Physical Property of New Liquid Crystal Materials and Mixture Design for Active Matrix LCD

Abstract

We studied the physical properties of three series of new fluorinated liquid crystal components and prepared some mixtures by using these components. Decahydronaphthalenes have low Δn with relatively high T _NI. Naphthalenes and Tetrahydronaphthalenes have large Δ? and variety range of Δn (0.08–0.21). Moreover, we have revealed that the fluoro- substituent at C-1 position for the naphthalene and the tetrahydronaphthalene ring has effects to increase T _NI and to reduce γ₁ with good solubility. Then, we have designed some LC mixtures for AM-LCD having good performance with 4V-driving, quick response, high birefringence, low birefringence, wide temperature range and low driving voltage.     

Heat Capacity and Thermodynamic Properties of p'-Substituted p-n-Hexyloxybenzylideneaniline. I. p-n-Hexyloxybenzylideneamno-p'-Benzonitrile (HBAB)

Abstract

The heat capacity of the nematogenic liquid crystal, HBAB, has been measured between 15 K and 385 K by using an adiabatic calorimeter. The crystal-crystal phase transition has been discovered at 27 K below the crystal-nematic phase transition temperature. The transition temperatures, the enthalpies and the entropies of the three phase transitions have been determined: T ₁ = 306.98 K, ΔH _t = 5.11 kJ mol^?1, ΔS _t = 16.7 JK^?l; T _m = 334.05 K, ΔH _m = 23.77 kJ mol^?1, ΔS_m = 71.2 J K^?l mol^?1; and T _c = 375.10 K, ΔH _c = 1.75 kJ mol^?1, ΔS _c = 3.2 J K^?1 mol^?1, respectively. The thermodynamic functions of HBAB from 0 K to 385 K have been determined from the heat capacity data and the enthalpies of the transitions. Two crystal modifications, one yellow and granular form and the other white and needle-like form, have been obtained during the course of the preparation of the sample. It turned out that the yellow form was the stable crystal and the white the metastable modification. The crystal-crystal phase transition has been discussed as an onset of partial melting from the entropy consideration. In this connection the total entropies of the transitions, 91.1 J K^?1 mol^?1 has been proposed to be an important measure of melting.     

Thermodynamic Anomalies Along the Isotropic-Nematic Phase Boundaries of two Component Systems

The entropy and volume changes at the N-I transition have been determined in two binary systems (80CB-60CB and 8OCB-CBOOA). We give evidence for an anomaly of ΔV_NI as a function of the concentration directly related to [dT/dP]_NI at P = 1 atm. This result might be due to the influence of a critical smectic-like compacity.     

AlGaAsSb and AlGaInAsSb Growth from Sb-rich Solutions

This work is related to the use of Sb as a solvent for the growth of antimony-based solid solutions by LPE. We have developed the growth technology of AlGaAsSb on GaSb substrates. A GaSb solid phase is eroded or melted back in contact with a saturated Al-Ga-As-Sb liquid due to the high non equilibrium degree on this system and the erosion increases with Al concentration. One of the techniques to diminish the erosion consists in increasing the initial supercooling but in this system, in the investigated area of compositions, it is impossible because of the low critical supercooling (ΔT_cr) of the liquid phase. We have conceived and developed a method to control ΔT_cr by adding In to the liquid phase. It was found that when the In concentration increased the ΔT_cr also increased. So the transition from the quaternary AlGaAsSb to the pentanary AlGaInAsSb allowed us to decrease the erosion process. This technique permits to grow high quality multilayer heterostructures based on antimonides.     

Crystal growth from concentrated aqueous solutions of calcium nitrate

The crystal growth kinetics was studied in the system of calcium nitrate – water at concentrations 14.3, 11.1, and 9.1 mole% of Ca(NO₃)₂ within the supercooling region ΔT = 0–65 K. The mechanism of the growth was suggested and the concentration dependence of the crystal growth rate was discussed.     

Optical properties of Ga1–xInxAs LPE-layers and p-n structures

The multiple layer structure nGaAs(n Ga_1–xIn_xAs) p Ga_1–xIn_xAs (0 ≦ × ≦ 0.18) was realized by liquid phase epitaxy from In–Ga–As-melts on (111)-oriented GaAs substrates. The InAs-content of the mixed crystal layers was found to be dominating for crystal perfection and growth rate. The cathodoluminescence spectra of p-and n-type Ga_1–xIn_xAs and spectral distribution of the electroluminescence from pn-junctions were measured at T = 77 K and 300 K. The external quantum efficiency wa found to have a maximum for diodes with x ≈ ≈ 0.006. This is caused by the decrease of the optical absorption with increasing x and increasing dislocation density on the other hand.     

Phase Characterization,Enthalpies and Entropies of Transition,of Five Substituted N-(1-Biphenylethylidene) Benzylamines

Five N-(1-biphenylethylidene) benzylamines expressed by the general formula C₆H₅C₆H₄C(CH₃) = N-CH₂-C₆4HX (X = H, m-F, m-Cl, M-Br and p-OCH₃) were synthesized and their thermal behavior studied within the temperature range of -75 to 250°C.

The solid-liquid, liquid-solid transition temperatures were recorded with a DSC analyzer and the thermodynamic parameters ΔH_m and ΔS_m were estimated. A relationship between these parameters and the molecular weigth was found. The compound m-fluoro N- (1-biphenylethylidene) benzylamine showed an l_i → l_n transition at 341.5°K, which was better observed by cooling the sample at 10°C/min. The liquid crystal behavior was confirmed by cross polarized microscopy.     

Phase transitions from density and order parameter from polarisabilities in symmetric dimeric liquid crystals

As a part of our systematic studies on liquid crystal dimers, we present in this article the nature of phase transitions across isotropic–nematic and nematic–smectic-A exhibited by DLCs, α,ω-bis-(4-n-alkylaniline benzylidene-4?-oxy) alkanes. Further, the orientational order parameter in the nematic phase of these DLCs are estimated from the molecular polarisabilities calculated using the experimental refractive indices and density results. The molecular polarisabilities α_e and α_o are obtained for the compounds using the above results for both Vuks and Neugebauer local field models applicable to nematic liquid crystal. α_e and α_o calculated in this way are used to obtain Δα. The polarisability anisotropy in the perfect order (absolute K) is calculated semi-empirically using the δ-function model developed by Lippincott et al. and molecular vibration method. The values of polarisability anisotropy for both local electric field models differ significantly. No criterion is known to decide which value is correct. To avoid the determination of uncertain α and Δα values considering different local field models, a simple procedure developed by Kuczynski et al. was used for evaluation of S, based solely on birefringence δn = (n_e-n_o) and this value of S is compared with those obtained from field models.     

Fluctuation mechanism of normal crystal growth during solidification of binary metallic melts

A recently published theory on the solidification of a one-component melt has been extended to the more complex case of binary systems. The theory is based on the model of a two-phase transitional zone existing between the crystalline phase and the melt. The concentration of solid state atoms within each mono-atomic layer of the transitional zone are assumed to fluctuate due to thermal fluctuations. A crystal growth law has been derived expressing the crystallization velocity in terms of probability functions describing these concentrations fluctuations. When certain restricting conditions concerning the atomic interaction energies within the transitional zone and the distribution of the atoms among the solid and liquid phases at supercooling are fulfilled the crystal growth law attains a simple form predicting for small supercoolings a growth rate proportional to supercooling (linear growth law), roughly proportional to physical parameter θ_AA, and with a weak dependence on another parameter Δ.     

Refractive Indices and Dielectric Studies of Three Phenylcyclohexane Liquid Crystals in the Nematic Phase

The refractive indices n_e, n_o and densities and the dielectric primittivities ε_∥ and ε_⊥ of three P-cyano-P-alkylcyclohexanes (PHC-3, PCH-5, PCH-7) have been measured at different temperatures. The order parameters calculated by using Neugebauer and Vuks' methods were comparable. A comparison of order parameters of the PCH with the corresponding alkylcyanobiphenyls at reduced temperatures τ (= T-T_NI/T_NI) shows that the replacement of a phenyl ring with a cyclohexyl ring decreases the order parameter appreciably. The experimental values of dielectric permittivities ε_⊥ in each of the PCHs are found to be less than half of the ε_⊥-value calculated from Maier and Meier equations using the polarizability and the order parameter obtained from refactive index measurements. This was explained as due to short range antiparallel ordering of strongly polar molecules in the nematic phase, as proposed by Chandrasekhar and Madhusudan, which was not taken into consideration in Maier and Meiers' theory     

Unusual Glassy Smectic-G Liquid Crystal: Heat Capacity of N-p-n-Pentyloxybenzylidene-p'-n-butylaniline between 11 and 393 K

Abstract

The heat capacities of the title compound (C₃H₁₁,O—C₆H₄,- CH=N—C₆H₄,—C₄H₉, abbreviation 5O ? 4) with a purity of 99.92 mole percent have been measured with an adiabatic-type calorimeter between 11 and 393 K. The transition temperature and the enthalpy and entropy of phase transition for stable crystal → S_G, S_G → N and N → isotropic liquid were T _c = 299.69 K/ΔH = 22.68 kJ mol^?1/ΔS = 75.70 JK^?1 mol^?1, 325.72/7.11/21.79 and 342.48/1.78/5.22, respectively. The crystal which melts at 285.5 K is a metastable modification. The S_A phase hitherto reported in between S_G and N does not exist. The glassy So state was realized by rapid cooling of the specimen from the So phase. The molar enthalpy of the glassy S_G state at 0 K was by (10.1±0.1) kJ mol^?1 higher than that of the stable crystalline state and the residual entropy of the glassy state was (9.40±0.83) JK^?1 mol^?1. The relaxational heat-capacity anomaly was observed from as low as 100 K and double glass transition phenomenon occurred around 200 K; a quite unusual phenomenon which has never been observed for the glassy states of nematic and cholesteric liquid crystals. The present results give a fair evidence that the unusual glass transition phenomenon previously found for the S_G state of 6O?4 (a homologous compound) is not exceptional at all but common to the smectic glasses; at least common to the glassy S_G states. Two possible origins responsible for the double glass transitions have been discussed.     

Thin thermosensitive film coating

Thin film thermosensitive coatings are obtained, representing liquid crystal microdroplets dispersed in a polymeric matrix. Gelatin is chosen as a polymeric material. The obtaining of microdroplets is carried out by condensation of the solution of liquid crystal in organic solvents at their mixing with gelatin aqueous solution. The obtained coating distinguishes with temperature stability, homogeneity of the colouring, stability of the time indicators.     

Investigation of microheterogeneities in Ga–Pb melts by acoustic methods

The pulse phase method of measuring the ultrasound velocity V_s was used for investigation of the microheterogeneity of hypermonotectic Ga–Pb melts. The method allows measuring V_s at various distances from the bottom of the crucible. An anomalous variation of the ultrasound velocity along the vertical axis of the crucible both in two-phase and the one-phase regions of the phase diagram was observed. The effect disappears irreversibly after a sufficient overheating the melt above the phase separation line. The phenomenon is linked with a metastable microheterogeneity of investigated melts. An experimental method to detect microdroplets inside the liquid solution is proposed and their volume fraction and mean size are calculated.     

Dielectric relaxation and electro-optical switching behavior of nematic liquid crystal dispersed in poly(methyl methacrylate)

Polymer dispersed liquid crystal composite films were prepared from poly(methyl methacrylate) and nematic liquid crystal E44 by solvent induced phase separation method. In the present investigation we report effect of liquid crystal concentration on the electro-optical and dielectric properties of the composite films. The results were interpreted in terms of phase separation of liquid crystal and polymer, shape and size of liquid crystal droplet, interfacial charge layer effect, liquid crystal loading and miscibility of liquid crystal in the polymer matrix. The miscibility between two phases at interface was investigated by employing Fourier‐Transform Infrared Spectroscopy and differential scanning calorimetry. Morphological study showed that liquid crystal phase is embedded in a spongy poly(methyl methacrylate) matrix and homogeneous distribution increased with increasing E44 content. Electro optical behavior of these composite films under the condition of an externally applied AC electric field (0–200 Vp-p, 50–1000 Hz) and wide range of temperature was determined using He–Ne laser (wave length 632.8 nm) as a light source. It was found that Poly(methyl methacrylate)/E44 (30/70) wt.% composite has more significant properties than the other concentrations. The performance of all composites showed variations with respect to applied voltage as well as temperatures. Dielectric measurement of polymer dispersed liquid crystals has been carried out in the frequency range from 20 Hz to 20 MHz and over the temperature range from 24 °C to 100 °C. The Maxwell–Wagner effect due to interfacial charge accumulation between boundaries of liquid crystal droplets and surrounding of polymer matrix has been observed.     

Synthesis,physical properties,and atomic structure of niobium-doped RbTiOPO<Subscript>4</Subscript> crystals

Single crystals of solid solutions Rb_1?xTi_1?xNb_xOPO₄(RTP: Nb) were grown and the temperature dependences of their dielectric and nonlinear optical properties and electric conductivity were studied. The maximum possible niobium content in these crystals is close to x = 0.1. The niobium impurities decelerate growth of {100} faces, and crystals take a plate-like habit. With increasing doping level, ferroelectric phase transitions diffuse and their temperature decreases. A specific feature of the dielectric properties of RTP: Nb crystals is the appearance of a broad relaxation maximum ε₃₃ in the temperature range 200–600°C caused by the formation of vacancies in the rubidium cation sublattice. The intensity of second-harmonic generation under laser irradiation decreases with increasing niobium content. The atomic structure of a crystal with x = 0.01 is studied and it is established that niobium substitutes for titanium only in Ti(1) positions.     

Measurement of the An isotropic Refractive Indices of Polybenzylglutamate Liquid Crystals. Molecular Factors and Dispersion

The ordinary and extraordinary refractive indices have been measured for lyotropic liquid crystal solutions of poly-γ-benzyl-L-glutamate. The onset of the liquid crystal formation is noted as an abrupt jump in the sample birefringence in the biphasic region. The concentration dependence is otherwise unremarkable. The polymer is found to add a small, anisotropic increment to the refractivity of the supporting solvent. Both n _o and n _e can thus be measured in an ordinary Abbé refractometer for the low refractive solvents common to these liquid crystal solutions. The optical birefringence does not depend significantly on polymer molecular weight. Data is also included for the wavelength dependence (dispersion) of n _o, n _e, and Δn.     

Magnetic and Electric Birefringence in the Isotropic Phase of a Nematic of Large Positive Dielectric Anisotropy

Abstract

Magnetic (Δn_H ) and electric birefringence (Δn_E ) in the isotropic phase of strongly positive (Δ 8)trans-p-n-octyloxy α-methyl-p'-cyanophenyl cinnamate (8 OMCPC) have been measured. It is established that they both exhibit a (T - T*)^?1 dependence, T _NI - T* being 1.4 K. Also, the induced birefringence is found to be proportional to the square of the applied field, magnetic or electric.     

Effect of Pressure on Antiferromagnetic Transition in Alkali-Electro-Sodalite

Abstract

Pressure (0–19 kbar) and temperature (4–300 K) dependent EPR study of Sodium-Electro-Sodalite (SES) is presented. SES, which consists of a bcc sub-lattice of F-centers supported by a zeolite-like framework, is known to be a Mott insulator at room temperature. On cooling, SES undergoes an AF transition at 48±2 K providing the first example of an s-electron antiferromagnet. We find that the width of the EPR resonance above T _N is influenced not only by a strong exchange interaction, but also by a fast spin-lattice relaxation. Also, with increasing pressure, T _N decreases linearly and extrapolates to 0 K at about 65 kbar. The reason for this seemingly unexpected behavior is briefly discussed.     

Surface morphology and growth mechanisms of argyrodite-type Cu6PS5 hal crystals

Single crystals of Cu₆PS₅Hal (Hal = Cl, Br, I) have been grown by dissociative sublimation and by chemical vapour transport with P, S, Hal, CuHal and combinations thereof as transporting agents in the temperature range 800 to 1000 K. Microscopic observation of the tetrahedral faces revealed several growth features. Macrosteps, closed loop steps and surface protuberances are always accompanied with the presence of liquid CuHal/Cu₂S droplets on the growing crystal surface. The phenomena are characteristic for a two-dimensional Vapour-Liquid-Solid growth mechanism. In the absence of CuHal/Cu₂S liquid phase, direct growth from the gas phase (VS growth) takes place leading to hillocks and growth spirals with low step heights (∼ 5–10 Å).