Thermal expansion and heat capacity of dysprosium hafnate

Dysprosium hafnate is a candidate material for as control rods in nuclear reactor because dysprosium (Dy) and hafnium (Hf) have very high absorption cross-sections for neutrons. Dysprosium hafnate (Dy₂O₃·2HfO₂-fluorite phase solid solution) was prepared by solid-state as well as wet chemical routes. The fluorite phase of the compound was characterized by using X-ray diffraction (XRD). Thermal expansion characteristics were studied using high temperature X-ray diffraction (HTXRD) in the temperature range 298–1973 K. Heat capacity measurements of dysprosium hafnate were carried out using differential scanning calorimetry (DSC) in the temperature range 298–800 K. The room temperature lattice parameter and the coefficient of thermal expansion are 0.5194 nm and 7.69 × 10⁻⁶ K⁻¹, respectively. The heat capacity value at 298 K is 232 J mol⁻¹ K⁻¹.     

Thermodynamic stability of structure-H hydrates of methylcyclopentane and cyclooctane helped by methane

The four-phase equilibria were measured for the methylcyclopentane+methane+H₂O hydrate system (274.28–287.40 K, 1.75–9.34 MPa) and the cyclooctane+methane+H₂O hydrate system (274.08–288.57 K, 1.60–9.33 MPa). Each structure-H hydrate has the lower equilibrium pressure than the pure methane structure-I hydrate in the temperature range of the present work. The isothermal equilibrium pressures of both methylcyclopentane and cyclooctane hydrates are slightly higher than that of methylcyclohexane hydrate.     

Homopolyimides containing both benzimidazole and benzoxazole with high Tg and low coefficient of thermal expansion

A pair of isomer diamines containing both benzimidazole and benzoxazole and derived homopolyimides were synthesized for the first time. Due to rich rigid and linear benzoazole units, as well as the strong intermolecular interactions from the hydrogen bonding and the charge transfer complexation (CTC), the obtained polyimides (PIs) exhibited outstanding thermal properties, including high thermal weight loss temperature (T_d5% = 540–561°C), high glass transition temperature (T_g = 392–421°C), and low coefficient of thermal expansion (CTE = 1.3–20.9 ppm/°C). In addition, the obtained PIs also showed ideal mechanical properties (T_S = 189–240 MPa, T_M = 4.1–5.0 GPa and E_B = 2.9%–4.7%). These potential novel PI films with high T_g and low CTE were expected to be applied to next generation of flexible display substrate material.     

Radiation deterioration in mechanical properties and ion exchange capacity of Nafion N117 swelling in water

The base form Nafion N117 samples swelling in the oxygen-saturated distilled water were irradiated with γ-rays or with electron beams at various doses up to 1600 kGy at room temperature or at 343 K to obtain detailed information on the effect of oxygen on the radiation deterioration in the Nafion mechanical properties and in the ion exchange capacity. The contribution of the radical reactions where oxygen molecules did not participate was dominant for the radiation deterioration in the mechanical properties of the Nafion N117 membrane swelling in the oxygen-saturated distilled water at room temperature. The effect of oxygen molecules was not significant due to the little oxygen concentration in the distilled water even though oxygen was saturated in the water. The Nafion N117 membrane irradiated with γ-rays at 343 K became a weak and brittle material, since the rise of the temperature activated the reactions. Oxygen molecules, in contrast, have negligible part in the reactions at 343 K due to their lower solubility in the water. We observed the negligible effect of the radiation sources as well as of the dose rate below 10 kGy/h on the radiation deterioration in Nafion N117 mechanical properties at room temperature. The irradiation of the Nafion membrane with γ-rays or with electron beams is one of the acceleration tests of the Nafion degradation. We made clear that the dissolved fluorine measured using a fluoride ion meter is a hopeful index for the in situ judging of the Nafion mechanical deterioration. The ion exchange capacity of the membrane irradiated up to 1600 kGy was the 20% decrease of the initial capacity at room temperature. Nafion side chains terminating with –SO₃⁻ M⁺ groups were radiation-durable compared with the backbone.     

Synthesis,physical, and thermodynamic properties of 1-alkyl-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide ionic liquids

Synthesis of new ionic liquids (ILs) viz. 1-butyl-3-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide, [BCN³Py][NTf₂], 1-hexyl-3-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide, [HCN³Py][NTf₂], 1-hexyl-4-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide, [HCN⁴Py][NTf₂], and 1-octyl-3-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide, [OCN³Py][NTf₂] were performed. The specific basic characterization of new compounds by NMR spectra, elementary analysis, water content and glass transition temperature as well as melting temperature, enthalpy of fusion and decomposition of compounds TG/DTA determined by the differential scanning calorimetry, DSC is presented. The heat capacity was measured at three temperatures (298.15, 323.15, and 353.15) K and at pressure 0.1 MPa. The effect of temperature on the density and viscosity is reported over the temperature range from (293.15 to 363.15) K and at 0.1 MPa. The density and viscosity correlation for these systems was provided by an empirical polynomial. From the density–temperature dependence, the isothermal expansion coefficient (volume expansivity), α, was calculated. The surface tension of pure ionic liquids was measured at 0.1 MPa at five temperatures (298.15, 308.15, 318.15, 328.15, and 338.15) K. The surface thermodynamic functions such as surface entropy and enthalpy, critical temperatures according to the Eötvös and Guggenheim definition and the total surface energy of the ILs studied were derived from the temperature dependence of the surface tension values. The parachor and speed of sound for pure ionic liquids were described within a range of temperature from (298.15 to 338.15) K. A qualitative analysis on these quantities in terms of molecular interactions is reported.     

Solubility of hydrogen in toluene for the ternary system H2 + CO2 + toluene from 305 to 343 K and 1.2 to 10.5 MPa

The solubility of hydrogen in toluene in the presence of the compressed CO₂ at the temperatures from 305 to 343 K and the pressures from 1.2 to 10.5 MPa was measured by using a continuous flow technique. The obtained data indicate that more hydrogen could be dissolved in toluene at the pressures higher than a certain value depending on temperature and the molar ratio of H₂ to CO₂ in gas. The Peng–Robinson equation of state associated with the van der Waals mixing rule were found to correlate the VLE data of the ternary system H₂ + CO₂ + toluene satisfactorily. From the volume expansion resulted from the dissolution of CO₂ in toluene calculated by the proposed model, it was found that hydrogen solubility was generally increased with increasing volume expansion. A large volume expansion was required to enhance hydrogen solubility when the mole fraction of hydrogen in gas was low.     

High pressure phase equilibria in the system 1,1,1,2-tetrafluoroethane + heptylbenzene

Vapour–liquid, liquid–liquid and liquid–liquid–vapour equilibria for the system 1,1,1,2-tetrafluoroethane + heptylbenzene were determined in the temperature range from 260 to 400 K and at pressures up to 12 MPa. The system was found to be a type II system according to the classification of Van Konynenburg and Scott. The (l₂=l₁)g critical endpoint was found at T=320.07 K and P=1.155 MPa. The mole fraction of heptylbenzene in the critical liquid phase in the critical endpoint is approximately 0.20.     

Multiferroicity in La1/2Nd1/2FeO3 nanoparticles

Nano-sized La_1/2Nd_1/2FeO₃ (LNF) powder is synthesized by the sol–gel citrate method. The Rietveld refinement of the X-ray diffraction profile of the sample at room temperature (303 K) shows the orthorhombic phase with Pbnm symmetry. The particle size is obtained by transmission electron microscope. The antiferromagnetic nature of the sample is explained using zero field cooled and field cooled magnetisation and the corresponding hysteresis loop. A signature of weak ferromagnetic phase is observed in LNF at low temperature which is explained on the basis of spin glass like behaviour of surface spins. The dielectric relaxation of the sample has been investigated using impedance spectroscopy in the frequency range from 42 Hz to 1 MHz and in the temperature range from 303 K to 513 K. The Cole–Cole model is used to analyse the dielectric relaxation of LNF. The frequency dependent conductivity spectra follow the power law. The magneto capacitance measurement of the sample confirms its multiferroic behaviour.     

Low thermal expansion behavior and electrical conductivity of Mn3(Cu0.5SixGe0.5−x)N at low temperatures

Anti-perovskite manganese nitrides with the general formula Mn₃(Cu_0.5Si_xGe_0.5?x)N (x = 0.05, 0.1, 0.15, 0.2) were fabricated by mechanical ball milling followed by solid state sintering. The temperature dependence of thermal expansions, magnetic properties and electrical conductivities were investigated in the temperature range of 77–300 K. The results show that the operation-temperature window of negative thermal expansion (NTE) shifts to lower temperature and the magnitude of NTE becomes smaller with increasing Si content. Very low average coefficients of thermal expansion of 1.3 × 10^?6 K^?1 and 1.65 × 10^?6 K^?1 were observed in Mn₃(Cu_0.5Si_0.1Ge_0.4)N and Mn₃(Cu_0.5Si_0.15Ge_0.35)N within the temperature range of 77–300 K, respectively. In addition, the electrical conductivities of all the samples are in the range of 2.5–3.5 × 10⁵ (ohm m)^?1.     

Ionic and excited species in irradiated poly(dimethylsiloxane) doped with pyrene

The influence of temperature (77–230 K) on the fate of pyrene (Py) radical ions and Py excited states in irradiated poly(dimethylsiloxane) (PDMS) doped with Py is described. At 77 K, the Py radical ions seem to be stable, whereas the Py excited states [fluorescence (λ = 395 nm) and phosphorescence (λ = 575–650 nm)] are generated via tunneling charge transfer. In the range of the glass‐transition temperature (T_g = 152–153 K), the Py radical ions start to decay, taking part in a recombination process and leading to the Py monomer and Py excimer fluorescence (λ = 475 nm). The wavelength‐selected radiothermoluminescence (WS RTL) observed at approximately 395, 475, and 600 nm has helped us to identify the T_g range (152–153 K). The absorption maximum at approximately 404 nm, found in the temperature range under consideration, is thought to represent PyH^?, cyclohexadienyl‐type radicals produced as a result of the reaction of Py^?? with protonated PDMS macromolecules. With the initial‐rise method of evaluating the activation energy (E_a) with the WS RTL peaks observed in the T_g range, E_a values of 123–151 kJ mol^?1 have been found. Such high E_a values can be explained by the contribution of energy connected to the molecular relaxation of the matrix in the T_g range. The well‐known Williams–Landel–Ferry equation, with universal constants C₁ = 17.4 and C₂ = 12.7, has been successfully applied to the interpretation of old pulse‐radiolysis/viscosity data found for crosslinked PDMS doped with Py. The mechanisms involved in these phenomena are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6125–6133, 2004     

Starch saccharification by carbon-based solid acid catalyst

The hydrolysis of cornstarch using a highly active solid acid catalyst, a carbon material bearing SO₃H, COOH and OH groups, was investigated at 353–393 K through an analysis of variance (ANOVA) and an artificial neural network (ANN). ANOVA revealed that reaction temperature and time are significant parameters for the catalytic hydrolysis of starch. The ANN model indicated that the reaction efficiency reaches a maximum at an optimal condition (water, 0.8–1.0 mL; starch, 0.3–0.4 g; catalyst, 0.3 g; reaction temperature, 373 K; reaction time, 3 h). The relationship between the reaction and these parameters is discussed on the basis of the reaction mechanism.     

Tribological behaviour of nanostructured Ti-C:H coatings for biomedical applications

The development of a mechanically stable, functionally graded Ti-doped a-C:H interface layer in combination with a functional a-C:H coating requires a reduction of the brittle phases which induce generally problems in the transitions from Ti to TiC/a-C:H. The core objective of this study was to develop an optimum interlayer between the substrate and the functional top layer for biomedical applications, namely for tooth implants. Since the interlayer may be exposed to the sliding process, in the case of local failure of the top layer it has to fulfil the same criteria: biocompatibility, high wear resistance and low friction.The functional Ti-C:H layers with thickness in the range 2.5–3.5 μm were deposited by a magnetron sputtering/PECVD hybrid process by sputtering a Ti-target in a C₂H₂ + Ar atmosphere in dc discharge regime. The sets of coating samples were prepared by varying the C and H concentrations controlled by the C₂H₂ flow during the deposition process. The tribological properties were evaluated on a pin-on-disc tribometer at room temperature (RT) and at 100 °C using 440C balls with a diameter of 6 mm. The tests at 100 °C were performed to investigate the effect of the sterilization temperature on the tribological properties and the coating lifetime as well. The tribological performance was examined with respect to the friction coefficient, the wear rates of the coating and the counter-parts and the analysis of the wear debris. The Ti/C ratio decreased almost linearly from 4.5 to 0.1 with increasing C₂H₂ flow; the hydrogen content showed a minimum of 5 at.% at C₂H₂ flow of 30 sccm, while for lower flows it was about 10 at.%. The coatings could be divided into three groups based on the C₂H₂ flow: (i) 10–15 sccm, exhibiting severe abrasive damage during the sliding tests, (ii) 20–45 sccm, showing the highest hardness and friction values, and (iii) 52–60 sccm, with moderate hardness and minimal values of the friction coefficient and the wear rate.     

Synthesis, characterization and thermal expansion studies on europium titanate (Eu2TiO5)

The lattice thermal expansion characteristics of europium titanate (Eu₂TiO₅) have been studied by measuring the lattice parameter by high temperature X-ray diffraction technique (HT-XRD) in the temperature range 298–1573 K. Percentage linear thermal expansion and mean linear thermal expansion coefficients were computed from the lattice parameter data. The percentage linear thermal expansion in the temperature range 298–1573 K along a, b and c axes are 1.05, 1.15 and 0.95 respectively.     

Microfluidic fabrication of novel polymeric core-shell microcapsules for storage of CO2 solvents and organic chelating agents

Monodispersed polymeric microcapsules loaded with CO₂ solvents or chelating agents were produced by capillary microfluidics by photopolymerisation of three different UV curable materials, 1,6-hexanediol diacrylate (HDDA), Norland Optical Adhesive (NOA) 81, and Semicosil® 949 UV A/B (PDMS). Polymerization of HDDA and NOA 81 started after exposure to UVA light for 5 s and was completed within a minute, as confirmed by continuous FT-IR. Corrosive aqueous solutions of tetraethylenepentamine and diisopropyl iminodiacetic acid were encapsulated with 100% efficiency into poly(HDDA) and cured NOA81 shells without any leakage during prolonged storage. Poly(HDDA) shells were mechanically more stable than cured NOA81 and PDMS shells and resistant to drying-induced shell buckling. NOA81 and PDMS capsules underwent morphological changes during freeze drying leading to the formation of dimpled and crescent-moon-shaped particles, respectively. The storage stability in a hypotonic solution and buckling resistance of PDMS shells were significantly improved by embedding carbon-based nanomaterials into PDMS matrix. The incorporation of 0.5 wt% multi-walled carbon nanotubes into PDMS matrix led to an increase in a Shore A hardness from 1.6 to 2.3. A uniform distribution of MWCNTs in the polymer network was confirmed by XRD. All fabricated shells were thermally stable up to the temperature of 300°C.     

High-pressure phase equilibrium for the binary systems of {carbon dioxide (1) + dimethyl carbonate (2)} and {carbon dioxide (1) + diethyl carbonate (2)} at temperatures of 273 K, 283 K,and 293 K

Phase equilibrium data for the binary systems {carbon dioxide (CO₂) + dimethyl carbonate (DMC)} and {carbon dioxide (CO₂) + diethyl carbonate (DEC)} were measured at temperatures of 273 K, 283 K and 293 K in the pressure range of 0.5 MPa to 4.0 MPa. The measurements were carried out in a cylindrical autoclave with a moveable piston and an observation window. The experimental data were correlated with the Peng–Robison (PR) equation of state (EOS) and the Peng–Robinson–Stryjek–Vera (PRSV) equation of state with van der Waals-1 or Panagiotopoulos–Reid mixing rules. The correlations produced reasonable values for the interaction parameters. The comparisons between calculation results and experimental data indicate that the PRSV equation of state coupled with the Panagiotopoulos–Reid mixing rule produced the better correlated results.     

The p–T phase diagram for ferroelectric bis-thiourea pyridinium nitrate

The effect of temperature and pressure on physical properties of the ferroelectric bis-thiourea pyridinium nitrate inclusion compound has been studied by dielectric spectroscopy and nuclear magnetic resonance (NMR). At ambient pressure the ferroparaelectric phase transition observed at T₂ = 216 K is continuous in contrast to the nonferroelectric phase transition observed at T₁ = 273 K. Under small pressures, the temperatures of the phase transitions T₁ and T₂ increase with increasing pressure. Starting from about 250 MPa, T₁ temperature decreases with increasing pressure, while T₂ temperature increases with increasing pressure. At 450 MPa and 245 K a triple point is observed. Bis-thiourea pyridinium nitrate undergoes a continuous phase transition from the ferroelectric to paraelectric phase under 450 MPa, while above this pressure the phase transition from the ferroelectric to paraelectric phase is discontinuous. The change in the phase transition character is related to the crystallographic change in the group–subgroup relation between the ferro- and paraelectric phases taking place with increasing pressure.     

Li7PS6 and Li6PS5X (X: Cl,Br, I): Possible Three‐dimensional Diffusion Pathways for Lithium Ions and Temperature Dependence of the Ionic Conductivity by Impedance Measurements

Possible three‐dimensional diffusion pathways of lithium ions in crystalline lithium argyrodites are discussed based on earlier studies of local dynamics and site preferences. The specific Li‐ionic conductivities of the lithium argyrodites Li₇PS₆ and Li₆PS₅X (X: Cl, Br, I) and their temperature dependences are measured by impedance spectroscopy using different electron‐blocking and ion‐blocking electrode systems. Measurements were carried out between 160 K and 550 K depending on the respective sample. Bulk and grain boundary contributions and the influence of sample preparation are discussed. Typical values for the ionic conductivities at room temperature are in the range 10^–7 to 10^–5 S ·  cm^–1 and at 500 K between 10^–6 and 10^–3 S ·  cm^–1. Thermal activation energies are in the range 0.16 to 0.56 eV. The electronic conductivity at room temperature was measured by polarization measurements for the samples Li₆PS₅X (X: Cl, Br) and was shown to be in the order of magnitude of 10^–8 S ·  cm^–1. Chemical diffusion coefficients of lithium were calculated based on the polarization measurements. For Li₆PS₅Br a high value of 3.5 × 10^–6 cm² · s^–1 was found.     

A low‐temperature phase of bis(tetrabutylammonium) octa‐μ3‐chlorido‐hexachlorido‐octahedro‐hexatungstate

The title compound, (C₁₆H₃₆N)₂[W₆Cl₁₄], undergoes a reversible phase transition at 268 (1) K. The structure at 150 and 200 K has monoclinic (P2₁/c) symmetry. Both crystallographically independent tungsten chloride cluster anions sit on crystallographic inversion centers [symmetry codes: (−x, −y + 1, −z) and (−x + 1, −y + 2, −z)]. Two previous studies at room temperature describe the structure in the space group P2₁/n with a unit‐cell volume approximately half the size of the low‐temperature unit cell [Zietlow, Schaefer et al. (1986). Inorg. Chem. 25 , 2195–2198; Venkataraman et al. (1999). Inorg. Chem. 38 , 828–830]. The unit cells of the room‐ and low‐temperature polymorphs are closely related. The hydrocarbon chain of one of the tetrabutylammonium cations is disordered at both 150 and 200 K.     

Temperature and pressure dependences of volumetric properties of two poly(propylene glycol) dimethyl ether lubricants

The densities at high pressures of two dimethoxy end-capped poly(propylene glycols), CH₃–O–[CH₂–CH(CH₃)–O]_m–CH₃, with average molar masses higher than 1300 g · mol^?1, were measured in the range (0.1 to 60) MPa at five different temperatures from (298.15 to 398.15) K. The measurements were performed in a high-pressure vibrating tube densimeter. A correction factor, due to the viscosity of the sample, was applied to the experimental density values. The pressure–volume–temperature behavior of these lubricants was evaluated accurately over wide temperature and pressure ranges and correlated successfully with the empirical Tammann–Tait equation. The experimental data and the correlations were used to study the behavior and the influence of temperature and pressure on the isothermal compressibility, the isobaric thermal expansivity, and the internal pressure, as well as the effect of the polyether molecular structure on these properties.     

Yellow-green luminescence and extreme thermal quenching in the Sr6M2Al4O15:Eu2+ (M = Y,Lu, Sc) phosphor series

A series of Eu²⁺-substituted yellow-green emitting phosphors based on the compound, Sr₆M₂Al₄O₁₅ (M = Y, Lu, Sc) were identified as potential efficient phosphors based on their high calculated Debye temperatures (Θ_D > 450 K), which acts as a proxy for photoluminescent quantum yield (PLQY). The crystal structure contains corner-sharing [MO₆] octahedra and [AlO₄] tetrahedra leading to a highly connected, densely packed crystal structure. However, contrary to prediction, these compounds all showed a low PLQY (<6.5%) at room temperature. Temperature dependent luminescence measurements indicate that the photoluminescence is intense at 80 K but loses ≈90% of the emission intensity by room temperature, with the thermal quenching temperature (T₅₀) occurring well below room temperature. These results suggest that even though Debye temperature (Θ_D) is a valid proxy for PLQY, it does not describe thermal quenching.