Phase transitions in liquid crystal 6O.4 (p-<Emphasis Type="Italic">n</Emphasis>-hexyloxybenzylidine-p′-<Emphasis Type="Italic">n</Emphasis>-butylaniline)

DSC measurements on p-n-hexyloxybenzylidine-p′-n-butylaniline (6O.4) showed that the crystalline to liquid crystalline (K-S _H) transition at 33.7°C observed in the heating cycle does not revert even when the sample is cooled down to −100°C. Hence it is inferred that a physically stable supercooled liquid crystalline phase is formed on cooling 6O.4. To investigate the K-S _H transition further the techniques of polarized microscopy and X-ray diffraction were used which concurred with the DSC results. Quasielastic neutron scattering measurements carried out to study the re-orientational motions in the ordered phases of 6O.4 (K and S _H) show that while in the crystalline phase (at RT) the re-orientational motion is found to involve only the core of the molecule, in the S _H phase (at 45°C) the dynamics involves the whole molecule and this motion is found to persist even when the sample cools back to room temperature corroborating the results of the DSC, microscopy and X-ray diffraction.      

Effect of proton irradiation on the physical properties of PC/PBT blends

Samples from polycarbonate/poly (butylene terephthalate) (PC/PBT) blends film have been irradiated using different fluences (1?×?10¹⁵– 5?×?10¹⁷ H⁺/cm²) of 1?MeV protons at the University of Surrey Ion Beam Center, UK. The structural modi?cations in the proton irradiated samples have been studied as a function of fluence using different characterization techniques such as X-ray diffraction and UV spectroscopy. The results indicate that the proton irradiation reduces the optical energy gap that could be attributed to the increase in structural disorder of the irradiated samples due to crosslinking. Furthermore, the color intensity ΔE, which is the color difference between the non-irradiated sample and those irradiated with different proton fluences, increased with increasing the proton fluence up to 5?×?10¹⁷ H^+/cm², convoyed by an increase in the red and yellow color components. In addition, the resultant effect of proton irradiation on the thermal properties of the PC/PBT samples has been investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). It is found that the PC/PBT decomposes in one weight loss stage. Also, the variation of transition temperatures with proton fluence has been determined using DSC. The PC/PBT thermograms were characterized by the appearance of two endothermic peaks due to the glass transition and melting temperatures. The melting temperature of the polymer, T_m, was investigated to probe the crystalline domains of the polymer, since the proton irradiation destroys the crystalline structure so reducing the melting temperature.     

A new high-pressure polymorph of Ti2O3: implication for high-pressure phase transition in sesquioxides

The post-corundum phase transition has been investigated in Ti₂O₃ on the basis of synchrotron X-ray diffraction in a diamond anvil cell and transmission electron microscopy. The new polymorph of Ti₂O₃ was found at about 19 GPa and 1850 K, and this phase was stable even at about 40 GPa. A new polymorph of Ti₂O₃ can be indexed on a Pnma orthorhombic cell, and the unit-cell parameters are a=7.6965 (19) Å, b=2.8009 (9) Å, c=7.9300 (23) Å, V=170.95 (15) Å³ at 19 GPa, and a=7.8240 (2) Å, b=2.8502 (1) Å, c=8.1209 (3) Å, V=181.10 (1) Å³ at ambient conditions. The Birch–Murnaghan equation of state yields K ₀=206 (3) GPa and K′₀=4 (fixed) for corundum phase, and K ₀=296 (4) GPa and K′₀=4 (fixed) for the post-corundum phase. The molar volume decreases by 12% across the phase transition at around 20 GPa. The structural identification was carried out on a recovered sample by the Rietveld method, and a new polymorph of Ti₂O₃ can be identified as Th₂S₃-type rather than U₂S₃-type structure. The transition from corundum-type to Th₂S₃-type structure accompanies the drastic change of the form of polyhedron: from TiO₆ octahedron in the corundum-type to TiO₇ polyhedron in the Th₂S₃-type structures.     

Time-Resolved ESR Study on Complex Radical Pairs Formed in the Photolysis of Methylene Blue Included in Water-Soluble Sulfonated Calixarenes

The photochemical reactions of methylene blue (MB) included in water-soluble sulfonated calix[n]arenes (n = 4, 6, 8) are studied using a time-resolved electron spin resonance method. The chemically induced dynamic electron polarization (CIDEP) spectra show the formation of the complex radical pair composed of the MB monocation radical and calixarene (phenoxyl-type) radical. The lifetime and broadened spectral shape are dependent on the size of the calixarene and are due to the longitudinal and transverse relaxation mainly induced by the tumbling motion of the radical pair with the spin dipole–dipole interaction. The pair dissociates in a few hundreds of nanoseconds in cases of n = 6 and 8.     

Shear Effect on Morphology of Poly(Butylene Terephthalate)/Poly(Styrene‐co‐Acrylonitrile) Blends

Abstract

The shear flow effect on the morphology of poly(butylene terephthalate)(PBT)/poly(styrene‐co‐acrylonitrile)(SAN) was studied by a parallel plate type shear apparatus. In PBT/SAN = 20/80 blend, particle size of dispersed domains was governed by both break‐up and coalescence processes, and it was much affected by shear rate. The minimum particle size was observed at a certain shear rate. This phenomenon can be explained by the shear matching effect of PBT and SAN; that is, the viscosity ratio of PBT to SAN changed with shear rate and the finest morphology was obtained at the appropriate viscosity ratio. Similar behavior was also observed for PBT/SAN = 70/30 (PBT was the matrix), even though the particle size was larger than that of PBT/SAN = 20/80. For PBT/SAN = 10/90 blend, the sample showed a complicated appearance during shearing. A translucent region correlated to the fine morphology was observed more than twice with increasing shear rate. This phenomenon could not be explained by the viscosity matching effect only. It was affected by small changes in the balance of breaking‐up and coalescence effects.     

Lanthanum Oxide Effects on the Structure of Calcium Phosphate Glasses

Calcium phosphate glasses, in which part of calcium oxide was replaced by lanthanum oxide, were prepared by using the conventional melt quench method. The structures of xLa₂O₃ · (50-x)CaO · 50P₂O₅ (x = 0, 1, 3, 6, 12 mol%) samples were investigated by X-ray diffraction (XRD), Raman spectrum, Fourier transform infrared spectrum (FTIR), and differential scanning calorimetry (DSC). The results show that lanthanum oxide acts as network modifier in the network space of glass structure. The glass formation occurs at an O/P ratio of about 3.0–3.12. At larger values, the crystalline phases calcium pyrophosphate (Ca₂P₂O₇) and calcium lanthanum phosphate [Ca₉La(PO₄)₇] are detected in the samples. Raman and FTIR spectra indicate that the structure of lanthanum-free sample is chain P–O–P bond metaphosphate–based Q² units. Glass structure will change to Q² and Q¹ units when the lanthanum oxide content is less then 6 mol%. When lanthanum oxide content increases to 9 and 12 mol% more nonbridging oxygen in the glass, resulting in the depolymerization of the phosphate network, the network of glass transforms to Q², Q¹, and Q⁰ units mixture. Based upon DSC results, T_g slightly decreases because of the depolymerization of microstructure. Endothermal peak of DSC curves indicate that crystal phases separate out from vitreous body with the addition of lanthanum oxide content.     

Structure and dynamics of liquid MgO under high pressure

Microstructure, dynamics, and diffusion mechanism in liquid MgO have been studied by molecular dynamics simulation. Models consisting of 2000 atoms were constructed under a wide range of pressure and at a temperature of 3800 K. The local structure is analyzed through the coordination number distribution and topology statistics of coordination units (basic structural units) MgO _x (x=2, 3, 4, 5, 6, 7). As regards the structural dynamics, the nearest-neighbor atomic exchange among coordination units, spatially heterogeneous dynamics, clustering, and structural stability (lifetime of basic structural units) are investigated in detail. Investigation of structural dynamics allows us to gain insight into various important atomic (molecular) properties and to clarify the diffusion mechanism in liquid MgO under high pressure.     

The B 2Σ+–X 2Σ+ Transition of 12C17O+: The 2‐υ″ Progression

Abstract

Three new bands of the B ²Σ⁺–X ²Σ⁺ system of ¹²C¹⁷O⁺ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the ¹⁷O₂ isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of ¹²C¹⁷O⁺ are ω_e=2185.9658(84), ω_e x _e = 14.7674(11), B _e=1.927001(38), α_e=1.8236(22)×10^?2, γ_e=?0.331(28)×10^?4, D _e=6.041(12)×10^?6, β_e=0.100(31)×10^?7 cm^?1, and the equilibrium constants for the excited state are σ_e=45876.499(15), ω_e=1712.201(12), ω_e x _e=27.3528(39), B _e=1.754109(35), α_e=2.8706(57)×10^?2, γ_e = ?1.15(19)×10^?4, D _e=7.491(20)×10^?6, β_e=2.13(12)×10^?7, γ_e = 2.0953(97)×10^?2, and α_γe=?9.46(59)×10^?4 cm^?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B ²Σ⁺ and X ²Σ⁺ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the B–X system.     

L-[1-13C]phenylalanine breath test in patients with chronic liver disease of different etiologies

The aim of this study was to compare the oxidation of l-[1-¹³C]phenylalanine (¹³C-PheOx) in patients with chronic liver failure due to different etiologies using l-[1-¹³C]phenylalanine breath test. Breath samples were collected before the administration of 100 mg l-[1-¹³C]phenylalanine, and every 10 min thereafter until completion of 1 h. Control subjects (n=9) presented a larger cumulative percentage of ¹³C dose recovery (CPDR) than patients (n=124) with chronic liver disease, regardless of the etiology (7.5±0.7 vs. 4.2±0.2, p=0.001). No differences in CPDR were found considering the Child-Pugh (CP) class or etiology: alcoholic (CP A=7.7±0.7, CP B=4.1±0.5, CP C=2.0±0.3), hepatitis C virus (CP A=5.4±0.5, CP B=4.0±0.2, CP C=2.2±0.3), hepatocellular carcinoma (CP A=5.5±1.6, CP B=3.6±1.8, CP C=2.2±1.0); or cryptogenic cirrhotic patients (CP A=7.4±1.5, CP B=4.4±0.4, CP C=2.1±0.7). Results confirm that ¹³C-PheOx decreases in patients with cirrhosis with respect to controls, notwithstanding the etiology.     

Influence of Ag2O on crystallisation and structural modifications of phosphate glasses

A series of phosphate glasses of composition 45P₂O₅–(40???x)CaO–15Na₂O–xAg₂O (x?=?0, 3, 6, 8, 10 and 12?mol%) with different Ag₂O contents were prepared using the melt-quenching technique. The incorporated Ag₂O highly influenced the increase of its transition tendency towards crystallisation and, on contrary, reduced the degree of glassification of phosphate glasses. The lowering of glass transition temperature and increase in thermal expansion were observed in glasses against Ag₂O inclusions. The crystalline phase transitions of amorphous material during thermal treatment were confirmed by employing X-ray diffraction studies. As revealed by X-ray photoelectron spectroscopy, the incorporated silver oxide into phosphate glass exists in two different oxidation states, Ag₂O and AgO. The pyrophosphate and metaphosphate units were predominantly occupied in glass and glass ceramics. The elastic moduli and Vicker's hardness values exhibited the decrease in phosphate glass structural compactness due to Ag₂O-incorporation and these values were found to improve because of crystalline transitions.     

Determination of the Solubility Parameter of Epoxidized Soybean Oil by Inverse Gas Chromatography

The thermodynamic parameters of epoxidized soybean oil (ESO) were determined by means of inverse gas chromatography (IGC) in the temperature range of 303.15 K-343.15 K. Two groups of probe solvents with different chemical natures and polarities were used to obtain information about ESO. The thermodynamic parameters—such as molar heat of sorption, weight fraction activity coefficient, Flory–Huggins interaction parameter, and partial molar heat of mixing—were obtained to judge the interactions between ESO and solvents at the studied temperatures. Also, the solubility parameters of ESO were found by plotting the graph of δ₁ ²/(RT) – χ^∞ ₁₂/V₁ vs. solubility parameters, δ₁, of the probes. The results showed that the selected solvent ethyl acetate was a moderate solvent for ESO; n-hexane was a moderate (but close to a better) solvent; while the probes n-heptane, n-octane, n-nonane, and chloroform were excellent solvents. From the extrapolation to 298 K, the solubility parameter value of ESO was 16.70 (J/cm³)^0.5.     

Mesomorphic behaviors of a series of heterocyclic benzothiazole-imine-ester-based liquid crystals

A series of new calamitic liquid crystals, 2-[4-(4-alkoxybenzoyloxy)benzylidenamino]benzothiazoles comprising a heterocyclic (benzothiazole) and two phenyl rings core system, terminal alkoxy chain, imine and ester linkers were prepared and characterized. This series comprises eight members wherein the members vary by the length of alkoxy chain (C_nH_2n+1O-, where n?=?4, 6, 8, 10, 12, 14, 16, 18). Spectral analysis results were in conformity with the expected structure. Their thermotropic behaviors were studied by using differential scanning calorimetry, optical polarizing microscopy and powder X-ray diffraction techniques. A single mesophase (nematic) was observed for the first member of the series (n?=?4). As the alkoxy chain increased to n?=?6, 8, 10, 12, 14, the nematic phase appeared together with an additional SmA phase. When moving from n?=?16 until the highest member (n?=?18), the nematic phase disappeared and these compounds only exhibited a single mesophase (SmA).     

Synthesis and characterization of wide range mesogenic esters based on asymmetrical 2,5-disubstituted 1,3,4-thiadiazole

A homologous series of new 13 esters, 4-(5-(p-tolyl)-1,3,4-thiadiazol-2-yl)-phenyl-4-alkoxybenzoate, (IV_n), based on 1,3,4-thiadiazole core has been synthesized. The structures of these esters were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and mass techniques. Their mesophases behavior was investigated with hot-stage polarizing optical microscope and differential scanning calorimetry. The thermal stability for most of these derivatives was measured by thermal gravimetric analysis. All the target esters showed enantiotropic mesomorphic behaviors with nematic and nematic/smectic C phases. The phase transition temperatures and liquid crystalline properties were affected by the nature of heterocyclic ring and the length of the alkoxy chain. Only the nematic phase was observed in the first 10 derivatives, (n = 1–10), while the last 3, (n = 12, 16 and 18) showed nematic and smectic C phases. These compounds demonstrated high liquid crystalline ranges, both in heating and cooling cycles. The mesomorphic results obtained were compared with the reported analogs of similar constituents.     

Study on the Supramolecular Interactions of p-Sulfonated Calix[4, 6, 8]arenes with Lomefloxacin

The supramolecular interactions between a homologous series of p-sulfonated calix[n]arenes (SCnA, n = 4, 6, 8) as hosts and lomefloxacin (LFLX) were studied by spectrofluorometry. LFLX was found to react with SCnA to produce stable complexes. The fluorescence intensity of the complexes decreased gradually with increasing SCnA concentration. The formation of complexes was further confirmed by ¹H NMR studies and molecular modeling calculations. Data of the stability constants and thermodynamic parameters of the obtained complex showed that the stability of the SC8A-LFLX complex is superior to that of SC6A-LFLX and SC4A-LFLX. A mechanism was proposed to explain the inclusion process.     

Effect of ion beam irradiation on palladium (II) acetyl acetonate dispersed in polymer matrix

Composites, containing different concentrations of palladium (II) acetylacetonate in polymethyl methacrylate (PMMA) matrix were prepared by vigorous mixing. PMMA was prepared by solution polymerization technique. The composites were irradiated with a 120 MeV Ni¹⁰⁺ beam at two different fluences of 1×10¹¹ and 5×10¹² ions/cm² to study ion-induced effects on their dielectric, structural properties and surface morphology. AC electrical properties of these samples were studied in the frequency range 100 Hz to 10 MHz. The dielectric permittivity/loss shows frequency dependent behavior and it obeys the universal law of dielectric (i.e. ?α f ^n?1) for pristine and irradiated samples at high frequency. The crystalline size and crystallinity of the composites were studied by X-ray diffraction analysis. Decrease in peak intensity after irradiation signifies the amorphization which is also responsible for decrease in T _g as obtained by means of differential scanning calorimetry measurement. Fourier transform infrared spectra also support this result. Surface roughness increases upon irradiation as observed from scanning electron microscopy.     

Self-aggregates formation of tetrachloroperylene acid esters in Langmuir and Langmuir-Blodgett films

Using Langmuir and Langmuir-Blodgett techniques molecular films of chlorinated perylene derivatives, namely tetra-n-butyl-1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylate (PCn for n = 1, 5, 9) have been studied. The Langmuir films of pure compounds and mixed with liquid crystalline 4-octyl-4′-cyanobiphenyl (8CB) were characterized by surface pressure-mean molecular area isotherms. An additive rule reveals miscibility of all the dyes with 8CB but shows different types of intermolecular interaction forces. The pure and mixed Langmuir films were transferred onto quartz plates and characterized spectroscopically. Absorption and fluorescence spectra were recorded for the samples in form of diluted chloroform solution, the dye with 8CB mixtures in monomolecular Langmuir-Blodgett films and in liquid crystal cells. Different tendency to aggregation of the dye with short and long alkyl chains was observed. It is shown that the dye molecule stacking and aggregation of the chlorinated perylene dyes depend on the dye concentration and are related to the torsion of the perylene core.     

Stabilisation of Ce-Cu-Fe amorphous alloys by addition of Al

The present work describes the formation of amorphous alloys in the (Al_1?xCe_x)₆₂Cu₂₅Fe₁₃ quaternary system (0 ≤ x ≤ 1). When the amount of Ce falls in the range 0.67 ≤ x ≤ 0.83, the alloys obtained exhibit a completely amorphous structure confirmed by powder X-ray diffraction. Otherwise, at compositions x = 0.5, 0.58, 0.92 and 1, a primary crystalline phase forms together with an amorphous matrix. The crystallisation temperature (T_x) decreases with increasing Ce content, varying from 593 K for x = 0.5–383 K for x = 1. Composition x = 0.75 is considered as the best glass former, exhibiting a large supercooled liquid region of 40 K width that precedes crystallisation. In order to form bulk amorphous alloys, ribbons with this later composition were consolidated into few millimetre thick discs using pulsed electric current sintering at different temperatures, yet preserving the amorphous structure. Meanwhile, increasing temperature above 483 K triggers crystallisation of a primary phase isostructural to AlCe₃. Further increase in the temperature up to 573 K yields a higher fraction of the crystalline phase. Testing mechanical properties, using nanoindentation, revealed that both elastic modulus (E) and hardness (H) depend on the Al content, ranging from E = 85.6 ± 3.7 GPa and H = 6.2 ± 0.7 GPa for x = 0.5 down to E = 39.8 ± 1.0 GPa and H = 3.1 ± 0.2 GPa for x = 0.92.     

Preparation and photocatalytic activity of Mo-doped WO3 nanowires

Mo-doped WO₃ nanowires were fabricated by a hydrothermal method in the presence of K₂SO₄. The physical properties of prepared nanowires were characterized by X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the obtained products are nanowires with diameters ranging between 10 and 20 nm, and lengths of about 600 nm. Its photoactivity was evaluated through the photodegradation of methylene blue (MB) in aqueous solution. Effects of the molybdenum concentration on the photoactivity of the obtained samples were investigated detailedly. The experimental results indicated that the Mo-doping enhanced the photoactivity of WO₃ nanowires.     

Wear resistance of CuZr-based amorphous-forming alloys against bearing steel in 3.5% NaCl solution

Abstract

To investigate the amorphous-crystalline microstructure on the tribocorrosion of bulk metallic glasses (BMGs), 6 mm diameter rods of Cu_46-xZr₄₇Al₇Ag_x (x = 0, 2, 4) amorphous-forming alloys with in situ crystalline and amorphous phases were fabricated by arc-melting and Cu-mould casting. Using a pin-on-disc tribometer, the tribo-pair composed by CuZr-based amorphous-forming alloys and AISI 52100 steel were studied in 3.5% NaCl solution. With the increase of Ag content from 0 to 4 at.%, the compressive fracture strength and the average hardness decrease firstly and then increase. Moreover, 4 at.% Ag addition increases the amount of amorphous phase obviously and inhibits the formation of brittle crystalline phase, resulting in the improvement of corrosion resistance and the corrosive wear resistance. The primary wear mechanism of the BMG composites is abrasive wear accompanying with corrosive wear. The tribocorrosion mass loss of Cu₄₂Zr₄₇Al₇Ag₄ composite is 1.5 mg after 816.8 m sliding distance at 0.75 m s^?1 sliding velocity under 10 N load in NaCl solution. And the volume loss evaluated from the mass loss is about 20 times lower than that of AISI 304 SS. Thus, Cu₄₂Zr₄₇Al₇Ag₄ composite may be a good candidate in the tribology application under marine environment.     

Phase transitions and electrical conduction in thermal energy storage compound (n-C12H25NH3)2CdCl4

Differential scanning calorimetry (DSC) and differential thermal analysis (DTA) are performed for the compound (n-C₁₂H₂₅NH₃)₂CdCl₄. The ac conductivity σ_(ω,T), and the complex dielectric permittivity ?*_(ω,T) are measured as a function of temperature (100 K < T < 375 K) and at some selected frequencies (3 → 100 kHz). Two structural phase transitions are detected at T = (330 ± 1) K and T = (343 ± 1) K as minor and major transitions, respectively. The analysis of the measured electrical parameters reveals that the frequency-dependent conductivity obeys the power law, and the quantum mechanical tunneling (QMT) model is the main conduction mechanism in the low-temperature phase (LTP; phase III). The role of hydrogen bond N–H…Cl as a trigger force for phase transitions has been discussed. While the LTP is of the order–disorder type, the high-temperature phase (HTP) or phase I seems to be conformational and represents the main transition.