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.     

Heat Capacity and Thermodynamic Properties of p'-Substituted p-n-Hexyloxybenzylideneaniline I I I. p-n-Hexyloxybenzyl ideneam i no-p'-fluorobenzene (HBAF)

Abstract

The heat capacity of HBAF has been measured between 15 K and 385 K. Four phase transitions were found at 328.07 K (crystal-smectic B); 330.33 K (smectic B-smectic A); 334.88 K (smectic A-nematic); and 336.33 K (nematic-isotropic liquid), respectively. The enthalpies and entropies of these transitions were determined to be 23.22 kJ mol^?1/70.7 JK^?1 mol^?1; 3.05/9.2; 3.41/10.2; and 1.17/3.5, respectively. The total transition entropy of HBAF agreed well with those previously reported for the present homologues. The standard thermodynamic functions were estimated up to 385 K. The heat capacity curve of HBAF in the transition region had a close resemblance to that of p-n-hexyloxybenzylideneamino-p'-chlorobenzene. The entropies of the smectic A-nematic and nematicisotropic liquid transitions were compared with those theoretically derived by McMillan. The smectic B-smectic A transition entropy was interpreted in terms of order-disorder phase transition associated with the orientation of molecule.     

Liquid-Crystalline Solvents as Mechanistic Probes. 10. Dynamics of Intramolecular Quenching of Pyrenyl Fluorescence in the Liquid-Crystalline and Isotropic Phases of a Cholesteric Solvent1

Abstract

The effect of cholesteric order in a 59.5/15.6/24.9 (w/w/w) mixture of cholesteryl oleate/cholesteryl nonanoate/cholesteryl chloride (CM) on the intramolecular fluorescence quenching of l,3-bis(l-pyrenyl) propane (P3P) has been explored. A comparison with fluorescence quenching of N,N-dimethyl-4-[3-(l-pyrenyl)propyl]aniline (P3D) in CM is made. From the Arrhenius activation parameters for quenching in the cholesteric and isotropic phases, it is concluded that the motions which take the ground state conformers of P3P to their quenching transition state are nearly impervious to macroscopic CM mesophase order: in the cholesteric phase, E'_a = 10.5±0.4 kcal mol^?1 and ΔS^? = 1 ± 1 eu; in the isotropic phase, E'_a = 10.0 ± 0.2 kcal mol^?1 and ΔS^? = 0 ± 0.5 eu. An explanation of these results is advanced.     

Thermal dehydration of the double salts K2Be(XO4)2·2H2O (X = S,Se)

The thermal dehydration of the title compounds was studied by TG, DTA and DSC methods and the enthalpies of dehydration were calculated (87.6 kJ mol^–1 and 167.5 kJ mol^–1 for the sulfate and selenate compound, respectively). The larger value of ΔH_deh of K₂Be(SeO₄)₂·2H₂O is due to the stronger hydrogen bonds formed in the selenate as compared to those formed in the respective sulfate owing to the stronger proton acceptor capabilities of the SeO₄^2– ions. The enthalpies of formation (ΔH_f⁰) of the dihydrates are also calculated from the DSC measurements (– 4467.4 kJ mol^–1 and – 3447.1 kJ mol^–1 for the sulfate and selenate compound, respectively). The anhydrous double salt, K₂Be(SO₄)₂, forms tetragonal crystals with lattice parameters: a = 7.232(2) Å; c = 14.168(2) Å; V = 741.0 ų, while the anhydrous salt, K₂Be(SeO₄)₂, forms monoclinic crystals with lattice parameters: a = 9.217(3) Å; b = 10.645(3) Å; c = 8.989(2) Å; β = 108.52(4)°; V = 836.2 ų. Vibrational spectra (infrared and Raman) of both the dihydrates and the anhydrous compounds are also presented and discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase Transition and Phase Diagram of Anion Radical Salts of [(C6H5)3PCH3]+ [(C6H5)3AsCH3]+ ×(TCNO)− 2 (0 ≤×≤ 1)

Abstract

Much attention has been paid to the solid anion radical salts of 7,7,8,8-tetracyanoquinodimethane (TCNQ), because of their prominent electronic properties.^1–4 In particular, the salts containing mixed cations represented by [(C₆H₅)₃PCH₃]⁺ _1–x [(C₆H₅)₃AsCH₃]⁺ _× (TCNQ)^? ₂, (0 ≤×≤ 1), are known to undergo phase transitions at 1 atm pressure in the solid state.^1–4 The phase transition of pure methyltriphenylphosphonium salt, (x = 0.00), takes place at 315.7 K. Heat-capacity measurements of this phase transition have been made by Kosaki et al. ³ The transition has thus been found to be of the first order. The enthalpy and the total entropy change associated with the phase transition were experimentally determined to be 485.18 cal/mol and 1.7206 cal/deg.mol, respectively. For the solid solutions, it was found that the transition temperature (T_c ) is increased, while the magnitude of the heat of transition (δH) is decreased, progressively with an increase in the composition parameter (x) and that pure methyltriphenylarsonium salt, (x = 1.00), has no such phase transition up to the decomposition temperature of about 480 K at 1 atm pressure.^1–3 Figure 1 shows the experimental relation between T _c and x, together with the relation between δH and x.⁴ In the present paper, we attempted to explain thermodynamically the phase diagram of Figure 1 for the solid solutions of those TCNQ anion radical salts.     

Etude par Calorimetrie,Diffraction des Rayons X et Diffusion Raman d'une Transition de Phase dans (C4 H4P) Mn (CO)3

Abstract

Heat capacity measurements (95-300K), X-ray diffraction (78-300K) and low frequency Raman spectroscopy (10-350K) have evidenced an order-disorder phase transition in phosphacymantrene, (C₄ H₄P) Mn (CO)₃. This transition has been characterized by a monoclinic ←→ triclinic structural change at about 110 K and by a pretransitional phenomenon. The measured transition enthalpy and entropy are 480 ± 10J.mil^?1 and 4.17 ± 0.08J.K^?1 mol^?1, at 115 K, respectively.

A complete assignment of the observed Raman bands in h₄ and d₄ derivatives is proposed. From the temperature dependence of frequencies, intensities and half-widths of some Raman bands we have discussed the order, the nature and the mechanism of the phase transition: intermolecular interactions appear to be mainly involved in the mechanism and an activation energy roughly equal to 2100 ± 840 J. mol^?1 has been determined.     

Elastic Anomalies at Charge Density Wave Transitions in TaS3 and NbSe3

Abstract

The temperature dependence of the Young's modulus and internal friction of TaS₃ (orthorhombic) and NbSe₃ have been measured by the vibrating reed technique. There is a large minimum 2%, in the modulus of TaS₃ at the commensurate Peierls distortion (T_c = 222K) and the internal friction increases below T_c(ΔQ^?1 = 5×10^?5), although no critical relaxation effects are observed. On the other hand, a very small minimum, ΔE/E ~ 0.06%, is observed at the upper incommensurate transition in NbSe₃, and a small broad increase (0.03%) at the lower transition. The measurements allow estimates to be made of the stress dependence of the transition temperature and of the electron-phonon coupling constant.     

1,2,3,4,5,6,7,8-Octahydroanthracene-9,10- dicarbonitrile at 172, 216, 256, and 297 K

Octahydroanthracenedicarbonitrile is monoclinic, space group P2₁/c, at 172 K, a = 4.723(7), b = 8.254(3), c = 16.190(7) Å, = 91.76(8)°, Z = 2, V = 630.8(12) ų. The molecule, located on a center of symmetry, is disordered between the two senses of puckering in the aliphatic ring. The structure was also determined at 216, 256, and 297 K. The disorder increases with increasing temperature and can be described by a van't Hoff relationship with H = 5.2(3) kJ mol^–1 and S = 13.8(12) J K^–1 mol^–1.     

Thermoelastic and Piezoelastic Properties of Hexagonal RbMnCl3

Temperature and pressure derivatives of the elastic constants, indices of refraction, dielectric constants, Faraday effect and thermal expansion of RbMnCl₃ near T_c = 278 K confirm the existence of a second-order phase transition. A strongly anomalous behaviour is observed with the elastic shear stiffness c₄₄ which possesses a positive temperature derivative and a negative pressure derivative. These properties and also the pressure derivative of the transition temperature, dT_c/dp = 6.2 K kbar⁻¹ closely resemble the anomalous behaviour of two other ferroelectric species, betaine borate and betaine hydrogen maleinate.     

Optical,X-ray,and calorimetric studies of phase transitions in ND4BeF3

Phase transitions in ND₄BeF₃ crystals at T₁ = 330 and T₂ = 245 K were studied by specific heat (DSC) and X-ray lattice parameters measurements in function of temperature. These ferroelastic transitions are accompanied by anomalous heat absorption, sudden changes in the unit cell parameters and crystal symmetry. Formation of domain structure in particular phases examined under a polarizing microscope is also described. Domain walls of the type (100), (010), and (001) observable at room temperature indicate on the triclinic symmetry of the Phase II. Above T₁ the crystal becomes orthorhombic. First-order phase transition at T₂ causes the symmetry of the crystal in the Phase III to be monoclinic with the c-axis unique. The phase transition diagram is proposed and compared with the phase situation in nondeuterated NH₄BeF₃ crystals.     

Investigation of zirconium phosphate Zr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>4</Subscript> during heating

Zirconium phosphate Zr₃(PO₄)₄ has been synthesized by the sol-gel technique and investigated using X-ray powder diffraction, IR spectroscopy, and differential scanning calorimetry. It has been established that the symmetry of the unit cell, R \(\bar 3\) c, which is characteristic of the NaZr₂(PO₄)₃ (NZP) family, is lowered to P \(\bar 3\) c. The behavior of the zirconium phosphate during heating has been examined using high-temperature X-ray diffraction at temperatures ranging from 25 to 575°C. It has been revealed that the structure of the zirconium phosphate is hardly subjected to expansion due to heating in the temperature ranges 25–125°C (α _a < 1 × 10^?6 K^?1, α _c < 1 × 10^?6 K^?1, Δα < 1 × 10^?6 K^?1) and 325–575°C (α _a = ?1.4 × 10^?6 K^?1, α _c < 1 × 10^?6 K^?1, Δα < ?2.4 × 10^?6 K^?1). In the temperature range 125–325°C, the synthesized compound undergoes a second-order phase transition (upon heating), which is accompanied by the contraction of the structure along all crystallographic directions. Upon cooling in the range from 75 to 25°C, the phase transition is accompanied by the expansion of the structure.     

Concentration Magnetic Phase Transitions in the (La1−xCaxMnO3 System

Comprehensive investigations into crystal structures, electrical and magnetic properties of the (La_1−xCa_x)MnO₃ (x = 0 ÷ 0.6) solid solutions are performed. Two concentration magnetic phase transitions are found: antiferromagnetic-ferromagnetic with x = 0.14 and ferromagnetic (T_c = 150 K) - ferromagnetic (T_c = 260 K) at f = 0.2. It is shown that the first of them is due to the crystal structure O′ O orthorhombic transition, the second - to the increase of ferromagnetic interaction at the expense of additional interaction through conduction electrons. A diagram of the magnetic states for (La_1−xCa_x)MnO₃ at x = 0 / 0.6 is given.     

Mathematical Description of Strongly Nonlinear Pressure Dependence of Phase Transition Temperatures

In order to describe mathematically the pressure dependence of phase transition temperatures we have derived an equation using the following assumption: i. The transition enthalpy Δ_tH = const. ii. The transition volume Δ_tV depends on the pressure p according to: The modified Simon-Glatzel-equation T = T₀(1 + p/b)^a exp (cp) allows to calculate the transition temperatures T also in cases of strongly non-linear relations.     

Molecular Statistical Theory of the Frank Elastic Constants of Liquid Crystals

Abstract

The Frank elastic constants K ₁, K ₂, K ₃ are calculated in the mean field approximation by assuming that the intermolecular force is the sum of hard rod repulsion (length L and width D) and Maier-Saupe's type attraction. The main conclusions are as follows. (1) the inequlaities K ₃? K ₁ > K ₂ necessarily hold. (2) All the K'_is are nearly proportional to the square of the orientational order parameter S. (3) In thermotropic system, K ₁/S ², K ₁/K and K ₂/K(K: mean elastic constant) increase slowly and K _3/K, K ₃/K ₁ decreases with L/D, whereas K/kT _c is nearly constant for L/D = 3 ～ 5. These tendecies agree fairly well with the observations on liquid crystals with almost rigid structure. (4) In the lyotorpic system in which L/D ? 1, K ₁/3 = K ₂ = cLk _T/3π D ² and k ₁/K ₃ = 4D/5cL are obtained (c: packing fraction). The estimate for PBLG solution nearly agrees with recent experimental data.     

Structure and phase transitions in trigonal Cs3Sb2I9 crystals

The atomic structure of Cs₃Sb₂I₉ single crystals was refined using X-ray diffraction data (sp. gr. P3m1; wR = 1.58% and R = 3.07%). The phase transitions revealed earlier were found to be accompanied by the appearance of superstructural reflections. At T _c1 = 86 K, the reflections indicating doubling of the c parameter. At T _c2 = 73 K, a first-order phase transition takes place accompanied by “freezing” of the satellites h, k + 1/2, l + 1/2 reflections. In the temperature range from 73 to 78 K, an incommensurate phase providing the satellites h, k + 1/2 + δ, l + 1/2 is formed.     

Thermodynamic characteristics of Ti-based glass-forming alloys

Based on thermodynamic characteristics of the stable metallic liquid at melting temperature and the supercooled liquid, the present work calculated the mixing enthalpy ΔH^mix, the mixing entropy ΔS^mix and the Gibbs free energy difference between the supercooled liquid and the resulting crystalline phases ΔG of typical Ti-based amorphous alloys. The results show that for the case of larger ΔS^mix, moderate ΔH^mix for the stable liquid and smaller ΔG for the supercooled liquid, Ti-based alloys tend to achieve high glass-forming ability (GFA). A new parameter, β, defined as (T_g ? T_k)/(T_l ? T_g), has been introduced to evaluate the GFA of Ti-based bulk amorphous alloys (wherein T_g, T_l, and T_k represent the glass transition temperature, the liquidus temperature, and the Kauzmann temperature, respectively). Experimental data imply that the larger the β, the better the GFA for Ti-based amorphous alloys.     

Magnetic Susceptibility in 2D Superconductor NaxHfNCl System

Abstract

Superconducting critical temperature, T_c and the shielding volume fraction, SVF, of layered nitride superconductor Na_xHfNCl have been studied as a function of x, i.e. Na concentration. Although T_c decreases gradually with increasing x from 20.0 K at x=0.11 to 16.5 K at x=0.85, SVF has a sharp peak around x=1/6, where strong coupling between local ordering of Na atoms and Fermi surface instability can be expected. Structural disorder in the samples above x=0.5, observed by powder neutron diffraction, does not affect the superconductivity appreciably. Electronic specific heat coefficient, γ, is estimated to be about 7.7 mJ/mol/K² by its difference of magnetic susceptibility between HfNCl and Na_0.5HfNCl. The γ value is relatively small compared with the high T_c value, revealing double honeycomb lattice system as new potential higher T_c superconductor series by intercalation.     

Formation Entropy of Schottky Defects and Free Formation Enthalpy of Vacancy Pairs in Alkali Halide Crystals

The melting of alkali halides occurs probably at a critical mole fraction x_c = 3.2 · 10⁻⁴ of thermally created vacancies (Schottky defects). Using this value the formation entropy of Schottky defects is found to be s_S = (962.1 K mol/kJ L/T_m – 16.1) k (L, T_m heat and temperature of fusion, respectively). As to the free association enthalpy g_A = h_A – T_sA of (impurity-vacancy) complexes it is s_A = (10.8 h_A/eV – 2.56) k. Using this relation the concentration vacancy pairs is found to be smaller than that of isolated vacancies up to the melting point.     

Nuclear Spin-Lattice Relaxation in the Linear Chain Metal,NbSe3

Abstract

The nuclear spin-lattice relaxation time T ₁ of ⁹³Nb in NbSe₃ has been observed as a function of frequency v _N in the range 6-40 MHz at 4.2 K and of temperature T in the range 1.3-77 K at 10 MHz. [T ₁ T]^?1 is found to be proportional to 1/√ν corresponding to characteristic divergence of spin correlation function in 1-D system. Below ~10 MHz, a break down of the divergence is observed. The important features of the T dependence observed are a sharp minimum at ~45 K and an asymptotical approach to the metallic relation, T ₁ T= const, with decreasing T down to helium temperature. This [T ₁ T]^?1 minimum is explained by the destruction of the Fermi surface due to the CDW gap formation. The re-increase of [T ₁ T]^?1 below the CDW transition may suggest a partial recovery of the destructed Fermi surface.