Phase behaviour of the thermotropic cubic mesogen 1,2-bis(4-n-decyloxybenzoyl)hydrazine under pressure

The phase transition behaviour of an optically isotropic, thermotropic cubic mesogen 1,2-bis(4-n-decyloxybenzoyl)hydrazine, BABH(10), was investigated under pressures up to 300 MPa using a high pressure differential thermal analyser, a wide angle X-ray diffractometer and a polarizing optical microscope (POM) equipped with a high pressure optical cell. The reversible change in structure and optical texture between the cubic (Cub) and smectic C (SmC) phases was associated with a change from a spot-like X-ray pattern and dark field for the Cub phase to the Debye-Sherrer ring pattern and sand-like texture for the SmC phase under both isobaric and isothermal conditions. The Cub phase was found to disappear at pressures above about 11 MPa. The phase transition sequence, low temperature crystal (Cr₃)-intermediate temperature crystal (Cr₂)-high temperature crystal (Cr₁)-Cub-SmC-isotropic liquid (I) observed at atmospheric pressure, is maintained in the low pressure region below 10 MPa. The transition sequence changes to Cr₃-Cr₂-(Cr₁)-SmC-I in the high pressure region. Since the Cub-SmC transition line determined by POM has a negative slope (dT/dP) in the T-P phase diagram, a triple point is estimated approximately at 10-11 MPa, and 143-145°C for the SmC, Cub and Cr₁ phases, giving the upper limit of pressure for the observation of the cubic phase.     

Phase behaviour of the thermotropic cubic mesogen 1,2-bis-(4- n -octyloxybenzoyl)hydrazine under pressure

The phase transition behaviour of an optically isotropic, thermotropic cubic mesogen 1,2-bis-(4- n -octyloxybenzoyl)hydrazine, BABH(8), was investigated under pressures up to 200 MPa using a high pressure differential thermal analyser, wide-angle X-ray diffraction and a polarizing optical microscope equipped with a high pressure optical cell. The phase transition sequence, low temperature crystal (Cr 2 )-high temperature crystal (Cr 1 ) - cubic (Cub)-smectic C (SmC)-isotropic liquid (I) observed at atmospheric pressure, is seen in the low pressure region below about 30 MPa. The cubic phase disappears at high pressures above 30-40 MPa, in conjunction with the disappearance of the Cr 1 phase. The transition sequence changes to Cr 2 -SmC-I in the high pressure region. Since only the Cub-SmC transition line among all the phase boundaries has a negative slope (d T /d P ) in the temperature-pressure phase diagram, the temperature range for the cubic phase decreases rapidly with increasing pressure. As a result, a triple point was estimated approximately as 31.6 ±2.0 MPa, 147.0 ±1.0°C for the SmC, Cub and Cr 1 phases, indicating the upper limit of pressure for the observation of the cubic phase. Reversible changes in structure and optical texture between the Cub and SmC phases were observed from a spot-like X-ray pattern and dark field for the cubic phase to the Debye-Sherrer pattern and sand-like texture for the SmC phase both in isobaric and isothermal experiments.     

Inversion of the phase sequence between the cubic and smectic C phases under pressure

The phase behaviour of a thermotropic cubic mesogen of 1,2-bis(4′-n-tetradecyloxybenzoyl)hydrazine BABH-14 was studied under hydrostatic pressure using a polarising optical microscope equipped with a high-pressure optical cell, and the P–T phase diagram was constructed. BABH-14 shows the Cr–Cub–I transition sequence under atmospheric and lower pressures, but the Cub phase is replaced completely by the high-pressure SmC, SmC(hp), phase under higher pressures. There is a narrow intermediate-pressure region between the low- and high-pressure regions, in which the Cr–SmC(hp)–Cub–I phase sequence is recognised. The SmC(hp)–Cub transition line has a positive slope with pressure and there are two triple points: one is for the Cr, Cub and SmC(hp) phases and the other is for the I, Cub and SmC(hp) phases. Comparing the phase sequence of BABH-14 with those for BABH-8 and -10, the pressure-induced inversion of the phase sequence between the cubic and SmC phases occurs in the BABH-n homologous compounds. Another new phenomenon is the formation of the monotropic cubic phase on cooling in the intermediate- and high-pressure regions, and an intriguing phenomenon of the cubic phase appearing twice, i.e. I–Cub–SmC(hp)– Cub–Cr phase transition, occurs in the intermediate-pressure region.     

Phase behaviour of the thermotropic cubic mesogen 1,2-bis-(4- n -octyloxybenzoyl)hydrazine under pressure

The phase transition behaviour of an optically isotropic, thermotropic cubic mesogen 1,2-bis-(4-n-octyloxybenzoyl)hydrazine, BABH(8), was investigated under pressures up to 200 MPa using a high pressure differential thermal analyser, wide-angle X-ray diffraction and a polarizing optical microscope equipped with a high pressure optical cell. The phase transition sequence, low temperature crystal (Cr₂)-high temperature crystal (Cr ₁)- cubic (Cub)-smectic C (SmC)-isotropic liquid (I) observed at atmospheric pressure, is seen in the low pressure region below about 30 MPa. The cubic phase disappears at high pressures above 30–40 MPa, in conjunction with the disappearance of the Cr₁ phase. The transition sequence changes to Cr₂-SmC-I in the high pressure region. Since only the Cub-SmC transition line among all the phase boundaries has a negative slope (dT/dP) in the temperature-pressure phase diagram, the temperature range for the cubic phase decreases rapidly with increasing pressure. As a result, a triple point was estimated approximately as 31.6 ±2.0 MPa, 147.0±1.0°C for the SmC, Cub and Cr₁ phases, indicating the upper limit of pressure for the observation of the cubic phase. Reversible changes in structure and optical texture between the Cub and SmC phases were observed from a spot-like X-ray pattern and dark field for the cubic phase to the Debye-Sherrer pattern and sand-like texture for the SmC phase both in isobaric and isothermal experiments.     

Phase behaviour of the thermotropic cubic mesogens 1,2-bis-(4-n-undecyl- and 4-n-dodecyl-oxybenzoyl)hydrazine under pressure

The phase transition behaviour of two optically isotropic, thermotropic cubic mesogens 1,2-bis-(4-n-undecyloxy- and 4-n-dodecyloxy-benzoyl)hydrazine, BABH(11) and BABH(12), was investigated under hydrostatic pressures up to 300 MPa using a high pressure differential thermal analyser, a wide angle X-ray diffractometer and a polarizing optical microscope equipped with a high pressure optical cell. It is found that for BABH(11) and BABH(12), a smectic C (SmC) phase is induced between the isotropic liquid (I) and the cubic (Cub) phases by applying pressures above 10-12 and 16-17 MPa, respectively. A sea-island texture consisting of bright sand-like sea regions (SmC phase) and areas of dark islands (Cub phase) appears in the mesophase under pressures up to 140 MPa, while the sand-like texture of the SmC phase is formed predominantly on cooling under pressure. These observations indicate the destabilization of the cubic phase with increasing pressure. The phase transition sequence of BABH(11) and BABH(12), Cr-Cub-I at atmospheric pressure, changes to Cr-Cub-SmC-I under intermediate pressures and would change to Cr-SmC-I under elevated pressure.     

Thermal behaviour under pressure of the thermotropic cubic mesogen 4'- n -alkoxy-3'-nitrobiphenyl-4-carboxylic acids

The thermal behaviour of members of a homologous series which exhibits the optically isotropic cubic phase, the 4'- n -alkoxy-3'-nitrobiphenyl-4-carboxylic acids having alkoxy chains containing 16, 20 and 22 carbon atoms (referred to as ANBC-16, -20 and -22, respectively) was investigated under pressures up to 200-400 MPa by high pressure differential thermal analysis. In the phase diagram of ANBC-16 obtained on heating, a triple point was estimated at 54 ±1 MPa and 205 ±1°C for the SmC, Cub and SmA phases. It was found that the X phase is formed on cooling under all pressures, while appearing on heating at high pressures above about 54 MPa. Thus the X phase appears monotropically between the SmA and Cub phases in the low pressure region and enantiotropically between the SmA and SmC phases under higher pressures. It is strongly suggested that the X phase is a columnar mesophase. For ANBC-20 and -22, the cubic phase tends to be destabilized with increasing pressure. The temperature region of the cubic phase of ANBC-20 becomes narrower with increasing pressure and a triple point for the SmC, Cub and I phases is estimated to be at about 309 MPa. On the other hand, the cubic phase of ANBC-22 is still observed at the highest pressure examined.     

Phase behaviour of a thermotropic cubic mesogen of 1,2-bis(4′-n-hexyloxybenzoyl)hydrazine under pressure

The phase behaviour of the thermotropic cubic mesogen 1,2-bis(4′-n-hexyloxybenzoyl)hydrazine [BABH(6)] was investigated under pressure up to about 55 MPa using a polarising optical microscope equipped with a high-pressure optical cell. BABH(6) shows the crystal (Cr)–cubic (Cub)–isotropic liquid (I) phase transition at ambient pressure on heating. The smectic C (SmC) phase was induced above 32 MPa, showing the unusual phase sequence of Cr–Cub–SmC–I, similar to those in BABH(n) (n = 8–10). The boundary between the Cub and SmC phases exhibited a negative slope dT/dP of about –1.0 ºC MPa^?1.     

Isotropic cubic phase of 4-n-pentadecyloxy-3-nitrobiphenyl4-carboxylic acid (ANBC-15): DSC, microscopic and dynamic viscoelastic studies

The phase behaviour of 4-n-pentadecyloxy-3-nitrobiphenyl-4-carboxylic acid (ANBC-15) was investigated by differential scanning calorimetry, polarizing optical microscopy, and dynamic viscoelastic measurements. The phase sequence for the virgin sample of ANBC-15 is crystalsmectic C (SmC)-cubic (D)-smectic A (SmA)-'structured liquid' (I1)-isotropic liquid (I2) on first heating. It was found that the appearance of the D phase on the second heating depends on the top temperature of the first heating. It was also shown that the D phase is formed on heating when the preceding SmC phase is 'solid-like' from the viscoelastic point of view, i.e. storage modulus (G) loss modulus (G) at 62.8 rad sec -1, while the 'liquid-like' SmC phase is transformed directly into the SmA phase without showing the D phase on heating. The isothermal frequency scans at a temperature in the D phase showed the existence of a cross-over point, G G , with G G in the lower frequency side, suggesting a structural fluctuation of the D phase. These results are ascribed to the molecular structure of ANBC-15, which has a critical alkoxy chain length in ANBC series.     

Phase behavior of a thermotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitro- biphenyl-4-carboxylic acid under pressure

The phase behavior of an optically isotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) was investigated under hydrostatic pressures up to 200 MPa using a high-pressure DTA, a polarizing optical microscope equipped with a high-pressure hot-stage and a wide-angle X-ray diffractometer equipped with a high-pressure vessel. In the T vs. P phase diagram constructed in the heating mode, a triple point exists at 54±1 MPa and 205±1°C for the SmC, cubic, and SmA phases. A new mesophase, denoted here as X, appears in place of the cubic phase under pressures above about 60 MPa, while the X phase appears on cooling in the whole pressure region studied. Thus the X phase is a monotropic (metastable) phase between the SmA and Cub phases in the low pressure region, while being an enantiotropic phase between the SmA and SmC phases in the high pressure range. The X phase exhibits broken-fan or sand-like textures under pressure and a spot-like diffraction pattern, indicating the birefringent feature and no layered structure. It is suggested that the X phase is tetragonal or hexagonal columnar phase. This revised version was published online in July 2006 with corrections to the Cover Date.     

Pressure-scanning DTA measurements of the cubic-smectic C phase transition of 1,2-bis-(4-n-octyloxy)- and 1,2-bis-(4-n-dodecyloxy benzoyl)hydrazines

The pressure-scanning differential thermal analyzer (DTA) measurements of the cubic (Cub)-smectic C (SmC) transition of thermotropic cubic mesogens of 1,2-bis-(4-n-octyloxybenzoyl)- and 1,2-bis-(4-n-dodecyloxybenzoyl)hydrazine, BABH(8) and BABH(12), were performed at isothermal condition using a high-pressure differential thermal analyzer. BABH(8) showed the same endothermic peak of the Cub-SmC transition in the pressurizing process as on heating at isobaric condition. On the other hand, BABH(12) showed only the cubic phase between the crystal and the isotropic liquid under pressures up to 16-17 MPa, but a high-pressure smectic C (SmC(hp)) phase was induced instead of the cubic phase under higher pressure. The Cub-SmC(hp) phase transition with a small exothermic peak occurred in the pressurizing process and the transition was observed reversibly. The Cub-SmC(hp) phase transition was in accordance with the morphological and structural observations mentioned before. The strange phenomenon of the inversion of sign of the Cub-SmC transition heat of BABH(n) homologues can be explained by the “Alkyl-chains as entropy reservoir” mechanism proposed by Saito et al.     

Light-driven phase transition in a cubic-phase-forming binary system composed of 4'-n-docosyloxy-3'-nitrobiphenyl-4-carboxylic acid and an azobenzene derivative

Binary mixtures were prepared from an azobenzene derivative and a liquid-crystal (LC) compound that exhibits smectic?C (SmC) and bicontinuous cubic (Cub(bi)) LC phases. Reversible switching between the two phases in response to UV-light irradiation was observed. This light-driven SmC-to-Cub(bi) transition is the first example showing the increased dimensionality of molecular ordering with isomerization of azobenzenes (see figure).     

Thermal behaviour of the thermotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) under hydrostatic pressure

The phase behaviour of 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) was investigated under hydrostatic pressures up to 200 MPa using high pressure differential thermal analysis. The phase transition sequence crystal 4 (Cr4)-crystal 3 (Cr3)-crystal 2 (Cr₂)-crystal 1 (Cr₁)-smectic C (SmC)-Cubic (Cub)-smectic A (SmA)-'structured liquid' (I₁)-isotropic liquid (I₂) was observed for a virgin sample on heating at atmospheric pressure. The stable temperature region of the optically isotropic cubic phase becomes narrower on increasing pressure and disappears at pressures above 65 MPa. The T vs. P phase diagram exhibits the existence of a triple point (65 MPa, 207.6°C) for the cubic phase, a new mesophase (X), and the SmA phase, indicating the upper limit for the cubic phase. The new mesophase, denoted here as X, appears in place of the cubic phase at pressures above 65 MPa. The phase diagram also indicates that the Cr₄-Cr₃, Cr₃-Cr₂, and Cr₂-Cr₁ transition lines merge at about 40-50 MPa and then only the Cr₄-Cr₁ transition is observed in the solid state at higher pressures. Thus the phase transition process on heating changes from the sequence Cr₄-Cr₃-Cr₂-Cr₁-SmC-Cub-SmA-I₁-I₂ at atmospheric pressure to Cr₄-Cr₁-SmC-X-SmA-I₁-I₂ in the high pressure region above 65 MPa, via Cr₄-Cr₃-Cr₂-Cr₁-SmC-(X)-Cub-SmA-I₁-I₂ in the low pressure region.     

Rheological evidence for the existence of subphases in the liquid crystalline 4-n-alkoxybenzoic acids

The rheological behaviour of the homologous series, the alkyloxybenzoic acids, has been studied at steady flow and small amplitude oscillatory shear. The temperature dependencies of the viscosity were compared with differential scanning calorimetry data in order to estimate pretransitional phenomena in mesophases. The values of the viscosity and flow activation energy (E) can be indicative of the mesophase state. 4-n-pentyloxybenzoic acid yields a classic nematic (N) phase while the next homologues show a cybotactic nematic phase having a higher E value. The N phase is a Newtonian fluid of lower viscosity than that of the isotropic phase. The cybotactic nematic phase by its rheological properties takes an intermediate position between the N phase and a smectic C (SmC) phase. The SmC phase is a viscoelastic and viscoplastic medium. The SmC phase of 4-n-octyloxy-, 4-n-nonyloxy-, 4-n-decyloxy- and 4-n-dodecyloxybenzoic acid can exist in high- and low-ordered states. The more ordered smectic phase is characterised by higher stiffness, viscosity and yield stress than those of the less ordered. The SmC phase of 4-n-hexadecyloxybenzoic acid is characterised by the only state with unstable value of apparent viscosity. The phase state and the transition temperature can be dependent on the thermal history of the sample and a mechanical shear.     

Dielectric spectroscopy of a smectic liquid crystal

Complex dielectric spectroscopy (frequency range 5 Hz–13 MHz) has been used to analyse the frequency, temperature and bias‐field dependences of the molecular dynamics of a very high‐spontaneous‐polarization ferroelectric liquid crystalline material exhibiting SmA, SmC* and unknown SmX smectic phases. Different smectic phase transition temperatures have been observed from the study of the temperature dependence of the dielectric strength and the relaxation frequency. The phase transition temperatures (crystalline to isotropic phases) have also been described very accurately from the temperature‐dependent symmetric and asymmetric shape parameters of the relaxation function and also the dc conductivity. In a planar aligned cell, two symmetric modes (Goldstone mode and domain mode) have been observed in both the SmX and SmC* phases. One asymmetric mode (X‐mode) observed in the SmC* and SmA phases could be related to the interaction of dipoles of the ferroelectric liquid crystals being affected by the surface of the cell. The soft mode, which usually appears very close to the SmC*–SmA phase transition was not observed until the bias field was applied. The second order nature of the SmC*–SmA phase transition was revealed.     

Ferroelectric liquid crystals from banana-shaped achiral molecules with vinyl end groups

Banana-shaped achiral compounds, the 1,3-phenylene bis[4-(alkenyloxyphenyliminomethyl)benzoate]s, were synthesized with varying length of the alkenyl group; their ferroelectric properties are described. The smectic mesophases, including a switchable chiral smectic C (SmC*) phase, were characterized by differential scanning calorimetry, polarizing optical microscopy and the triangular wave method. The presence of vinyl groups at the ends of the linear side-wings in the banana-shaped achiral molecules, containing a Schiff's base mesogen, induced a decrease in melting temperature and formation of the switchable SmC* phase in the melt. The compound having the octenyloxy group exhibited a spontaneous polarization of 120 nC cm^-2 on reversal of an applied electric field.     

Dielectric properties of four room temperature ferroelectric and antiferroelectric multi-component liquid crystalline mixtures

Dielectric properties of four recently formulated room temperature multi-component liquid crystalline mixtures with paraelectric (SmA*), ferroelectric (SmC*) and antiferroelectric (SmC*_A) phases have been studied as a function of temperature and frequency. Under planer anchoring condition, dielectric spectroscopy revealed all the characteristic modes: low frequency P_L and high frequency P_H mode in SmC*_A phase, Goldstone mode (GM) in SmC* phase and soft mode (SM) in SmA* phase. Dielectric behaviour has also been studied under the application of DC bias electric field. With bias electric field, we have been able to study the soft mode dielectric behaviour in the SmC* phase. An unknown high frequency mode (X-mode) with and without bias is also observed in SmC* phase. Dielectric results are explained in the light of generalised Landau theory. The mixtures show very high soft mode electroclinic coefficient in the SmA* phase in addition to fast switching in SmC*_A and SmC* phases [30].     

Dielectric investigation of the liquid crystal compound with the directSmA*–SmCA* phase transition

New compound showing a direct SmA*–SmC_A* phase transition was synthesised. As far as authors know there are a few pure compounds showing para- and antiferroelectric phases without SmC* between them. Direct current (DC) field applied into a planar-oriented cell induces ferroelectric SmC* phase in an investigated compound. Typical for SmC*, Goldstone mode starts to be detectable. DC field also shifts down the temperature of a SmC_A* phase creation. Moreover, modes in the appearing antiferroelectic phase are enhanced by DC field. This paper shows and discusses relations between modes detected in SmA*, SmC_A* and SmC* (SmC* phase – nucleated by DC field) phases. Parameters of observed modes are calculated using the Cole–Cole relaxation model and a calculation procedure useful especially for high frequency relaxations (higher than 200 kHz).     

Ferroelectric liquid crystals from banana-shaped achiral molecules with vinyl end groups

Banana-shaped achiral compounds, the 1,3-phenylene bis[4-(alkenyloxyphenyliminomethyl)benzoate]s, were synthesized with varying length of the alkenyl group; their ferroelectric properties are described. The smectic mesophases, including a switchable chiral smectic C (SmC*) phase, were characterized by differential scanning calorimetry, polarizing optical microscopy and the triangular wave method. The presence of vinyl groups at the ends of the linear side-wings in the banana-shaped achiral molecules, containing a Schiff's base mesogen, induced a decrease in melting temperature and formation of the switchable SmC* phase in the melt. The compound having the octenyloxy group exhibited a spontaneous polarization of 120 nC cm^?2 on reversal of an applied electric field.     

Chirality transfer between weakly birefringent and electric-field-induced highly birefringent B2 phases in a bent-core mesogen

Electric-field-induced transition was observed for the weakly birefringent chiral B2 phase, which is formed from the banana molecule based on the naphthalene bent core. This phase is considered to possess the twisted grain boundary (TGB)-like helical structure. When an electric field is applied, the TGB-like helix unwinds. The resulting large domain of the SmC(A)P(A) phase shows the high birefringence and simultaneously the antiferroelectric switching between SmC(A)P(A) and SmC(S)P(F) states. Through this field-induced transformation, two interesting features are obtained. First, the initially formed chiral domains are preserved even after the field-induced transformation to the unwound SmC(A)P(A) phase. This indicates the close correlation between the TGB-like helix and the layer chirality in such a way that the helical sense of the TGB-like helix is memorized as the layer chirality of the homochiral SmC(A)P(A) phase. Second, there is a critical temperature, above which the helicoidal structure is stable against the electric field. There is a competition between winding into a TGB-like structure and unwinding due to the electric field, and at higher temperatures, the helicoidal power is too strong to surpass the effect of the electric field.     

Dielectric spectroscopy of a smectic liquid crystal

Complex dielectric spectroscopy (frequency range 5 Hz-13 MHz) has been used to analyse the frequency, temperature and bias-field dependences of the molecular dynamics of a very high-spontaneous-polarization ferroelectric liquid crystalline material exhibiting SmA, SmC* and unknown SmX smectic phases. Different smectic phase transition temperatures have been observed from the study of the temperature dependence of the dielectric strength and the relaxation frequency. The phase transition temperatures (crystalline to isotropic phases) have also been described very accurately from the temperature-dependent symmetric and asymmetric shape parameters of the relaxation function and also the dc conductivity. In a planar aligned cell, two symmetric modes (Goldstone mode and domain mode) have been observed in both the SmX and SmC* phases. One asymmetric mode (X-mode) observed in the SmC* and SmA phases could be related to the interaction of dipoles of the ferroelectric liquid crystals being affected by the surface of the cell. The soft mode, which usually appears very close to the SmC*-SmA phase transition was not observed until the bias field was applied. The second order nature of the SmC*-SmA phase transition was revealed.