the dielectric constant and the specific heat capacity. The compounds used in the comparison are MBBA, 5CB, 8CB, 5NCS, 5CN, 8CHBT, and D7AB. From our analysis we find, contrary to the assertion in the above reference, no correlation between the strength of the NI transition of a given compound and the pretransitional effects observed, neither dielectrically, nor thermally.

Dielectric spectroscopy of aerosil-dispersed liquid crystal embedded in Anopore membranes.

The complex dielectric permittivity epsilon* values are presented for aerosil-dispersed 4-pentyl-4-cyanobiphenyl (5CB) confined in Anopore membranes. The dielectric permittivities are measured in the frequency range from 10(-2) Hz to 1 GHz at temperatures ranging from 50 degrees C down to -20 degrees C. In bulk 5CB, which has only a nematic phase, there exist two main relaxation processes: one due to the rotation of molecules around their short axes for parallel orientation of the director to the probing field and another fast relaxation process due to the librational motion of molecules for perpendicular orientation. Inside Anopore membranes both these main relaxation processes can be observed, but with subtle differences. The relaxation process due to the rotation of molecules around the short axis is faster in Anopores at all temperatures in comparison with the bulk process. Hydrophilic aerosil particles, when dispersed in the liquid-crystal (LC) phase, attach to each other via hydrogen bonds and form a three-dimensional interconnecting aerosil network, thus dividing the LC phase into small domains. Dispersing 5CB with different concentrations of hydrophilic aerosils leads to a decrease in relaxation time with aerosil concentration. In these dispersed systems a slow additional relaxation process emerges. This slow process becomes stronger with higher concentrations of aerosil. From our experiments we conclude that this process is the relaxation of 5CB molecules homeotropically aligned to the surface of the aerosil particles. In the case of 5CB-aerosil dispersions enclosed in Anopore membranes this slow process still exists and increases also with aerosil concentration. The relaxation time of the rotation of the 5CB molecules around their short axis systematically increases in these 5CB-aerosil samples in Anopore membranes with aerosil concentration from the 5CB-Anopore behavior towards the behavior observed for 5CB-aerosil dispersions. We explain the evolution as resulting from opposing tendencies from size effects (in the Anopore membranes) and disorder effects (in the aerosil dispersions).

Influence of nanosized confinements on 4-n-decyl-4'-cyanobiphenyl (10CB): a broadband dielectric study.

Real (epsilon') and imaginary (epsilon") parts of the complex dielectric permittivity (epsilon*) of the liquid crystal (LC) 4-n-decyl-4'-cyanobiphenyl (10CB) embedded in Anopore membranes and Vycor porous glass, as well as dispersed with hydrophilic aerosils, have been studied by means of broadband dielectric spectroscopy in the frequency range from 10(-2) Hz to 1 GHz . In bulk 10CB, which has a direct transition from an isotropic to a smectic- A phase, there exists one main relaxation process for the parallel orientation of the director with respect to the probing field and a faster one for the perpendicular orientation. All molecular relaxation processes in 10CB are of Debye type and have Arrhenius like temperature dependence. For 10CB embedded in untreated and surface treated cylindrical pores of Anopore membranes the dielectric spectra are similar to the bulk with the exception that both the rotation around the short axis and the libration motion are faster in the pores. In the case of 10CB dispersed with two different concentrations of hydrophilic aerosils an emergence of a slow relaxation process, which is stronger for the higher concentration, is additionally observed along with the bulklike processes. The slow process in the LC-hydrophilic aerosil system is attributed to the relaxation of the molecules that are homeotropically aligned close to the surfaces of the aerosil particles. This process also has an Arrhenius type of temperature dependence. For 10CB embedded in narrow channels of Vycor porous glass three relaxation processes are observed. Two of these processes are bulklike and are due to the librational motion of molecules and the rotation of molecules around their short axes. The slowest process seems to be a surface process, similar in origin to that observed for 10CB dispersed with hydrophilic aerosils, and is prominent amongst all. The material in the Vycor porous glass could be supercooled by at least 185 degrees below bulk crystallization temperature. The slow process has a Vogel-Fulcher-Tamman (VFT) type of temperature dependence typical for glass formers in this wide temperature range. In addition, the bulklike processes are found to be strongly modified and also have a VFT like temperature dependence from measurements done in a wide temperature range. This behavior is in contrast to other reports of glassy behavior in confined LC, where the glassy behavior as concluded from a slow relaxation process observed in a narrow temperature range.

Effect of aerosil dispersions on the nematic-to-isotropic interface.

The effect of silica aerosils on the kinetics of the first-order nematic-isotropic (NI) phase transition is phenomenologically described in the framework of the time-dependent Landau-Ginzburg equation. A steady-state solution to the equation is presented such that the NI interface may propagate with a solitary-like wave profile under constant quenching. The results provide a plausible basis for the interpretation of the dynamical effects of quenched disorder in the liquid-crystal systems, caused by randomly interconnected porous media, such as aerosils. In the low silica aerosil rho(s) ( < or =0.1 g/cm;3) regime, the calculated values of the interface velocity v(T,rho(s)), the interface thickness kappa(T,rho(s)), and the critical radius of a spherical nucleus of new nematic phase in a bulk isotropic environment, composed of polar molecules, such as 4-n-octyl- 4(')- cyanobiphenyl and 4-n-heptyl- 4(')- cyanobiphenyl shows that the effect of silica aerosils on the kinetics is reflected in a shifting of the set of temperature-dependent curves to lower temperature values.-1.

Characterization of the smectic-A-hexatic-B transition in 650BC by adiabatic scanning calorimetry.

We investigated the smectic-A-hexatic-B (SmA-HexB) transition in the liquid-crystal n-hexyl-4'-n-pentyloxybiphenyl-4-carboxilate (650BC) with adiabatic scanning calorimetry. We were able to prove in a direct way that this transition is indeed very weakly first order, as was already suggested in the literature. The latent heat at the transition was determined to be deltaHL = 0.04 +/- 0.02 J/g. Our experiments confirm the high value for the heat capacity critical exponent earlier reported, yielding alpha = 0.64 +/- 0.05.

Static and dynamic thermal quantities near the consolute point of the binary liquid mixture aniline-cyclohexane studied with a photopyroelectric technique and adiabatic scanning calorimetry.

We studied the thermal conductivity, thermal effusivity, and specific heat capacity at constant pressure of the critical binary liquid mixture aniline-cyclohexane near the consolute point, using a photopyroelectric (PPE) technique and adiabatic scanning calorimetry (ASC). According to recent theoretical predictions based on renormalization group theory calculations, a substantial (but not diverging) enhancement in the thermal conductivity in the homogeneous phase near the critical temperature was expected for this binary system near the consolute point. However, within an experimental precision of 0.05%, we found no deviation from linear behavior in the range of 5 K above Tc down to Tc. The specific heat capacity calculated from the results for the thermal conductivity and effusivity is in good agreement with that measured by ASC. For the ASC results, the theoretical power law expression with the Ising critical exponent was fitted to the specific heat capacity both above and below the transition temperature. Good agreement with theory was found both for the amplitude ratio and the two-scale universality.

Thermal relaxation of glycerol and propylene glycol studied by photothermal spectroscopy.

In this paper we report on experimental data for the frequency and temperature dependence of the thermal properties of supercooled glycerol and propylene glycol. By using a photopyroelectric method the specific heat capacity and thermal conductivity were separately determined in a bandwidth of several decades. We have recently shown that the thermal conductivity has no relaxation behavior, which simplifies the analysis of our results. The relaxation behavior of the specific heat capacity is compared with literature results for other physical quantities and a detailed analysis of the temperature dependence of the relaxation parameters is presented.

Pretransitional anomalies in the shear flow near a second-order nematic-smectic- a phase change.

Pretransitional anomalies in a shear flow near a second order nematic-smectic- A ( NA ) phase transition temperature T(NA), for liquid crystals (LC's), taking into account the fluctuations of the local smectic order parameter above the T(NA), are investigated. It is shown that the tumbling instability of the Couette shear flow for polar LC compounds, such as 4-n-octyl- 4(') -cyanobiphenyl (8CB), in the vicinity of T(NA), e.g., at a few tens of mK from T(NA) in the nematic phase, occurs at any shear rate gamma;.

Thermal conductivity, thermal effusivity, and specific heat capacity near the lower critical point of the binary liquid mixture n-butoxyethanol-water.

Experimental investigations on binary liquid mixtures near the critical mixing point are presently leading to a controversy about the anomaly in the thermal conductivity. A photopyroelectric technique is used to determine the thermal conductivity and the effusivity of the binary liquid mixture n-butoxyethanol-water at its critical concentration near the critical mixing point. It is proven that, contrary to previous reports, there is no critical enhancement in the thermal conductivity. The specific heat capacity is calculated from these results and compared with the results from measurements performed by adiabatic scanning calorimetry.

Broadband dielectric spectroscopy study of molecular dynamics in the glass-forming liquid crystal isopentylcyanobiphenyl dispersed with aerosils.

The glass-forming liquid crystal isopentylcyanobiphenyl (CB15) filled with different concentrations of hydrophilic and hydrophobic aerosils has been investigated by broadband dielectric spectroscopy in the frequency range from 10(-2) Hz to 10(7) Hz over a temperature range of 173 K-300 K. CB15 that consists of chiral molecules has a monotropic system of phases nematic (N*) and smectic-A upon supercooling and forms a glass further on. In the isotropic phase a single Davidson-Cole process exists in the substance, which is due to the rotation of the molecules around their short axes. In the supercooled N* phase a Cole-Cole process that is an order of magnitude faster is additionally present and is due to the rotation in a cone around the local director. The relaxation times of the process due to rotation around short axes obey the empirical Vogel-Fulcher-Tamman behavior typical for glass-forming systems. Filling of the liquid crystal (LC) with different concentrations of hydrophilic aerosils leads to the emergence of a slow relaxation process that grows with the increasing concentration of the aerosils. The aerosil particles, which form a three-dimensional network dividing the LC phase into domains, have little effect on the relaxation times of the bulk processes. As a consequence the glass transition temperature is merely affected. On the other hand, in LCs dispersed with hydrophobic aerosils the slow process is quite weak. The slow process is attributed to the relaxation of the molecules that are homeotropically attached at the surfaces of the aerosil particles. The LC-aerosil surface interaction leads to a considerable slowing down of the molecular rotation around their short axis. The process has an Arrhenius-like temperature dependence of the relaxation times with an activated type of dynamics, which can be explained by considering a nonincreasing rearranging region of cooperativity in surface layers.

Effect of silica aerosils on the nematic to isotropic transition: A theoretical treatment.

The effect of silica aerosils on a first-order nematic-isotropic (NI) transition temperature shift DeltaT(NI)(rho(s)) and on the enthalpy jump DeltaH(rho(s)) is phenomenologically described in the framework of the Landau-de Gennes theory. It is shown that the aerosil network dispersed in the liquid crystal phase creates an additional curvature perturbation, resulting in linear and nonlinear slopes both in the transition temperature shift DeltaT(NI)(rho(s))=-T(NI)(0)alpharho(s) and in the enthalpy jump DeltaH(rho(s))=1 / 4DeltaH(0)(1+sqrt[1-kapparho(s)])(2)(1-alpharho(s)), where rho(s) is the aerosil density, and both alpha and kappa are constants of the theory. In the low rho(s)(

Diabetes mellitus: a risk factor affecting visual outcome in branch retinal vein occlusion.

PURPOSE: The prognosis of visual acuity (VA) after branch retinal vein occlusion (BRVO) in patients with diabetes mellitus is unknown compared to the VA in non-diabetic patients with BRVO. The aim of this study was to evaluate the visual outcome of BRVO in diabetic and non-diabetic patients. METHODS: A retrospective case-control study of diabetic and non-diabetic patients with BRVO was performed. VA and commonly known risk factors and complications of BRVO were compared in a follow-up period of at least 1 year. RESULTS: A total of 28 eyes of patients with diabetes and 49 eyes of non-diabetic patients with BRVO were included. One year after BRVO, the VA in the patients with diabetes decreased significantly more than that of the non-diabetic patients. During the second year after BRVO, the VA did not change significantly in either group. BRVO in patients with diabetes occurs at an earlier age. Diabetic patients needed more outpatient visits. CONCLUSIONS: The VA 1 year after BRVO in patients with diabetes is worse compared to the VA in patients without diabetes. The VA stabilizes 1 year after onset in both groups. Diabetic patients tend to need more frequent follow-up in order to treat the sequelae of BRVO.

First-order character of the smectic-A to chiral nematic transition in chiral liquid-crystal mixtures.

An investigation into the smectic-A to chiral nematic (N'A) transition in liquid crystals is presented by using adiabatic scanning calorimetry (ASC). It is predicted theoretically that chirality drives this transition to first order. This transition is studied in mixtures of the nonchiral liquid crystal octyloxycyanobiphenyl (8OCB) and the chiral 4-(2-methylbutyl)-4(')-cyanobiphenyl (CB15), a system with a large (chiral) nematic region that widens upon increasing the chiral (CB15) fraction. An ASC measurement on pure 8OCB showed no evidence for a latent heat, in agreement with previous ac calorimetric studies, with an upper boundary for the latent heat (if any) of 1.8 J/kg. Since pure 8OCB has no measurable latent heat, and taking into account the widening of the chiral nematic region, the possibility of a continuous to first-order crossover due to the coupling of the nematic and the smectic order parameters, as occurring in several cases of smectic-A to nematic (NA) transitions, can be excluded. However, for all examined mixtures a latent heat could be determined at the smectic-A to chiral nematic transition. This confirms theoretical predictions of the first order character of this transition. Quantitatively, theoretical predictions of the evolution of the entropy discontinuities and latent heats of this transition were not consistent with the experimental results. It was further observed that the transition temperature decreases linearly in agreement with theoretical predictions and a previous ac calorimetric study. Finally, it was observed that the pretransitional specific heat capacity shows an interesting evolution upon increasing chiral fraction, and it may be concluded that any theoretical model based on Landau theory is not sufficient to describe this transition.