Reflection Spectra of the Crystalline Electron Donor-Acceptor Complexes of TCNQ

The polarized reflection spectra were measured on the crystals of TCNQ complexes with phenothiazine, anthracene, pyrene, acenaphthene, carbazole, hexamethylbenzene and 1,10-phenanthroline. The crystalline absorption spectra have been obtained by the K-K transformation of the reflection spectra. The charge transfer degree and the stabilization energy in the ground state were estimated for each complex by analysing the CT bands in the solid state.     

Study of the Smectic a Nematic Transition in Octyl and Nonyl Cyanobiphenyl

A new DSC method is used to study a smectic A to nematic transition. The measurement of the height of the DSC transition peak gives the order of the transition. The smectic A to nematic transition of octyl cyanobiphenyl was found to be second order while the same transition was found to be first order for nonyl cyanobiphenyl.     

The Dielectric Anomaly Near the Transition from the Smectic A* to Smectic C* Phase and Visco-Elastic Properties of Ferroelectric Liquid Crystals

A pyro-electric technique is developed which allows the measurement of the dielectric response near the A*-C* phase transition in ferroelectric liquid crystals. The temperature dependence of the elastic modulus K _θ(T) corresponding to the molecular tilt in smectic layers is calculated from the experimental data. Direct pyro-electric measurements of the relaxation time for the spontaneous polarization P _s and the data on K _θ(T) allow us to calculate the temperature behaviour of the twist-viscosity γ₁(T) for the smectic C* phase. The curves γ₁(T) are compared for the smectic C* and the nematic phase of the same compound and the dependence of the twist viscosity on the molecular tilt angle in the C* phase is investigated. The results of the dielectic measurements are discussed in terms of the mean-field approximation.     

ENDOR Study of the Phase Transition in Benzil

ENDOR spectroscopy was used to elucidate the domain structure of benzil accompanying its phase transition at 84°K. Spectral twinning was observed on a single-crystalline sample as a result of multidomain formation below the phase transition temperature. This twinning was explained by applying the Landau theory of phase transitions. With knowledge of the anisotropy of the proton hyperfine interaction, we extracted the angle between the domains and the morphologic two-fold axis to be 1.55° at 2°K.     

Experimental Determination of the Curvature-Induced Reduction in the Smectic A-Nematic Transition Poin

On the basis of an analogy between smectic A-nematic and superconductor-normal metal transitions, de Gennes has predicted that a twist or bend distortion should reduce T _AN with respect to that of a curvature-free sample. We report measurements of the reduction of T _AN on samples prepared in two different geometries. In the first, a magnetically induced twist distortion has been used to obtain preliminary data on 8 OCB and CBOOA samples. In the second, a wedge-shaped twisted nematic cell has been used to get quantitative data on the reduction of T _AN of CBOOA as a function of twist distortion.     

Pitch Behavior of the Cholesteric Helix at the Phase Transition Point Cholesteric/Smectic A up to 2500 Bars. Study of Some Cholesteryl n-Alkanoates

Experimental evidence is given, for the first time, for a finite pitch of the cholesteric helix at the phase transition point cholesteric/smectic A (Ch/S_A). This finite pitch changes into an infinite one at a given point on the phase equilibrium line Ch/S_A. Therefore this point is called the pitch infinity point (PIP).

With increasing n-alkyl chain length of the investigated cholesteryl n-alkanoates the pressure coordinate of the PIP is shifted to higher values up to a chain length of 13 C atoms. For the alkanoates with 13,15 and 17 C atoms the same PIP pressure of about 1000 bars was determined.

The Ch/S_A phase equilibrium line of the cholesteryl esters could at best be followed up to 2600 bars. The respective transition enthalpies were measured at normal pressure and the corresponding changes in volume calculated by means of the Clausius-Clapeyron equation.     

Order Parameters and Distribution Function of 4'-(N-(p-Pentyloxy Carbonyloxy-Benzylidene)Amino) Valerophenone in Smectic Phase from X-ray Diffraction Measurements

Abstract

X-ray diffraction studies of 4'-(N (p-pentyloxycarbonyloxy-benzylidene)amino)valerophenone (PCBAV in short) oriented by a magnetic field is reported here. The compound has a smectic A phase which is identified by X-ray studies and texture studies. Orienta-tional order parameters (p ₂) and (P ₄) have been determined from the calculation of f(β), the orientational distribution function. An approximate expression for the angular part of the potential of the mean field is obtained from the temperature variation of the orientational distribution function. The value of d, the layer thickness, and D, the intermolecular distance, have been calculated. An approximate value for the translational order parameter τ₁ and average value of the root mean square displacement ?z²?½ are given. We could not get an accurate estimate of the translational order parameter due to the inaccuracy in the measurement of the intensity of the inner ring.     

SiO2气凝胶小球热处理过程中的相变研究

以无机硅溶胶为先驱物,通过溶胶-凝胶过程和常压干燥工艺制备出SiO2气凝胶.将SiO2气凝胶在不同温度条件下进行热处理,采用DSC、XRD、TEM、BET和IR等手段表征了SiO2气凝胶由无定形态向多晶态转化过程中,其多孔结构特征的变化.研究结果表明,在600℃以下进行热处理,样品表现出良好的热稳定性;当热处理温度在600～1060℃,随着温度的升高,多孔结构特征因无定形SiO2微粒团聚而逐渐消失;当热处理温度高于1060℃,无定形SiO2发生相变形成多晶态,导致SiO2气凝胶多孔结构特征完全消失.     

Structural Phase Transition of an Intercalation Compound Mn1/4NbS2

Abstract

A structural phase transition of an intercalation compound Mn_1/4NbS₂ has been investigated by X-ray diffraction at high temperatures. The lattice parameter c exhibited a discontinuous change at 640K. The superlattice reflections observed below 640K disappeared suddenly above 640K. The phase transition at 640K took an aspect of the first-order phase transition. The precise structure analyses were performed at various temperatures above and below the phase-transition temperature. It was revealed that Mn atoms were arranged in disorder in the high-temperature phase, while the Mn atoms were ordered forming the 2a ₀ × 2a ₀ × c ₀ superlattice in the low-temperature phase. The Nb and S atoms around the ordered Mn atoms slightly shifted from the high-symmetry position in the low-temperature phase. The order parameters were the degree of order of the Mn atoms and the degree of displacement of the Nb and S atoms.     

Phase Diagram Involving the Thermal Stability of TGB and Induced Smectic Phases in Binary Mixture of Thermotropic Liquid Crystals

We report the results of our studies on the optical and thermal properties of the mixture of terephthalidene-bis-4, n-alkylaniline and cholesteryl nonanoate, which exhibits very interesting liquid crystalline mesophases such as cholesteric, twisted grain boundary, smectic-A, smectic-C^*, smectic-C, smectic-I, and smectic-G, sequentially when the specimen is cooled from its isotropic phase. These phases have been characterized by using microscopic techniques. The temperature variations of optical anisotropy, electrical conductivity, ultrasonic velocity, and molar and adiabatic compressibility have also been discussed.     

Induction of B1, B6 and Biaxial Smectic A Phases in Binary Mixtures of Compounds with Rod-Like and Bent-Core Molecules

Abstract

We have studied a binary mixture of compounds, one of which has rod-like molecules and the other bent-core molecules. The rod-like molecules are biphilic in nature with a long alkoxy chain attached to an aromatic moeity only at one end, and exhibit the bilayer SmA₂ phase, even though they do not have the highly polar cyano or nitro groups. The compound with bent-core molecules exhibit the B₂ phase which has polarized layers with tilted molecules. Three liquid crystalline phases are induced in the binary mixtures, depending on the concentration: the 2-dimensionally ordered B₁ phase for compositions with 15 to 63 mol% of the rod-like molecules and the B₆ phase for 63 to 87 mol%. The sequence obtained on increasing the concentration of rod-like molecules is the same as that seen on shortening the chain length of the BC molecules. Between 87 to 95.5 mol% of the rod-like molecules, a new biaxial smectic A₂ (SmA_2b ) phase is induced. On the basis of several observations, we argue that it corresponds to a structure in which the BC molecules are reoriented with their arrow directions pointed along the layer normal. The SmA₂ to SmA_2b transition corresponds to an orientational transition of the bent-core molecules in the anisotropic SmA₂ background medium.     

Effect of Molecular Structure on Mesomorphism: 5. Comparison of Methyl and Trifluoromethyl as Lateral Substituents in the Solid and Nematic Phases.1

Two laterally-substituted nematogenic liquid crystals, methyl-p-phenylene-di-p-butoxybenzoate and trifluoromethyl-p-phenylene-di-p-butoxybenzoate, have been studied by differential scanning calorimetry, powder x-ray diffraction, and polarized light microscopy (hot stage microscopy and hot-wire stage microscopy). Comparison of thermodynamic data for the nematicisotropic transitions of these two compounds suggests a strongly repulsive electronic interaction between molecules in the nematic phase of the trifluoromethyl compound. Detailed molecular structural augments are presented to rationalize the thermodynamic data. The room temperature solid phases of the two compounds were found to have different crystal structures. However, the high temperature solid phases were found, by a novel application of hot-wire stage microscopy, to be isomorphous.     

A Spectroscopic Study of the Second Order Phase Transition in Bis (p-toluene sulfonate) Diacetylene Polymer Crystals

The second order phase transition at 195 K which occurs in bis (p-toluene sulfonate) diacetylene polymer crystals has been studied by optical reflection and transmission, Raman and far-infrared spectroscopy. Order parameter fitting to the data suggests that at low temperatures the transition has a two dimensional character while closer to the transition it appears to be three dimensional. There are indications of a broad transition region which might be expected for a predominately two dimensional phase transition in which fluctuations dominate the behaviour of the system. Analysis of new X-ray crystallographic data gives some support to a structural model in which the transition would have a substantial two dimensional character.     

Study of group-III binary and ternary nitrides using X-ray absorption fine structure measurements

It is demonstrated that the NEXAFS spectra are a “fingerprint” of the symmetry and the composition of the binary nitrides GaN, AlN and InN, as well as of their ternary alloys In_0.16Ga_0.84N and Al_yGa_1−yN. From the angular dependence of the N-K-edge NEXAFS spectra, the hexagonal symmetry of the under study compounds is deduced and the (p_x, p_y) or p_z character of the final state is identified. The energy position of the absorption edge (E_abs) of the binary compounds GaN, AlN and InN is found to red-shift linearly with the atomic number of the cation. The E_abs of the Al_yGa_1−yN alloys takes values in between those corresponding to the parent compounds AlN and GaN. Contrary to that, the E_abs of In_0.16Ga_0.84N is red-shifted relative to that of GaN and InN, probably due to ordering and/or phase separation phenomena. The EXAFS analysis results reveal that the first nearest-neighbour shell around the N atom, which consists of Ga atoms, is distorted in both GaN and Al_xGa_1−xN for x<0.5.     

Quasielastic Neutron Scattering Study of Reorienting di-heptyloxyazoxybenzene (HOAB) Molecules in the Nematic and Smectic C Phases

Quasielastic neutron scattering (QNS) measurements carried out for heptyloxyazoxybenzene (HOAB) revealed the existence of fast molecular reorientation in the nematic and smectic C phases. The correlation time of this process, derived by fitting to a uniaxial rotational diffusion model, is of order of 10–20 ps in both liquid crystal phases. An explanation of the reasons for the disagreement between the correlation time values obtained by methods based on QNS and dielectric relaxation in the microwave region is suggested.     

Calorific Effect of the Magnetically Induced Phase Transition in Induced Chiral Nematic Systems

The study of the calorific effect of the magnetically-induced phase transition in doped nematic phases is described. The systems examined consisted of PCB as a nematic host phase and S-N-1-phenylethyl-4n-alkylbenzamides as non-mesogenic optically active dopants. The calorific effect was estimated indirectly from the temperature dependence of the magnetic-field-threshold of the helical unwinding and of the reverse process; i.e. the helical winding. It appears that it is the ratio of the length of an optically active dopant and that of the nematic host which determines the temperature dependencies of such parameters as the helical pitch, microscopic twisting power, and latent heat. A comparison with the magnetocaloric effect in nematic liquid crystals¹ is also made.     

Surface growth mechanisms and structural faulting in the growth of large single and spherulitic titanosilicate ETS-4 crystals

Morphological, surface and crystallographic analyses of titanosilicate ETS-4 products, with diverse habits ranging from spherulitic particles composed of submicron crystallites to large single crystals, are presented. Pole figures revealed that crystal surfaces with a-, b- and c- axes corresponded to 110, 010 and 001 directions, respectively. Thus, technologically important 8-membered ring pores and titania chains in ETS-4 run along the b-axis of single crystals and terminate at the smallest crystal face. Height of the spiral growth steps observed on 1 0 0 and 0 0 1 surfaces corresponded to the interplanar spacings associated with their crystallographic orientation, and is equivalent to the thickness of building units that form the ETS-4 framework. Data suggest that the more viscous synthesis mixtures, with a large driving force for growth, increased the two- and three-dimensional nucleation, while limiting the transport of nutrients to the growth surface. These conditions increase the tendency for stacking fault formation on 1 0 0 surfaces and small angle branching, which eventually results in spherulitic growth. The growth of high quality ETS-4 single crystals (from less viscous synthesis mixtures) occurred at lower surface nucleation rates. Data suggest that these high quality, large crystals grew due to one-dimensional nucleation at spiral hillocks, and indicate that under these conditions un-faulted growth is preferred.     

Twist Grain Boundary Phases in the Binary Mixtures of Smectic and Cholesteryl Compounds

Abstract

The binary mixture of Terephthal-bis-p-n-hexadecylaniline (TB16A) and cholesteryl nonanoate (CN) exhibits I - N* - TGB _A - TGB _c*- Sm A - Sm I - Sm F - Sm G - K phases in the concentration region between 95 to 98% of TB16A at higher temperature range. The 90% of TB16A exhibits I - N* - TGB _A - TGB _c - Sm A - Sm I - Sm F - K phases. The mixtures of concentration between 50 to 80% of TB16A exhibits I - Sm A - Sm I - K phases. The frustrated blue phase is also observed in the mixtures of lower concentration of TB16A in CN at higher temperature. Optical, DSC and X-ray studies were carried out for the identification of the different phases. The phase diagram of the Chen-Lubensky model in this context is discussed.