Nematic Range Research Articles

Study of mesomorphic, thermal and optical properties of 4-pentylbenzoic acid (5BA) and 4-n-alkyl-4́-cyanobiphenyl (nCB; n = 5, 6) supramolecular hydrogen bonded mesogenic complexes

Within the scope of this study, the process of producing and analyzing a liquid crystalline substance (supramolecular hydrogen-bonded mesogen) is presented. The formation of this mesogen involves the use of two chemicals, namely 4-pentylbenzoic acid (5BA) and 4-n-alkyl-4́-cyanobiphenyl (nCB; n = 5, 6). Equimolar (1:1) 5BA/5CB and 5BA/6CB binary combination samples have been organized by using one at a time mixing 5CB and 6CB liquid crystal chemical substances with 5BA. Differential scanning calorimetry (DSC) and polarized optical microscopy (POM) are employed for the examination of phase transitions, and liquid crystalline phase texture properties of the produced mesogens. The phase transformation sequence that occurred during heating and cooling is Crystal (Cr) ↔ Smectic A (SmA) ↔ Nematic (N) ↔ Isotropic (I) with the 1st order or weakly 1st order transition. The nematic range value observed for 5BA/6CB is considerably smaller than the nematic range value observed for 5BA/5CB, but the thermal mesophase range value for both is approximately the same. Fourier-transform infrared (FTIR) evaluation of 5BA, 5CB, and their hydrogen-bonded combos (5BA/nCB; n = 5, 6) confirmed attribute peaks. The X-ray diffraction (XRD) study revealed that the produced mesogens possess a crystalline structure. In addition, UV–Vis experiments demonstrated that the increase in alkyl chain length in the combination resulted in a decrease in absorbance and wavelength values, while leading to an increase in absorbency and band gap energy values. These results propose workable purposes for the synthesized substances in liquid crystal displays and other optoelectronic devices. Overall, the findings display the feasibility and viability of these novel hydrogen-bonded liquid crystalline mesogens in various technological applications.

Topological defects as nucleation points of the nematic-isotropic phase transition in liquid crystal shells.

The transition from a nematic to an isotropic state in a self-closing spherical liquid crystal shell with tangential alignment is a stimulating phenomenon to investigate, as the topology dictates that the shell exhibits local isotropic points at all temperatures in the nematic phase range, in the form of topological defects. The defects may thus be expected to act as nucleation points for the phase transition upon heating beyond the bulk nematic stability range. Here we study this peculiar transition, theoretically and experimentally, for shells with two different configurations of four +1/2 defects, finding that the defects act as the primary nucleation points if they are co-localized in each other's vicinity. If the defects are instead spread out across the shell, they again act as nucleation points, albeit not necessarily the primary ones. Beyond adding to our understanding of how the orientational order-disorder transition can take place in the shell geometry, our results have practical relevance for, e.g., the use of curved liquid crystals in sensing applications or for liquid crystal elastomer actuators in shell shape, undergoing a shape change as a result of the nematic-isotropic transition.

Exploring the nematic to twist-bend nematic phase transition: calorimetric and optical measurements

ABSTRACT We investigate the nematic (N) to twist-bend nematic (NTB) phase transition in binary mixtures of a symmetric liquid crystal dimer (CB7CB) and a calamitic bi-phenyl mesogen (7OCB). As the molar concentration of 7OCB increases, both the Iso–N and N–NTB transition temperatures decrease gradually, consequently, the width of the nematic phase above the NTB phase can suitably be varied from ~12 K to 46 K. Notably, as the nematic range expands, there is a remarkable reduction in transitional entropy, eventually approaching negligible or zero values. Additionally, the heat capacity peak and the phase shift disappear when transitional entropy reaches zero. This behaviour diverges from typical N–SmA and N–SmC phase transitions, where transitional entropy decreases near the tricritical point but the heat capacity peak persists. Our findings indicate a finite positive δ(∆n) across all concentrations at the N–NTB phase transition, suggesting a gradually weakening first-order nature. This contrasts with theoretical predictions of a second-order N–NTB phase transition, as our experimental data consistently supports a first-order nature. The self-consistent mean-field Landau Model successfully validates our experimental data, establishing the universal first-order nature of the N–NTB phase transition, with experimental entropy values in good agreement with theoretical prediction.

Mixing twist-bend and ferroelectric nematic liquid crystals.

Twist-bend (N_{tb}) and ferroelectric (N_{F}) nematic liquid crystals exhibit several novel effects and new physical properties. Here, we report experimental studies on the phase diagram and some physical properties of binary mixtures of CB9CB and RM734 mesogens. Both N-N_{tb} and N-N_{F} phase transition temperatures and the corresponding enthalpies decrease significantly and, eventually, these transitions disappear at some intermediate compositions, stabilizing wide nematic phase (N). Temperature-dependent birefringence several degrees above the N-N_{tb} phase transition shows strong director tilt fluctuations. The critical range of the fluctuations increases with the nematic range and the critical exponent is consistent with the mean field. The spontaneous polarization of RM734 decreases drastically with the addition of CB9CB mesogen. The temperature dependence of the splay elastic constant of the mixtures' high-temperature nematic (N) phase strikingly differs from that of the pristine CB9CB and RM734 mesogens. The study shows that a small inclusion of either compound has a substantial effect on the phase diagram and physical properties.

Synthesis and characterization of liquid crystal methyl methacrylic monomers

AbstractThree liquid crystalline monomers were systematically designed, synthesised and characterised. Methyl methacrylic unit was linked to the mesogenic compound, 4′-Undecycloxybiphenyl-4-yl 4-octyloxy-2-(pent-4-en-1-yloxy) benzoate, (Me), using disiloxane, ester and siloxane units respectively. In the first compound, 4′-(undecyloxy)-[1,1′-biphenyl]-4-yl 2-((5-(3-(4-(methacryloyloxy)butyl)-1,1,3,3-tetramethyldisiloxanyl)pentyl)oxy)-4-(octyloxy)benzoate, (M1), the methyl methacrylic unit was linked to the mesogen by disiloxane group, (Si–O–Si), while ester group, (COOC), was used in the second compound, 4′-(undecyloxy)-[1,1′-biphenyl]-4-yl 2-((5-(methacryloyloxy)pentyl)oxy)-4-(octyloxy)benzoate, (M2), and siloxane unit, (Si–O), in the third compound, 4′-(undecyloxy)-[1,1′-biphenyl]-4-yl 2-((5-((4-(methacryloyloxy)butyl)dimethylsilyl)pentyl)oxy)-4-(octyloxy)benzoate, (M3). The introduction of the methyl methacrylic unit caused the melting point of the compounds to reduce with Me melting at 53.3 °C, M1 at −8.1 °C and M2 at −12.5 °C. The three compounds showed characteristic nematic textures when observed under POM and when compared to the mesogenic compound (Me, 71.7 °C), there were remarkable reduction in the clearing points of the compounds, with M1 clearing at 18.6 °C, M2 at 68.8 °C and M3 at 10.3 °C. Finally, there was appreciable increment in the nematic phase range for the compounds when compared to the mesogen, Me, 18.4 °C. The range was 26.7 °C for M1, 81.3 °C for M2 and since there was no observable crystallization point for M3, the range was not determined.

On the critical behaviour of the N-SmA phase transition in an induced system: an exploration from high-resolution calorimetric and optical studies

ABSTRACT A systematic study of a binary system composed of 4-n-pentyl 4′-cyanobiphenyl (5CB) and 4-n-pentyl phenyl 4-n′-hexyloxy benzoate (ME6O.5) mesogens showing an induced smectic A at different molar concentrations has been done. Heat capacity and optical birefringence measurements have been performed around the N-SmA phase transition region. The heat capacity peaks could be fitted well below the N-SmA transition by means of an extended Landau mean-field model. The first-order nature of the transition throughout the composition range can be inferred. This transition is rather close to the tricritical point when the nematic range is sufficiently increased. The latent heat decreases with the increase in the nematic range. For large nematic range, the latent heat drops to zero and the heat capacity peak associated with N-SmA phase transition disappear, contrary to previously reported most of the usual N-SmA phase transition. Precision birefringence measurements also agree well with the heat capacity data.

The relaxation dynamics and dielectric properties of cyanobiphenyl-based nematic tripod liquid crystals

We present a detailed investigation of the phase behaviour, molecular relaxation dynamics, rheology and dielectric properties of two cyanobiphenyl-based liquid crystal (LC) tripods, differing only in the length of their spacer units (6 or 9 carbons). These LC tripods combine properties of low molecular weight LCs and LC polymers, resulting in a range of advantageous properties including a wide nematic range (ΔT>90 K) and a large birefringence (0.3 at T−TNI=-80 K for the 6 spacer tripod). Using broadband dielectric relaxation spectroscopy, calorimetry, oscillatory and steady state shear rheology, we identified four molecular relaxation processes: the structural (α) relaxation (defining the glass transition temperature, Tg); the δ relaxation (reorientation of the mesogen unit around its short axis); the β relaxation (reorientation around its long axis); and the γ relaxation (internal tripod arm fluctuations). The β and γ relaxations follow Arrhenius temperature dependencies in the glass, whereas the α and δ relaxations merge above, but near Tg, where they follow a non-Arrhenius VFT behaviour. For higher temperatures, the two relaxations separate and for T>T⁎, where T⁎ marks a dynamic crossover, the α relaxation transitions from VFT to Arrhenius behaviour. For the two tripods, ratios of T⁎/Tg=1.14 and T⁎/Tg=1.13 were observed respectively, consistent with the ratio observed for many side-chain LC polymers (and other LC systems), and consistent with the ratio where a dynamic crossover is typically observed also for non-LC glass-formers. However, for non-LC systems, the transition to Arrhenius behaviour happens at significantly higher temperatures relative to Tg and the dynamic crossover at T⁎ is typically observed as a transition between two different VFT behaviours. We argue that for the tripods these differences arise from differences in the molecular relaxation mechanisms induced by the LC order. Finally, for temperatures where δ and α relaxations are separated, we find that ion conductivity decouples from the α relaxation, instead following the δ relaxation; this demonstrates that the ion transport properties for the tripods can be tuned by the design of the tripod mesogen arm.

EFFECT OF HEATING AND COOLING ON 6CB LIQUID CRYSTAL USING DSC TECHNIQUE

In this research, details of the heating and cooling of the liquid crystal (LC) 4-cyano-4'-hexylbiphenyl (6CB) were collected through the use of Differential Scanning Calorimetry (DSC), and then analyzed with Logger Pro. The sample of 6CB was heated from -40 °C to 80 °C and then cooled to -40 °C again at a constant rate of 20 °C/min. DSC provided data for the time, temperature, and heat flow, which was used to calculate thermal speed, acceleration, and jerk, as well as the specific heat capacity at each point. Graphs of this data contain endothermic and exothermic peaks that indicate phase transitions, revealing information such as the enthalpy of the peak and the nematic range. One focus of this study was to compare 6CB to other liquid crystals that are part of the n-alkyl-cyanobiphenyl (nCB) family to see if the difference in tail length affects the behavior of the liquid crystal. Results show that 6CB may be of interest as an alternative to other liquid crystals for liquid crystal displays (LCD).

Effect of shape of ZnO nanoparticle on electro-optic and dielectric properties of nematic liquid crystal

Properties of liquid crystal incorporated with various shapes of a nanomaterial are expected to show multifaceted behaviour as properties of nanomaterial are extremely dependent on its size and shape. In view of this, we have investigated the effect of shape of ZnO nanoparticle on electro-optic and dielectric properties of nematic liquid crystal (NLC), PCH5. Nanocomposites of 0.01 wt% ZnO nano- sphere, rods, and wires in NLC are prepared. The addition of ZnO nanoparticles to NLC leads to increase in the order parameter and reduction in threshold voltage, response time as well as ionic conductivity as compared to the pure NLC host. Dielectric permittivity measurements indicate nanoparticle induces short range order in isotropic phase. Dielectric measurements also show increase in order parameter in nanocomposites with 1D nanoparticles whereas negligible change is observed in nanocomposites with spherical nanoparticles in NLC in deep nematic range. The ATR-FTIR measurements support the enhancement in parallel correlation of dipole moments in ZnO nanocomposites as compared to pure NLC.

13C Nuclear Magnetic Resonance Investigations of Molecular Mesogens with a Terminal Phenyl Ring Linked via a Spacer: Odd-Even Effect.

A set of mesogens considered as model molecules to the technologically important twist-bend (NTB) nematogens are investigated. They consist of a three-ring core connected to a phenyl ring via a flexible spacer and displayed enantiotropic nematic and smectic C mesophases. In such systems, odd or even number of atoms present in the spacer could influence the orientation of the terminal phenyl ring and thus have a bearing on designing the NTB phase, considered as intermediate between the nematic and the cholesteric phases. One-dimensional (1D) and two-dimensional (2D) 13C NMR spectra have been recorded in the liquid crystalline phases and the alignment-induced chemical shifts (AIS) and the 13C-1H dipolar couplings obtained. The order parameters of the phenyl rings reveal features relatable to the odd/even number of atoms of the flexible spacer and the type of linkage. The AIS plots of the phenyl rings of the even spacer-based mesogen showed the usual behavior for all of the phenyl rings with a decrease in AIS with increasing temperature. However, for the odd-spacer mesogens, unusual behaviors are noted for the terminal phenyl ring. Thus, two of the mesogens showed an increase of AIS in the smectic C phase that continued till the middle of the nematic phase temperature range, followed by a decrease. The other two odd-spacer mesogens also showed different behaviors. These observations indicate that the terminal phenyl ring is oriented at an angle with respect to the long molecular axis for the odd-spacer mesogens that changes as a function of temperature. The angles have been found to depend on the nature of the atom/group connecting the spacer to the terminal ring and the spacer length. Thus, the present study provides critical information on the design of the odd dimers that are recognized to generate fascinating NTB mesophases.

English

This paper reports details of phase transitions of a new generation “Tertiary Liquid Crystal System” (TLCS). This TLCS was made with a mixture of 5CB, 6CB, and 7CB liquid crystals. The TLCS was run in DSC to find changes taking place in its heat flow as a function of time and temperature analyzed with Logger Pro. The sample of TLCS was run from -40 °C to 80 °C with a 20 °C/min ramp rate in DSC. It was observed that the TLCS shows two phase transitions on heating and one transition on cooling. All these transitions were found to shift when compared to their single members. The unique behavior of TLCS is that it never shows crystallization in cooling, even though the sample was cooled to -40 °C. This indicated an increase in its Nematic range, making it more useful in the Liquid Crystal Display (LCD) field.

Critical behaviour near the nematic-smectic-C and nematic-smectic-A phase transitions of a binary system: a comparative study from calorimetric, optical and dielectric measurements

ABSTRACT Detailed heat capacity, birefringence and dielectric anisotropy measurements have been carried out near the nematic – smectic-C (NC) and the nematic – smectic-A (NA) phase transitions of a mesogenic binary system. Important feature is the existence of two tricritical points one for the NC transition and other for the NA transition. The dependence of critical exponent (α) is well explained in terms of temperature ratios (TNC/TNI and TNA/TNI) for the NC and NA phase transitions. Both transitions exhibit non-universal behaviour and showing effective critical exponents in between tricritical and 3D-XY values. However, the nematic range necessary for the NC tricritical point is quite large (>20°C). The enthalpy, phase shift and imaginary heat capacity are also analogous to the nature of the critical exponent (α). Moreover, within a very small concentration range, the smectic-A – smectic-C (AC) transition line appears. Although the smectic-A width above the AC transition is quite small~2K, heat capacity and birefringence data clearly confirm second-order nature. Additionally, there exists a region where the NC, NA and AC line segments converge, i.e. a NAC multicritical point. At this point, the latent heat for the NC, NA and AC transition lines disappears, indicating an obvious second-order nature of the NAC multicritical point.

Enhancement of electro-optical properties and phase transition temperature of thermotropic liquid crystal 5CB by doping with 4-n-pentylbenzoic acid

ABSTRACT Liquid crystalline materials that have been used in the display industry need to have a wide temperature-range nematic phase while remaining functioning in different climate conditions. In this work, a new binary mixture of thermotropic liquid crystal materials, particularly the nematic phase, has been studied. A widely used material 5CB (4-Cyano-4’−pentyl biphenyl), exhibiting nematics phase, and PA (4-Phenylbenzoic acid) were preferred. Mixtures of different concentrations of 5CB-PA were prepared and investigated using dielectric spectroscopy, phase transition and electro-optical responses techniques. It was found that not only was an improvement to the dielectric anisotropic achieved but also the nematic temperature range extended from 35 ºC to just above 50°C by adding 10 wt.%. On the other hand, the threshold voltage is increased by 10% for the same sample. In addition, elastic constants and response time showed similar behaviours upon increasing the loading concentration of PA, whereas the visco-elastic coefficient significantly declined. All the estimated values for the pure 5CB are in good agreement with the literature. This improvement in the operating temperature range is unique and suggests that the doping can lead to cheap and mass production of a stable liquid crystalline material for their application in the display industry.

P‐12.12: Development and Application of High Birefringence Liquid Crystal Materials

The development of new liquid crystal optoelectronic devices, including laser phase modulation, microwave and terahertz devices, requires liquid crystal materials with high birefringence. In this paper, three new molecular design strategies are proposed, including the introduction of olefin chain, lateral fluorine substitution and new ring core. Four new series of isothiocyanate liquid crystal compounds with high birefringence, low melting point and wide nematic temperature range were synthesized. Based on these new liquid crystal compounds, a liquid crystal mixture with nematic temperature range of ‐40~146 ºC and birefringence of 0.42 was developed. At 19 GHz, the new liquid crystal mixture shows excellent dielectric properties, with dielectric anisotropy of 1.28 and dielectric loss of 0.0087. The new liquid crystal mixture also has very low viscoelastic coefficient. The results at 1550nm and 60 ºC show that the response speed can reach 3.6 milliseconds with 2π phase modulation in the reflection mode.

Difluorovinyl Liquid Crystal Diluters Improve the Electro-Optical Properties of High-∆n Liquid Crystal Mixture for AR Displays.

A liquid crystal (LC) mixture in liquid crystal on silicon (LCoS) is the core material for augmented reality (AR) displays. However, a LC mixture with high birefringence (Δn) and large dielectric anisotropy (Δε) possesses high viscosity (γ1), which results in a slow response time of LCoS devices for AR displays. This work proposes to apply difluorovinyl-based LC diluters to fine balance the low viscosity, high ∆n, and large ∆ε of the LC mixture for a fast response time. Through studying their effects on the key electro-optical properties of a high-∆n LC mixture, it is found that doping these diluter molecules to a high-∆n LC mixture can decrease the viscoelastic coefficient (γ1/K11), increase ∆ε and the figure of merit, maintain a wide nematic phase temperature range, a high clearing point, and ∆n. It also means that these diluters could effectively regulate the relationship between ∆n, ∆ε, and γ1 in the LC mixtures to achieve a fine balance of various excellent properties and further improve the LC device's response time. The widespread applications of these liquid crystal diluters in emerging liquid crystal optical devices are foreseeable.

Optical and Thermal Investigations of Eutectic Metallomesogen Mixtures Based on Salicylaldiaminates Metal Complexes with a Large Nematic Stability Range

The mesomorphic behavior and the miscibility properties of binary mixtures of a new series of Schiff base metallomesogen (MOM) are evaluated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Nuclear magnetic resonance (NMR), elemental analysis (CHNX), Fourier-transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) were used to certify the molecular structure of the compounds. The results revealed that the studied mixtures are completely miscible throughout the composition field and exhibit a nematic phase which covered the whole composition range. In the mixtures, the stability of the nematic phase varies continuously, and it is possible to highlight the presence of a eutectic composition with a wide mesogenic stability range.

The helical twisting power of chiral dopants in lyotropic chromonic liquid crystals

ABSTRACT Chiral dopants with different levels of lipophilicity were synthesised, and their helical twisting power (HTP) and thermal phase behaviour in mixtures with lyotropic chromonic liquid crystal (LCLC) were investigated. The experimental approach involved measurement of the positions of disclination lines in Θ-cells, where one surface is linearly rubbed, and the other is circularly rubbed. This technique allowed the use of minimal dopant concentrations. Experimental conditions were selected such that nematic temperature range of LCLC remained constant. We found that the twisting power of the used chiral dopants varies over nearly an order of magnitude between the molecules with positive and negative lipophilicity. All chiral molecules of hydrophobic nature investigated showed much higher effectiveness in twisting LCLC than hydrophilic ones, and in addition, the hydrophilic molecules had a much smaller effect on the transition temperatures of LCLC. The dependences were interpreted as a variation of the partition between the concentration of dopant dispersed in the host phase, between the columns and that adhering to the columnar stacks – with hydrophobic molecules better able to adhere, thus creating sources of chirality for the whole system.

Phase diagram, dielectric and electro optic properties of binary liquid crystals mixtures

ABSTRACT Nematic phase at room temperature with wide stability and high birefringence is particularly desirable for functional devices. Two thermotropic liquid crystals (tolane and the 4-pentyl-4-biphenylcarbonitrile nematic also known as 5CB) are mixed by varying the weight fraction (wt%) in order to investigate the phase sequences and their physical properties using differential scanning calorimetry (DSC), polarised optical microscopy (POM) and dielectric spectroscopy techniques. Phase coexistence was observed for a concentrations 20 ≤ C ≤ 60 wt% of tolane in 5CB and the phase diagram was established. In addition, the nematic-isotropic temperature TNI increases with increasing the concentration of tolane LCs. A eutectic mixture at room temperature with large nematic range and high birefringence is obtained for C = 10 wt%. The increase in the nematic range is due to an enhancement of the nematic order induced by the LCs. It is found that the electro optical parameters like the threshold voltage, the response time were relatively increased. This increment can be attributed to an increase in the viscoelastic properties of the mixture.

Influences of nanoparticles and chain length on thermodynamic and electrical behavior of fluorine liquid crystals

Hydrogen-bonded polar nematic liquid crystal series with the general formula nOBAF (n = 7–12) is studied. The mesomorphic characterization is demonstrated through differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The complexes with short alkyl chains (n = 7, 8) present a wide nematic range and monotropic smectic F mesophase, whereas the longer alkyl chain (n = 10–12) analogues show high melting and low clearing mesomorphic liquid crystals. The thermal range of the mesophase and the birefringence increase with chain length decreasing. Furthermore, the effect of the nanoparticles (LiNbO3) on the thermal and the electrical behavior of 8OBAF are investigated. The presence of LiNbO3 nanoparticles increases the conductivity and reduces the resistivity of the complex.

New multi-fluorinated benzofuran liquid crystals with large dielectric anisotropy and improved solubility

ABSTRACT Multi-fluorinated liquid crystal compounds with benzofuran core were synthesised and their structures were identified using 1 H NMR, 13 C NMR and mass spectra. Thermal analysis shows that further fluorination of the central benzene leads to a significant decrease in melting point and broadening of the nematic temperature range. Physical property test reveals that the compounds with tetrafluoro substituent have large dielectric anisotropy, high birefringence, and improved solubility in the host mixtures. The optimal geometry, polarisability and dipole moment of liquid crystal molecules were calculated by density functional theory, and the experimental results are explained. The new compounds show an excellent application of prospects in liquid crystal display.