Growth Mechanism and Twinning of Sucrose Effected by Surface Adsorption Processes

Growth experiments with sucrose dependent on temperature and supersaturation of solutions were carried out to find the conditions for appearance of the three different growth types. Measurements of growth rates of {110} and {1 1 0} faces at 50°C and supersaturation c_s = 10% resulted in the known feature that in pure solutions a crystal grows faster in positive b-direction than in the negative one. Addition of raffinose stopped growth of {110}. In an electric field generated by 20 kV direct voltage (crystal orientation: negative pole of b-axis pointed towards the negative electric pole) the crystal grew in negative b-direction three times faster than in the positive one. In the presence of raffinose the growth rates in both directions become equal. If the crystal is turned by 180° in the solution (pure solution and in the presence of raffinose) the growth behaviour is the same as without an electric field. These results can be interpreted in such way that in pure solutions sucrose molecules adsorb to {1 1 0} (bonds exist between the fructose rings of molecules in liquid and solid phases) and that in presence of raffinose these molecules adsorb to {110} (bonds exist between glucose (solid) and galactose rings (liquid phases)). By the electric field the adsorption is hindered. The theory is in accordance with the fact that crystals situated in a suspension of the solution can intergrow with a host crystal in twin positions (in pure solutions on {1 1 0} and in the presence of raffinose on {110}).     

Dynamic Layer Response under Electric Field in Antiferroelectric Liquid Crystal Cells Measured by Synchrotron Microbeam Time Resolved X-Ray Diffraction

Abstract

Direct observation of the local layer response of an antiferroelectric liquid crystal to the step form electric field has been carried out by a time resolved synchrotron X-ray micro diffraction measurement. When an electric field was changed from high voltage to OV, corresponding to the ferroelectric to antiferroelectric phase transition, the local layer transformed from the bookshelf to the quasi-bookshelf structure within 0.3 ms. The horizontal chevron structure was found in both the phases, though the decrease in the horizontal chevron angle was observed during a period of 0.2 ms after turning off the electric field. In the antiferroelectric to ferroelectric phase transition process (from OV to high voltage), the layer structure transformed to the bookshelf within 0.04 ms.     

Optical absorption spectra and related parameters of ammonium zinc chloride crystal in the antiferroelectric and commensurate phases

Optical absorption along the three crystallographic axes of (NH₄)₂ZnCl₄ single crystals is reported over a temperature range from 276 K to 350 K. Our results clearly confirm the antiferroelectric to commensurate phase transition at 319 K. Analysis reveals that at the absorption edge the type of transition is the indirect allowed one. The indirect band gaps at various temperatures are determined and their temperature dependence is estimated in the antiferroelectric and commensurate phases. Optical parameters related to the temperature dependence of the energy gap are evaluated. The single‐effective oscillator model was used to describe the imaginary part of the dielectric constant, which facilitate calculation of the dipole moment parameters. The steepness parameter is given, its value is used to estimate the temperature dependence of the indirect energy gap and the result is compared with that calculated graphically. In the region of the absorption edge, the absorption coefficient obeys Urbach's rule. Urbach characteristic parameters are determined and their temperature dependence is investigated. Correlation between different parameters is considered. Most of the results confirm the optical isotropic nature of AZC crystals. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fluid Biaxial Banana Smectics: Symmetry at Work

Abstract

Perhaps one of the most surprising results in the past 10 years was the prediction of Brand et al. [1] that fluid biaxial smectics made from comopunds without asymmetric carbons could, by symmetry, have a spontaneous polarization, P, in the layer plane. They called this construct, which can be either ferroelectric or antiferroelectric, smectic C₉. Advances gained from their prediction include the development of highly efficient electrets for broad-band telecommunications [2, 3] as well as a basic non-linear model [4] for TLAFs, thresholdless antiferroelectrics [5], now seen in beatiful, CMOS compatible, active matrix liquid crystal displays [6] (figure 1).     

Structures and Non-linear Optical Properties of Multi-Sulfur π-Conjugated Compounds 4,5-Vinylenedithio-1,3-dithiole-2-thione (C5H2S5) and 4,5-Vinylenedithio-1,3-dithiole-2-one (C5H2OS4)

Abstract Both the title multi-sulfur molecules C₅H₂S₅ (1) and C₅H₂OS₄ (2) have a chair conformation, while molecule 1 has a higher degree of π-conjugation. Both the crystals are characterized by short S···S intermolecular contacts and by face-to-face column-like packing style, but crystal 1 has been more stabilized which may be the result of its stronger π–π intermolecular interactions. Compound 1 crystallizes in non-centrosymmetric polar space group Pmn2₁ with a = 10.6826(17), b = 9.3633(11), c = 4.0764(6) ?, V = 407.74(10) ?³, and Z = 2. The molecular dipole moment of 1 is ±62.5(1)° away from the macro-polarization direction along the c-axis. Consequently, the crystalline powder of crystal 1 exhibit a second harmonic generating (SHG) intensity 0.5 time strong as that of urea standard powder crystals when irradiated by a 1,080 nm of Nd:YAP laser beam. Compound 2 shows no SHG effect because it crystallizes in centrosymmtric space group Pbca with a = 11.4208(8), b = 7.8843(9), c = 33.587(3) ?, V = 3024.3(5) ?³, and Z = 16. Index Abstract Structures and Non-linear Optical Properties of Multi-Sulfur π-Conjugated Compounds 4,5-Vinylenedithio-1,3-dithiole-2-thione (C₅H₂S₅) and 4,5-Vinylenedithio-1,3-dithiole-2-one (C₅H₂OS₄) Gang Xue, Qi Fang,* Wen-Tao Yu, Xia Chen, and Hong Lei Compound C₅H₂S₅ crystallizes in the polar space group Pmn2₁ and its crystalline powder exhibits a second harmonic generating (SHG) intensity 0.5 times that of urea standard (1080 nm → 540 nm), while the similar compound C₅H₂OS₄ has no SHG effect because of its centrosymmetric space group Pbca.      

Hydrogen Bonded, π···π Stacked and X···π Framework Structures in Bis(2,6-Lutidinium) Tetrahalocuprate(II) Complexes

Abstract  

In the crystal structures of (2,6-lutidinium)₂[CuCl₄], 1 and (2,6-lutidinium)₂[CuBr₄], 2, the anion CuX₄ ²⁻ is connected to eight and four surrounding cations in 1 and 2, respectively, through (N–H···X) (H₂C–H···X) and (C–H···X) hydrogen bonds to form two-dimensional layers approximately normal to the crystallographic b-axis. These layers are further connected by means of offset face-to-face interactions (parallel to b-axis) to give three-dimensional structures. The hydrogen bonding (type and number) around each anion could be influenced by the anion size, as same cation is used, allowing different cation…anion interpenetrations.     

Real domain structure in orthorhombic phase of NaNbO3 crystals

Systematics and essential elements of real domain structures in antiferroelectric phases of NaNbO₃ crystals is presented. Observed deviations from ideal model can be caused by crystal defects and conditions of the phase transition.     

Flux growth of La‐doped lead zirconate stannate titanate antiferroelectric crystals

Relaxor antiferroelectric single crystals lead lanthanum zirconate stannate titanate (PLZST) with the composition around the morphotropic phase boundary (MPB) have been grown by flux method using 50 wt% PbO‐PbF₂‐B₂O₃ as a flux. The obtained crystals are light yellow in color. The XRD patterns revealed that the habitual faces of the obtained crystal are (001). The crystal morphology was studied and related to a layer growth mechanism controlled by two‐dimensional growth. The chemical composition of as‐grown crystal was analyzed by inductively coupled plasma atomic emission spectrometry (ICP), indicating a slight decrease of the amount of Ti compared to the starting materials. The result was verified by the XRD patterns with the phase transformation from the co‐existence of tetragonal and rhombohedra phases to the single tetragonal phase. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Cu Ions on the Dipole Moments and Polarization of Strontium Barium Niobate Single Crystals

The crystal growth, the ferroelectric hysteresis loops, and the infrared reflectivity spectra of coppermodified strontium barium niobate (SBN) single crystals are reported. Compared with the undoped SBN crystals, the copper-modified crystals have stable hysteresis loops, the spontaneous polarization of which is about 0.30 C/m², but that of the undoped SBN crystals is only about 0.12 C/m². Their coercive field strength is all about 340 V/mm. The experimental results of the infrared spectra show that the infrared reflectivities vary as the orientations of the dipole moments owing to the copper-doping. The c-axis becomes the most stable orientation of the dipole moments, and the polarization will be locked and won't recede if the copper-modified crystals are polarized into monodomains.     

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.     

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.     

Thermoanalytical and morphologic study of gel-grown silver (I) chromate single crystals

Rhombic single crystals of silver (I) chromate were grown in silica gels. They were of tabular shape with a size of a = 0.3, b = 30 and c = 3 mm. The morphology of the crystals was interpreted by a detailed discussion of the structure. Silver (I) chromate consists of (100) layers connected along the a-axis by silver atoms in octahedral coordination. The crystals were characterized by their powder diffraction data. Differential thermal analysis studies were made by use of single crystals. The enthalpy of the phase transformation taking place at 485.2 °C is found to be ΔH_tr = 8.8 kJ/mol.     

The crystal and molecular structures of isoperezone, aminoperezone, and isoaminoperezone: a comparative study of their crystal packing

The crystal structures of isoperezone (1), aminoperezone (2), and isoaminoperezone (3) have been determined by single-crystal X-ray diffraction. Compound (1) yields orange crystals, orthorhombic space group P2₁2₁2₁ with unit cell dimensions a = 6.271(6), b = 30.373(7), c = 7.257(1) Å, and Z = 4; compound (2) yields purple crystals, orthorhombic space group P2₁2₁2₁ with unit cell dimensions a = 6.498(3), b = 7.500(1) c = 29.200(6) Å, and Z = 4; compound (3) yields purple crystals, monoclinic space group P2₁ with unit cell dimensions a = 7.354(1), b = 7.511(1), c = 13.283(1) Å, = 102,07(1)°, and Z = 2. The side chains in (1)–(3) are oriented out of the plane of the quinone ring at an angle of 124, 144, and 97°, respectively. The molecules in the crystal are held together by hydrogen-bonding networks and van der Waals interactions.     

Single crystals of calcium and strontium phenylphosphonate grown via hydrothermal crystallization

Single crystals of Ca(HO₃PC₆H₅)₂ (1) and Sr(HO₃PC₆H₅)₂ (2) have been obtained via the crystallization of their respective amorphous powders. The amorphous compounds were synthesized by traditional solution routes and were subsequently crystallized at 160°C in a Teflon-lined autoclave containing 1–3 mL distilled water. The resultant single crystals were physically isolated and their structures determined by single crystal X-ray diffraction. The two compounds are isostructural and crystallize in space group C2/c with lattice parameters of a = 31.267(3) ?, b = 5.6185(6) ?, c = 7.7202(8) ?, β = 101.924(2)°; and a = 31.514(4) ?, b = 5.8098(8) ?, c = 7.8218(10) ?, β = 102.063(3)° for the calcium and strontium phenylphosphonate, respectively.     

MOLECULAR AND COLLECTIVE PROCESSES IN THE ANTIFERROELECTRIC PHASE OF A CHLORINATED COMPOUND

Abstract

New liquid crystalline substance, (S) 4-(1-methylheptyloxycarbonyl)-3-chlorophenyl 4′-(4-butanoiloxybut-1-oxy)biphenyl-4-carboxylate, exhibiting ferroelectric and antiferroelectric phases have been studied by means of frequency domain dielectric spectroscopy. DSC calorimetric and electrooptic measurements were done to study its phase transitions and electrooptic behaviour. In the antiferroelectric SmC_A* phase one of the dielectric relaxation modes exhibits a non-Arrhenius behaviour. The plots of critical frequencies and dielectric increments vs. temperature show an anomalous behaviour of the relaxation processes in the neighbourhood of the ferroelectric — antiferroelectric phase transition. Reversal current method reveals one current peak in the ferroelectric phase and two in the antiferroelectric one. Temperature dependencies of tilt angle, spontaneous polarization, switching time and transmittance are also presented and discussed in scope of the mean-field theory.     

FLUCTUATION-INDUCED KERR EFFECT NEAR THE SMECTIC-A‒SMECTIC-Cα* PHASE TRANSITION

Abstract

The anomalous increase of Kerr effect due to pretransitional fluctuations has been investigated in the SmA phase close to the SmA-SmC_α* transition point in antiferroelectric liquid crystals MHPOBC and MHPOCBC. We have developed a Landau theory taking into account the fluctuations and shown that there are two contributions to the Kerr effect. On the basis of theoretical results, the experimental results obtained in MHPOBC and MHPOCBC were discussed and a clear evidence of the fluctuation-induced Kerr effect was presented.     

Supramolecular hydrogen-bonding networks in cytosine salicylic acid hydrate (2 : 3 : 2) complex

Cytosine-cytosinium base pairs are interconnected by triple hydrogen bonds thereby resembling a pseudo-Watson-Crick pattern and generates two characteristic R ₂²(8)-motifs. Both molecules of the salicylic acids interconnect the base pair and lead to the formation of one dimensional supramolecular hexameric tape along b-axis. This hexameric tape are sandwiched by the water molecules, one of the salicylic acid and salicylate anion which form one dimensional and two dimensional supramolecular hydrogen bonded networks in the crystal packing. Macrocylic rings of cavities are also noticed in the crystal structure.     

DISTORTIONS INDUCED BY A MAGNETIC FIELD IN PLANAR ALIGNED SAMPLES OF SMECTIC-C LIQUID CRYSTALS

Abstract

This article presents some preliminary theoretical results for the onset of the Helfrich-Hurault transition in smectic-C liquid crystals induced by a magnetic field applied parallel to the smectic layers. An energy in terms of the smectic layer displacement u is minimized via averaging to enable the calculation of a critical field strength H _c for the onset of layer distortions.     

Resonant scattering from liquid crystal devices: an in-situ structural probe for the smectic phases

Resonant X-ray scattering is a relatively new technique in the field of liquid crystals and in recent years has been used to investigate the structures of the SmC* sub-phases. This work has been carried out on several materials which include either a sulfur or selenium atom and has revealed the detailed biaxial structure of the four layer intermediate (ferrielectric) phase. Resonant X-ray scattering has also been used to produce the first in-situ measurements of the chiral smectic sub-phases in a liquid crystal device. Both the antiferroelectric and the four-layer intermediate phases have been observed via this technique in a device geometry. Electric field studies have also been carried out in these phases whilst monitoring phase structure simultaneously. In this paper I will summarize the most up-to-date results from resonant scattering in free-standing films and discuss resonant scattering experiments on liquid crystal devices.     

Synthesis and Crystal Structure of the Fluorite-Related Ruthenate, Trilanthanum Ruthenium Septaoxide La3RuO7

Abstract Single crystals of the lanthanum-containing ruthenate, trilanthanum ruthenium septaoxide, La₃RuO₇, were prepared via high-temperature flux growth and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Cmcm with a = 11.2077(6) ?, b = 7.4531(4) ?, and c = 7.6042(4) ? and is a member of a well-known family of compounds with the general formula Ln₃MO₇. Graphical abstract Synthesis and crystal structure of the fluorite-related ruthenate, trilanthanum ruthenium septaoxide La ₃ RuO ₇ William R. Gemmill, Mark D. Smith and Hans-Conrad zur Loye* Single crystals of La₃RuO₇ were isolated from a high-temperature KCl flux and characterized by single crystal X-ray diffraction. A view of the crystal structure approximately along [001] of La₃RuO₇ and displacement ellipsoids drawn at 50% probability level. The vertex-sharing RuO₆ octahedra are shown in blue, La³⁺ are shown in yellow, and O²⁻ are shown in red.