Texture transitions in binary mixtures of 6OBAC with compounds of its homologous series

Recently the authors have observed in compounds of the 4,n-alkyloxybenzoic acid series, with the homologous index n ranging from 6 to 9, a texture transition in the nematic range which subdivides the nematic phase in two sub-phases displaying different textures in polarised light analysis. To investigate a persistence of texture transitions in nematic phases, we prepared binary mixtures of 4,6-alkyloxybenzoic acid (6OBAC) with other members (7-, 8-, 9-, 12-, 16OBAC) of its homologous series. Binary mixtures exhibit a broadening in the temperature ranges of both smectic and nematic phases. A nematic temperature range of 75°C is observed. In the nematic phase, in spite of the microscopic disorder introduced by mixing two components, the polarised light optics analysis of the liquid crystal cells reveals a texture transition. In the case of the binary mixture of 6OBAC with 12OBAC and with 16OBAC, that is of compounds with monomers of rather different lengths, the texture transition temperature is not homogeneous in the cell, probably due to a local variation in the relative concentrations of compounds.     

Positron lifetimes in five phases of BEA

Positron lifetimes have been measured as a function of temperature in 4-butyloxybenzal-4′-ethylaniline (BEA). BEA has been previously reported to have two liquidcrystalline phases (smectic and nematic) with transition temperatures as follows: solid → smectic, 40.5° C; smectic → nematic, 51.0° C; and nematic → isotropic liquid, 65.5° C. Positron life time spectra were resolved into two components, with the shorter component τ₁ remaining approximately constant in all phases, and τ₂ exhibiting reversible changes at all of the above transitions. In addition, an irreversible discontinuity in the τ₂ lifetime was observed in the vicinity of 28° C, indicating the presence of a new phase (phase X) of BEA. The τ₂ andI ₂ values obtained for the various phases of BEA are: solid (1.25 nsec, 7.1%), phase X (1.97 nsec, 26.2%), smectic (2.36 nsec, 23.6%), nematic (2.72 nsec, 28.3%), and isotropic liquid (2.69 nsec, 29.8%).     

Parameters of LC molecules’ movement measured by dielectric spectroscopy in wide temperature range

Dielectric properties of a nematic liquid crystal (NLC) mixture ZhK-1282 were investigated in the frequency range of 10²–10⁶Hz and a temperature range of ?20 to 80?°С. On the basis of the Debye’s relaxation polarization model dielectric spectra of temperature dependence of the orientational relaxation time τ and the dielectric strength δe were numerically approximated at the parallel orientation of a molecular director relative to alternating electric field. Influence of ester components in the mixture plays crucial role in relaxation processes at low temperature and external field frequency. The activation energy of the relaxation process of a rotation of molecules around their short axis was measured in a temperature interval of ?20 to ?+15?°С in which the dispersion of a longitudinal component of the dielectric constant takes place. The energy of potential barrier for polar molecules rotation in the mesophase was calculated. The value of the transition entropy from the nematic to isotropic phase was obtained from this calculation. The values of the coefficient of molecular friction and rotational diffusion were obtained by different methods. The experimental data obtained are in a satisfactory agreement with the existing theoretical models.     

Structural transformation study of TiO2 nanoparticles annealing at different temperatures and the photodegradation process of eosin-Y

Hydrothermal method was used to prepare TiO₂ nanoparticles with annealing temperature at 500 °C–700 °C. The mixture of anatase-rutile phase was investigated by powerful tool of X-ray diffraction (XRD). The structural parameters of anatase and rutile mixture phaseTiO₂ nanoparticles were calculated from the Rietveld refinement. The transformation rate of rutile was increased linearly with an annealing temperature of 500 °C–700 °C. The spherical morphology of the anatase and rutile mixed phase were obtained by scanning electron microscope and transmission electron microscope. The spherical particle of the anatase and rutile TiO₂ shows with great aggregation with different size and within the range of few tens nm. The EDAX study revealed the presence of titanium and oxygen. The best photocatalytic activity was identified as the 87.04% of anatase and 12.96% of rutile mixer phase of TiO₂. Various factors could be involved for a better photocatalytic activity.     

Crystal → nematic phase transition in the liquid crystalline system 1‐isothiocyanato‐4‐(trans‐4‐propylcyclohexyl) benzene (3CHBT) probed by temperature‐dependent micro‐Raman study and DFT calculations

Raman spectra of 3CHBT in unoriented form were recorded at 14 different temperature measurements in the range 25–55 °C, which covers the crystal → nematic (N) phase transition, and the Raman signatures of the phase transition were identified. The wavenumber shifts and linewidth changes of Raman marker bands with varying temperature were determined. The assignments of important vibrational modes of 3CHBT were also made using the experimentally observed Raman and infrared spectra, calculated wavenumbers, and potential energy distribution. The DFT calculations using the B3LYP method employing 6‐31G functional were performed for geometry optimization and vibrational spectra of monomer and dimer of 3CHBT. The analysis of the vibrational bands, especially the variation of their peak position as a function of temperature in two different spectral regions, 1150–1275 cm⁻¹ and 1950–2300 cm⁻¹, is discussed in detail. Both the linewidth and peak position of the ( C H ) in‐plane bending and ν(NCS) modes, which give Raman signatures of the crystal → N phase transition, are discussed in detail. The molecular dynamics of this transition has also been discussed. We propose the co‐existence of two types of dimers, one in parallel and the other in antiparallel arrangement, while going to the nematic phase. The structure of the nematic phase in bulk has also been proposed in terms of these dimers. The red shift of the ν(NCS) band and blue shift of almost all other ring modes show increased intermolecular interaction between the aromatic rings and decreased intermolecular interaction between two  NCS groups in the nematic phase. Copyright © 2009 John Wiley & Sons, Ltd.     

The properties of some derivative autocorrelation functions computed with the atom-atom potential

High-resolution quasi-elastic neutron-scattering measurements have been made on two nematogens: DMBCA with a nematic range 108 to 119°C, and 5CB and a tail-deuteriated sample (D5CB), having a nematic range 22·6 to 35·1°C.

Results on 5CB in the crystal phase at ～18°C showed no significant quasielastic broadening, which means that any random motions of the alkyl chain are slower than about 5 × 10⁹ rad s^-1. Measurements were made at a single temperature in the nematic phases on specimens aligned in a magnetic field of 0·25T; for DMBCA with scattering vector Q⊥n (n is the nematic director) and for 5CB and D5CB with Q⊥n and Q∥n and also on the isotropic liquid phase of D5CB at 45°C. Analysis of the coherent scattering from nematic D5CB at Q = 1·2 Å^-1 and 25°C gave an order parameter <P ₂>=0·55, close to the simple mean field value for this temperature. The coherent scattering from DMBCA is too weak to allow this experiment to be performed.

The most remarkable qualitative feature of the results is the close similarity of the scattering law S(Q, ω) for D5CB (and 5CB) with Q⊥n and Q∥n. Analysis of the results in all cases was made using values for the translational diffusion constants measured previously. Corrections for multiple scattering are shown to be important and a single simple model has been devised which fits the line shapes of all the results for D5CB in nematic (Q⊥n and Q∥n) and isotropic liquid phases and DMBCA. The model involves uniaxial rotational diffusion about the long molecular axis m coupled to a displacement along the rotation axis giving a net rotation in a plane whose normal makes an angle ∝ relative to the direction m. Values for the rotational diffusion constant D _rd ns^-1 are as follows: D5CB, 25°C, 6 (∝ ～ 50°); 45°C, 10. DMBCA, 112°C, 16, (all ±10–15 per cent).

The results for D5CB and 5CB are so similar that no additional detailed model fitting was attempted for the fully hydrogenous sample and it is concluded that while the motion of the alkyl tails is freer, the time scale of the motions is not more than about a factor of 2 faster than that of the molecular cores.     

Phase transformation of Ni/Si thin films induced by nanoindentation and annealing

Thin Ni/Si films are prepared by depositing a Ni layer with a thickness of 100 nm on a Si (100) substrate. The as-deposited thin-film specimens are indented to a maximum depth of 500 nm using a nanoindentation technique and are then annealed at temperatures of 200°C, 300°C, 500°C and 800°C for 2 min. The microstructural changes and phases induced in the various specimens are observed using transmission electron microscopy (TEM) and micro-Raman scattering spectroscopy (RSS). Based on the load-displacement data obtained in the nanoindentation tests, the hardness and Young’s modulus of the as-deposited specimens are found to be 13 GPa and 177 GPa, respectively. The microstructural observations reveal that the nanoindentation process prompts the transformation of the indentation-affected zone of the silicon substrate from a diamond cubic structure to a mixed structure comprising amorphous phase and metastable Si III and Si XII phases. Following annealing at temperatures of 200∼500°C, the indented zone contains either a mixture of amorphous phase and Si III and Si XII phases, or Si III and Si XII phases only, depending on the annealing temperature. In addition, the annealing process prompts the formation of nickel silicide phases at the Ni/Si interface or within the indentation zone. The composition of these phases depends on the annealing temperature. Specifically, Ni₂Si is formed at a temperature of 200°C, NiSi is formed at a temperature of 300°C and 500°C, and NiSi₂ is formed at 800°C.     

High-temperature vibrational densitometer for high-pressure aggressive media

High-temperature vibrational densitometer for chemically active media was developed. The principle of operation of the densitometer is based on recording and analyzing the natural frequency of a U-shaped high-pressure capillary filled with the test medium. The placement of the capillary in a thermostat capable of maintaining its temperature to within ±0.1°C makes it possible to measure the density and study the phase behavior of aggressive media over pressure and temperature ranges of 0.1–50 MPa and 20–500°C, respectively. Measurements of the carbon dioxide density with the densitometer developed at temperature below, near, and above its critical point (31°C), as well as water density measurements at temperatures up to 375°C demonstrated good agreement with the data from the NIST (National Institute of Standards and Technology) interactive database. The density of a methanol-water mixture was measured at temperatures up to 300°C.     

A structural and Mössbauer study of Y3Fe5O12 nanoparticles prepared with high energy ball milling and subsequent sintering

The influence of ball milling and subsequent sintering of a 3:5 molar mixture of Y₂O₃ and α-Fe₂O₃ on the formation of nanocrystalline Y₃Fe₅O₁₂ (YIG) particles is studied. Pre-milling the mixture for 100 h lowers the onset temperature at which the material forms to 900°C which is 200°C lower than that reported when a similar mixture of reactants was premilled for shorter times. A single-phased nanocrystalline Y₃Fe₅O₁₂ phase develops as a sole product when the pre-milled mixture is heated at 1,000°C (12 h). This temperature is ~300–400°C lower than those used to prepare the material conventionally. The bulk and surface crystal structure of the nanoparticles is studied with X-ray diffraction, Mössbauer spectroscopy, Atomic Force Microscope (AFM) and X-ray photoelectron spectroscopy.     

Mössbauer and X-Ray studies of MgO-Fe nanocomposite

XRD phase analysis and Mössbauer spectroscopy are used to study the structure of magnesiowustite (Mg_0.9Fe_0.1) obtained via the decomposition of mixed iron-magnesium oxalate in different atmospheres, the structure of MgO-α-Fe composite after reduction by hydrogen in Ar + 5% H₂ gas mixture at 800°C and 1000°C, and the structure of iron at every stage. It was shown that fine particles of α-Fe are obtained upon the decomposition of iron-magnesium oxalate in vacuum at 1000°C. If a precursor is decomposed in high purity Ar, α-Fe particles form during reduction at lower temperature (800°C) due to the partial decomposition of one of the phase components—magnetite.     

Slow tumbling of paramagnetic probes in the solid phase of the liquid-crystal p (p methoxybenzlidene) amino benzonitrile

A marked broadening of the extrema resonances of the electron paramagnetic resonance spectra of vanadyl acetylacetonate and copper benzoyl acetonate doped into the solid phase of the nematic liquid-crystal p (p methoxybenzlidene) amino benzonitrile is observed as the temperature is increased to the solid to liquid-crystal transition at 106°C. The effects are a result of slow tumbling of the paramagnetic probes which is shown to follow a thermally activated Arrhenius behavior. The motion is consistent with previous Raman and neutron scattering studies in the solid phase which suggest the possibility of large amplitude fluctuations and a soft disordered regime in the solid near the transition to the liquid-crystal phase.     

The effect of annealing temperature on the morphology and piezoelectric characteristics of BaTiO3 nanofibers and domain switching under different temperatures

Effects of annealing temperature (600–750 °C) on crystalline structure, the morphology and piezoresponse hysteresis loops of BaTiO₃ nanofibers prepared by electrospinning are characterized by X-ray diffraction, scanning electronic microscopy, transmission electron microscope and piezoresponse force microscope. When the annealing temperature is 700 °C, the nanofibers become smoother and have a diameter of 100–300 nm. Meanwhile the typical butterfly-shaped amplitude loop and 180°phase change represents the best ferroelectric and piezoelectric properties at 700 °C. So the 700 °C was found to be optimum for good piezoelectric characteristics at annealing temperature of 600 °C–750 °C. In order to give more clear evolution of domain states at different external fields, the three dimensional topographic and phase images of the nanofiber at different temperatures are observed by piezoresponse force microscope. The 90° domain switching is observed during heating from room temperature to 125 °C and the domain switching tends to be stable when the temperature exceeds a critical value. The thermal stress due to the high temperatures is responsible for switching mechanism from the perspective of equilibrium state free energy. This work suggests that the temperature variation should be considered while designing the ferroelectric devices based on one dimensional material.     

Unusual structural phase transition in nanocrystalline zirconia

The present work is the first example demonstrating that a hydrous zirconia formed by precipitation can yield a nearly pure nanocrystalline monoclinic zirconia at a temperature as low as 320 °C. The X-ray diffraction pattern of the hydrous zirconia heated to 310 °C shows that diffraction peaks begin to emerge and reveals a just crystallized mixture of predominantly monoclinic zirconia (70%) with some tetragonal zirconia(30%). In other words, the hydrous zirconia formed in the present work yields the predominantly monoclinic structure coexisting with the tetragonal one as soon as crystallization starts at low temperature (310 °C). This is an important exception to the general principle that amorphous zirconia precursors first convert to the tetragonal structure of zirconia with increasing calcination temperature and then transform to the monoclinic one at a higher temperature (∼600 °C). At the crystallization temperature (310 °C), the monoclinic crystallite size is about 17 nm and the tetragonal one 28 nm. The monoclinic crystallite is much smaller than the tetragonal one with which it co-exists. This result is also not consistent with the traditional view that a critical particle size effect is responsible for the stability of the tetragonal and monoclinic structures. When the temperature (310 °C) is slightly raised to 320 °C, the XRD pattern shows a nearly pure monoclinic zirconia. The crystallite size of the monoclinic zirconia is around 15 nm, and it does not change appreciably as calcination temperature is increased from 320 to or above 400 °C. The unusual structural phase transition has been investigated by several complementary experimental tools: X-raydiffraction and surface analyses, and infrared and Raman spectroscopies. PACS 81.07.-b; 64.70.Nd; 82.80.-d; 78.67.-n; 81.05.Je     

Influence of the thermal power of a Fe atomic flux on the formation of Cu/Fe nanofilms on a Si(001) substrate

The growth of a Fe sublayer 1.5–14.0 monolayers (MLs) thick and a Cu film (about 5 MLs) on this sublayer is studied at a reduced temperature (1240°C) and an elevated temperature (1400°C) of a Fe source and at a reduced temperature (900°C) of a Cu source. The films are examined by Auger electron spectroscopy, low-energy electron diffraction, and atomic force microscopy. As metal sources, thin Fe and Cu strips on a Ta foil are used. It is shown that a nonequilibrium 2D phase forms in the Fe-on-Si(001) film up to a thickness of 4–5 MLs. This phase appears as closely packed atomically smooth nanoislands. When the thickness of the film exceeds 4–5 MLs, the nonequilibrium Fe phase changes to the bulk (3D) phase of Fe and its silicide Fe _x Si. At Fe source temperatures of 1240 and 1400°C, the nonequilibrium phase consists of Fe with Si segregated on the Fe surface, and a Fe-Si mixture. Copper on the nonequilibrium Fe and Fe-Si phases grows, respectively, as a smooth layer Cu with Si segregated on the top and in the form of Cu-Fe and Cu-Si mixtures. Cu islands growing on the bulk Fe and Fe _x Si phases have smaller and larger sizes, respectively.     

Differential thermal analysis at high pressures—VII: Phase behaviour of solid methanol up to 3kbar

The phase behaviour of solid methanol was investigated from -196°C to the melting temperature and up to 3 kbar, using a low-temperature high-pressure dta apparatus. The melting temperature rises from -98°C at 1 atm to -64°C at 2775 bar. Solid methanol exhibits a transition at atmospheric pressure at approximately -115°C; the transition has a strong tendency to superheat and to occur at -110°C. The transition temperature rises from approximately -115°C at 1 atm to -81°C at 2725 bar. Small impurities of water induce a “second transition” at -117.3°C that must be attributed to the water-methanol eutectic. Volume changes accompanying the phase transition have been calculated using the Clausius Clapeyron equation.     

The synthesis of the chiral non-mesogenic d-seco estrone derivatives and their influence on the phase transitions of cholesteric liquid crystals

The synthesis of new chiral seco-estrone derivatives is presented, as well as their influence on the phase transition of binary mixtures of cholesteryc liquid crystals. The new chiral derivatives do not posses any liquid crystalline phases and were synthesized in several synthetic steps, starting from estrone. We have studied the mixtures of cholesteryl non-anoate (40%) with cholesteryl myristate (40%) and addition of new chiral derivatives 3 4, or 5 (20%). It was concluded that the addition of chiral derivative 3 to the binary mixture stabilizes smectic A and cholesteric phase and shifts the phase transition temperature with respect to pure binary mixture for about 5°C towards lower temperatures. The extension of the temperature range of the cholesteric phase from 5°C to 15°C was established in the case when the derivatives 3 and 4 are added to the binary mixture of cholesteryl nonanoate with cholesteryl myristate. The phase diagrams of investigated compounds are formed on the basis of data obtained by the optical microscopy. Using X-ray diffraction on the crystalline powder of unoriented samples we have determined the molecular parameters: the thickness of smectic and cholesteric layers and average distance between the long axes of neighboring molecules.     

High Pressure and High Temperature Studies on Manganese Oxides

High pressure and high temperature quench experiments on f -MnO 2 , Mn 2 O 3 and sol gel derived manganese oxides have been carried out to identify any new phases to which the materials may transform under high pressure and high temperature conditions. Results of ESR, DTA and TGA investigations on sol gel derived manganese oxide have shown it to be hausmannite Mn 3 O 4 , instead of n -Mn 2 O 3 as reported earlier in the literature. The sol gel derived manganese oxide transforms to n -Mn 2 O 3 when heated above 700°C. Sol gel derived Mn 3 O 4 , when quenched from 5 GPa and temperature range 800-1200°C, gives a mixture of Mn 3 O 4 (hausmannite) and a phase having CaMn 2 O 4 (marokite)-type structure. f -MnO 2 undergoes partial amorphization when pressure-quenched from 8 GPa at room temperature. The high pressure and high temperature quench experiments up to 5 GPa and 700°C showed that the decomposition temperature of f -MnO 2 increases with pressure. The new phase reported by Liu (1976) from diamond-anvil cell (DAC) experiments on pyrolusite MnO 2 is identified to be a low-density polymorph f -MnO 2 . This unusual result of formation of low-density f -MnO 2 , having an open structure at high pressure and high temperature, is probably due to quenching of a non-equilibrium phase in Liu's (1976) laser-heated DAC experiment.     

Translational order parameter in the smectic-B phase of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl

4-Hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1-1′-biphenyl, a liquid crystalline material shows smectic-B (SmB) and nematic phases, respectively, between 60.3–98.5°C and 98.5–130.8°C. X-ray diffraction patterns were recorded at different temperatures in the SmB phase and were used to compute translational order parameters. For this purpose, we have employed a theoretical model recently reported by Kapernaum and Giesselmann. The results obtained are discussed in terms of the basic understanding of the SmB phase.     

An infrared spectroscopic study of the structural phase transitions of n-C10H21NH3Cl

Infrared spectroscopy was used to study the phases of n-decylammonium chloride in the temperature range 20 to 65°C. The infrared spectra of virgin crystals at room temperature are indicative of a well-ordered phase, while the spectra of the high temperature phase demonstrate extensive motional and conformational disorder. The phase obtained by cooling from 65 to 25°C also presents motional and conformational disorder. However, it is metastable and annealing for 13 days at room temperature (25°C) results in a phase similar but not identical to the virgin crystals.     

Phase Transformations in Nd–Fe–B-Based Alloys under High Pressure Torsion at Different Temperatures

In this work, we studied the behavior of the Nd–Dy–Fe–Co–Cu–B alloy for permanent magnets under high pressure torsion (HPT). In the initial state of the studied alloy, it mainly contained the crystalline phase τ₁ (Nd, Dy)₂(Fe, Co, Cu) ₁₄B. After HPT at room temperature (T_HPT = 30°C), a mixture of an amorphous phase with nanocrystalline inclusions of the τ₁ phase is observed in the alloy. In the equilibrium phase diagram, this state is equivalent to a mixture of the τ₁ phase with the melt at the temperature T_eff= ∼1100°C. The thus determined T_eff value is called the effective temperature. When the T_HPT temperature of the HPT treatment increases to 300 and 400°C, the amorphous phase disappears, and the Fe₂B and γ-Fe phases appear instead. In the equilibrium phase diagram, this state is equivalent to a mixture of phases τ₁+ Fe₂B + γ-Fe, which is observed in the temperature range from ∼950 to ∼1050°C. We explain this phenomenon by the fact that with an increase in the HPT temperature T_HPT, the rate of formation of defects during deformation remains constant, but the rate of their thermal relaxation (annihilation) increases. This is equivalent to decrease in the effective temperature T_eff in the equilibrium phase diagram. The previously predicted decrease in T_eff with an increase in T_HPT is observed for the first time.