Thermotropic liquid crystal behaviour of alkaline-earth-metal dihexadecyl phosphate salts

Alkaline-earth-metal dihexadecyl phosphate salts were synthesized, and their thermal stability was evaluated by thermogravimetry. Their thermotropic liquid crystal behaviour was investigated by differential scanning calorimetry, polarizing optical microscopy, dilatometry, and X-ray diffraction. On heating, the calcium, strontium, and barium salts exhibit columnar liquid crystal phases, whereas the less ionic beryllium and magnesium salts melt directly into isotropic liquids.     

Converse flexoelectric effect in homeotropic nematic layers with asymmetric surface anchoring

The dc electric field-induced deformations of conducting flexoelectric nematic layers were studied numerically. Asymmetric boundary conditions expressed by different anchoring strengths on the limiting surfaces were assumed. Nematic material was characterised by negative dielectric anisotropy. Both signs of the sum of flexoelectric coefficients were taken into account. The electric properties of the layer were described in terms of a weak electrolyte model. Mobility of cations was assumed to be one order of magnitude lower than that of anions. Quasi-blocking electrode contacts were assumed. The threshold voltages for the deformations and the director distributions in the deformed layers were calculated for low, moderate and high ion concentrations. The director distributions were also determined. The results show that asymmetry caused by difference between the anchoring strengths and by difference between mobilities of anions and cations lead to two threshold values for a given layer corresponding to two polarities of the bias voltage. Additionally, the values of both thresholds depend on the sign of the flexoelectric parameter. In every case under consideration, the threshold is significantly lowered when the ion concentration is high.     

Dynamics of electric field induced deformations in flexoelectric nematic layers

The dynamics of deformations induced by DC electrical fields in homeotropically aligned layers containing a flexoelectric nematic material with negative dielectric anisotropy has been studied numerically. The rise time constants, characterising the development of deformations after switching on the external voltage, and the decay time constants, describing the decay of deformation after switching off the voltage, were calculated as a function of the parameters essential for the behaviour of the layer. In particular, the influence of flexoelectricity was studied. It was found that the stronger the flexoelectric properties of the nematic, the lower is its viscosity, the higher is the bias voltage, the weaker is the surface anchoring, the thinner is the layer and the higher is the ion concentration, the more rapid was the onset of deformation. Similarly, the lower the viscosity, the thinner is the layer, the stronger the anchoring and the larger the ion content, the more rapid was the decay of deformation. Neither the voltage previously applied nor the flexoelectric properties were found to affect the decay time.     

Influence of the surface pretilt angle on spatially periodic deformations in nematic layers

The deformations induced by electric field in twisted or untwisted flexoelectric nematic layers can be homogeneous (i.e. one-dimensional) or spatially periodic (i.e. two-dimensional). The periodic deformations are undesirable from an applicative point of view since they destroy the homogeneous appearance of the area of an excited pixel of a display. They are particularly favoured when the nematic material possesses flexoelectric properties. In order to check whether the unwanted periodic deformations can be eliminated by means of suitable surface pretilt angle, the small deformations arising just above the corresponding threshold voltage were investigated numerically. The nematic materials exhibiting both weak and strong flexoelectricity were taken into account. The surface pretilt angles ranging from 0° to 30° were adopted. It was shown that the periodic patterns, arising in the case of planar surface alignment, disappear if sufficiently large surface pretilt angle is applied.     

Contrast ratio of twisted nematic liquid crystal cells and its improvement

The light leakage of twisted nematic (TN) liquid crystal displays is investigated. While the TN mode has a robust structure in regard to light scattering, due to thermal fluctuations of the liquid crystals and light leakage from imperfect rubbing defects, it maintains significant residual retardation of the liquid crystal layer in the black state. The residual retardation is induced by the azimuthally twisted liquid crystal alignment near substrate surfaces and causes major light leakage in the black state. We investigated several methods to compensate for the residual retardation, and the methods include the adjustment of the helical power of the liquid crystal material, the increase of driving voltage, the control of rubbing direction and a newly designed compensation film with a small angle twist. Though all these methods improve the contrast ratio by about 30%, each method has its own weaknesses and limitations. The development of a new compensation film would provide a good chance for future TN applications.     

Thermotropic liquid crystal behaviour of gemini imidazolium-based ionic amphiphiles

Thermotropic ionic liquid crystals (LCs) are useful for a number of applications such as anisotropic ion transport and as organised reaction media/solvents because of their ordered fluid properties and intrinsic charge units. A large number of different ionic LC architectures are known, but only a handful of examples of gemini (i.e. paired or dimeric) ionic LCs have been prepared and studied. In this work, a series of 20 new symmetric, imidazolium-based, gemini cationic LCs containing two bridged imidazolium cations and two pendant alkyl chains was synthesised, and the thermotropic LC behaviours were characterised. The imidazolium unit provides a highly tunable and modular platform for the design and synthesis of gemini cationic LCs which offers excellent structure control. As expected, the thermotropic LC properties of these new amphilphilic, gemini ionic LCs were found to be strongly influenced by the length of the spacer between the imidazolium units, the length of the pendant alkyl tails, and the nature of the anion. Smectic A (SmA) thermotropic LC phases were observed in more than half of the gemini imidazolium LC systems studied.     

Refractive index matched liquid crystal cell for laser metrology application

There exists a problem in advanced numerically controlled automatic laser metrology. Reported study is related to minimising the system generating three or more coherent laser measuring beams. These rays, generated in a proper rangefinder, are necessary to determine the spatial coordinates and spatial orientation of the measured details. The simplest solution is to generate laser coherent light beams of wavelength λ = 0.6328 µm with a given light polarisation plane and then to direct them along three or more independent optical paths. To form these optical paths, a special refractive index matched liquid crystal cell (MLCC) might be applied. To ensure a stable laser operation during the measurement process, the back reflection of the laser beam from MLCC should not exceed 0.7%. The main task of this work is developing such a MLCC transducer. To reach the critical back reflection low enough, the MLCC is constructed as multilayer structure. MLCC operates in positive twisted nematic (TN) mode. Owing to the high-birefringence nematic liquid crystal mixture used and rather big cell gap, the elaborated low reflective MLCC (with R < 0.7%) works at TN mode above the sixth interference maximum of transmitting linearly polarised light.     

Strong deformations induced by a DC electric field in homeotropic flexo-electric nematic layers

Elastic deformations of homeotropic nematic liquid crystal layers subjected to a DC electric field were studied numerically in order to determine their development under increasing voltage. Both signs of the dielectric anisotropy, Δ?, and of the sum of flexo-electric coefficients, e ₁₁ + e ₃₃, were considered, as were also low, moderate and high ion concentrations. The electrical properties of the layer are described in terms of a weak electrolyte model. Quasi-blocking electrode contacts and a finite surface anchoring strength were adopted. Director orientation, the electric potential and the ion concentrations were each calculated as a function of the coordinate normal to the layer. The director distributions turned out to depend not only on the sign of Δ? but also on the sign of e ₁₁ + e ₃₃, due to the difference in the mobility of anions and cations. The importance of ion content was also confirmed.     

Ferroelectric polymer nanocomposite alignment layer in twisted nematic liquid crystal devices for reducing switching voltage

Twisted nematic liquid crystal device (TNLCD) was fabricated using a ferroelectric zinc oxide (ZnO)-doped polyimide alignment layer. The ferroelectric nanoparticle can produce a local electric field, which can trigger the orientation of liquid crystal molecule and reduces the switching voltage. The uniform dispersion of ferroelectric ZnO nanoparticles in the alignment layer was studied using field emission scanning electron microscopy and atomic force microscopy. The ferroelectric property of ZnO-doped polyimide was investigated using dynamic contact electrostatic force microscopy. An increased local electric field due to the presence of nano ZnO was confirmed with the help of scanning tunnelling microscopy. An augmentation of capacitance was observed with an increase in concentration, which substantiates the reduction of switching voltage of TNLCD with the modification of ferroelectric nanoparticle-doped alignment layer.     

Accurate measurement of the twist elastic constant of liquid crystal by using capacitance method

In this study, the twist elastic constant (k₂₂) of liquid crystals (LCs) was accurately measured using capacitance method. The constant can be obtained on the basis of accurate measurement of other LC parameters, such as parallel and vertical dielectric constants (ε_// and ε_⊥), splay and bend elastic constants (k₁₁ and k₃₃), and rotational viscosity coefficient (γ₁). First, by using dual-cell capacitance method and an LC cell capacitance model to measure ε_// and ε_⊥, k₁₁ and k₃₃ can be obtained from the threshold voltage determined from the voltage–capacitance curve of the parallel-aligned nematic LC layer and the comparison between the experimental and theoretical results based on the Frank elastic theory, respectively. In addition, γ₁ can be obtained from the measurement of the dynamic response in the parallel-aligned nematic cell. Finally, k₂₂ can be accurately determined using the threshold voltage of the twisted nematic LC cell. By adopting the above method, the measured k₂₂ for LC E7 was 6.7 × 10^?12 N. The proposed method is more rigorous and yields a more accurate measurement result than the other methods reported in the literature.     

Improvement of the crystal rotation method to measure the flexoelectric difference (e1–e3) in achiral materials using AC electric fields

We show that the crystal rotation method for measuring the difference between splay and bend flexoelectric coefficients (e₁–e₃) [Outram and Elston, Liq. Cryst. 39, 149 (2012)] can be improved by using AC instead of DC fields. The field frequency is small (~0.05 Hz), yet sufficient to get rid of the difficulties connected with the migration of charge carriers. The method is sensitive enough so as to use fields with amplitudes as small as 1 V/mm. This has the advantage of avoiding the consideration of the interaction due to the dielectric anisotropy, and greatly simplifies the analysis of data. The results are extracted from a simple fitting scheme, which involves two parameters. In particular (e₁–e₃) is obtained from a scale factor in a one-parameter fit. Measurements of the temperature dependence of (e₁–e₃) are presented for two classical nematic materials.     

Thermotropic liquid crystals based on ferrocenylbiphenyl and ferrocenylterphenyl

4′‐Ferrocenyl‐1,1′‐biphenyl‐4‐yl 4‐alkoxybenzoates Fc–(C₆H₄)₂–OC(O)–C₆H₄–O–C _n H_2n+1 (n = 8, 10, 12) (3a–c), representing a new class of ferrocene‐containing thermotropic mesogens with nematogenic properties, were prepared. Two approaches were used for the construction of these mesogens: (i) reaction of 4′‐ferrocenyl‐1,1′‐biphenyl‐4‐ol with 4‐alkoxybenzoylchlorides, and (ii) crosscoupling of tris(4‐ferrocenylphenyl)boroxine with the corresponding halobenzenes. Crosscoupling was also applied for the synthesis of terphenyl‐containing mesogens Fc–(C₆H₄)₃–OC(O)–C₆H₄–O–C _n H_2n+1 (n = 10, 12) (6a,b) and (RC₅H₄)Fe‐[C₅H₄–(C₆H₄)₃–OC(O)–C₆H₄–O–C₁₀H₂₁] (11a, R = Et; 11b, R = n?Bu). The latter compounds also form nematic phases. Mesogens 6a,b form mesophases with wider temperature ranges than their biphenyl‐containing counterparts 3b,c. The most pronounced mesomorphism was displayed by compounds 11a and 11b, which have mesophases in the ranges 141–253°C and 120–238°C, respectively. The purity of compounds was established by ¹H NMR spectra and elemental analysis. Mesophases were identified by polarizing optical microscopy and differential scanning calorimetry.     

Thermotropic liquid crystal behavior on PBLG‐PDMS‐PBLG triblock copolymers

In this contribution, the preparation of rod‐coil‐rod triblock copolymers based on polydimethylsiloxane and polypeptide [poly(γ‐benzyl‐L ‐glutamate)] is reported. Firstly, self‐assembly in rod‐like structures was demonstrated via polarized optical microscopy and small‐angle light scattering. Further structuration details were obtained using X‐ray scattering and AFM imaging to establish the formation of a double‐hexagonal structure and to accurately define the morphological dimensions of the rodlike structures. The thermal behavior of these structures was investigated using dynamic mechanical analysis and differential scanning calorimetry. We conclude by addressing an unexpected reversible thermal transition within the 130–150 °C temperature range and the ensuing associated organizational modifications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4668–4679, 2006     

The influence of chirality on the difference in flexoelectric coefficients investigated in uniform lying helix,Grandjean and twisted nematic structures

Measurements of the difference in flexoelectric coefficients (e ₁ – e ₃), using the sign convention as originally defined by Meyer, are reported from three experiments employing the flexoelectro-optic effect in different geometries. The uniform lying helix (ULH) structure is used to measure the tilt angle of the liquid crystal director with respect to the helix axis for an applied electric field, in order to infer a value for (e ₁ – e ₃). Alternatively, measurements of the flexoelectric difference can be made by considering the transmission through a device with an in-plane electric field aligned in either the Grandjean structure for highly chiral materials, or a twisted nematic (TN) structure for largely achiral materials. The results from the Grandjean and ULH structures show the equivalence of the measurement techniques with helix axis either perpendicular or parallel to the substrates. Further comparison of these results with the measurement from the achiral TN device shows that the difference in flexoelectric coefficients displays no dependence on chirality, demonstrating that flexoelectricity is purely associated with splay and bend director deformations, as expected from symmetry considerations.     

TN型废液晶热解产物研究

氮气气氛下,以TN型液晶为实验材料,利用TGA-FTIR联用仪研究热解失重特征及过程产物;同时利用GC-MS对管式炉实验系统热解产物进行分析。结果表明,TN型液晶热解失重起始温度为120℃,剧烈失重温度为220℃~430℃;热解产物除了含CO2外,还含有1~5个碳原子官能团的苯、苯酚、苯呋喃等组成的芳香族化合物、多环芳烃以及丙烷为主的烃类有机物。这些有机物绝大多数是有毒有害物质,可进一步通过焚烧热解产物来实现TN型废液晶无害化处理。     

Investigation of alignment direction in wide view film and rubbing angle of twisted nematic liquid crystal display mode

Wide view (WV) film is an important material in the polariser. It is a hybrid-aligned, discotic liquid crystal (DLC) on an alignment layer on the tri-acetyl cellulose film, which is used as compensation film in twisted nematic (TN) mode liquid crystal display (LCD). The relation between the alignment direction of the DLC in the WV film and the rubbing direction of the polyimide on the glass substrate in the TN mode LCD was investigated. The results indicated that the contrast ratio (CR) of the TN mode LCD can be increased by adjusting this angle . When an 88°?rubbing angle was used in this work, the CR of the TN mode LCD could reach 1000:1 and the horizontal and vertical viewing angles were 170 and 160°, respectively.     

High-birefringence nematic liquid crystal for broadband THz applications

Liquid crystals (LCs) have been studied extensively in the visible range for their dielectric tunability, and the characterisation in the terahertz (THz) range has gained increasing interest due to the need for active THz modulation and switching devices. In this paper, we use THz time-domain spectroscopy to measure the frequency-dependent birefringence and the absorption coefficient of a number of commercial and non-commercial nematic LCs, including E7, BL037, MDA-98-1602, LCMS-107, GT3-23001 and 1825, over a range of bias voltages at room temperature. Furthermore, several basic components of LC mixture are analysed to establish their contributions to birefringence and theoretical model is used to fit the absorption spectra. The large tunability and low loss measured for a range of samples show that the LCs are useful tunable dielectrics for compact, efficient and broadband THz devices.     

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.     

Thermotropic liquid crystalline behaviour of piperazinium and homopiperazinium alkylsulphates

A series of 1,4-piperazinium di- n -alkyl sulphates was synthesized and compared with an analogous series of 1,5-homopiperazinium di- n -alkyl sulphates. Their thermotropic liquid crystalline behaviour was studied by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. For the piperazinium salts, two ordered smectic phases were established, in which the lateral packing of the molecules within the layers is rectangular or tetragonal. Both phases are characterized by an alternate periodic packing of the positive and negative ionic groups in the polar sublayer, while the lipophilic sublayers of the alkyl chains are in a disordered conformation. Substitution of the piperazinium by the less symmetrical homopiperazinium group disfavours organization within the smectic layer and as a result smectic A phases were obtained.     

Photoaligned bistable twisted nematic liquid crystal displays

Novel, optically bistable, twisted nematic liquid crystal display configurations obtained using photoaligned and photopatterned substrates are presented. Switching by 360° between two stable twist configurations is shown. Undesired intermediate states which reduce bistability are effectively suppressed by photopatterned domains around picture elements which exhibit different azimuthal- and zenithal-aligning directions. The high degree of stability of the new, domain-stabilized bistable configurations enables the formation of nematic displays with inherent long term optical memory. Display switching at a few volts is demonstrated.