Temperature dependence of birefringence of atactic polystyrene: The liquid—liquid transition

The birefringence of solvent-cast atactic polystyrene films was measured as a function of annealing temperature. The birefringence was found to disappear at a temperature which corresponds to the liquid-liquid transition, as measured by differential scanning calorimetry. It is concluded that this experiment is a proof of the molecular origin of the liquid-liquid transition.     

Ultrasonic attenuation investigation of liquid hydrogen

Ultrasonic attenuation in liquid hydrogen has been messured withthe pulse-echo technique as a function of temperature from 13.84K to 20.50K,at 45MHz.The results indicate that the temperature dependence ofultrasonic attenuation in liquid hydrogen is mainly determined by volumeviscosity effect.Ultrasonic attenuatin due to volume viscosity is gettingmore and more with cooling.The ratio between volume viscous coefficientand shear viscous coefficient is from 1.4 to 4.2 within the measured tempera-ture region.     

Ionic liquids screening for desulfurization of natural gasoline by liquid–liquid extraction

Seventy five ionic liquids (ILs) were tested as a sequestering agent of sulfured compounds in natural gasoline (NG). Desulphurization of NG was performed by means of liquid–liquid extraction method at room temperature and atmospheric pressure. Experimental ILs containing imidazolium, pyridinium, and ammonium cations along with organic and inorganic anions were synthesized conventionally and under microwave and sonochemical conditions. The effect of the molecular structure of ILs on the desulfurization efficiency of NG with high sulfur content was evaluated. Analysis indicated that the anion type played a more important role than the cation on the desulphurization process. ILs based on halogen–ferrates and halogen–aluminates exhibited the highest efficiency in sulfur removal, and their efficiency is further improved when there is an excess of metallic salt in a ratio of at least 1:1.3 during the synthesis of the corresponding IL. An explanation for the ability of metallic ILs to remove sulfur-containing compounds from natural gasoline based on the ratio of the ionic charge to the atomic radius is proposed. Furthermore, a method to recover and reuse water-sensitive to halogenated precursors is described.     

Effects of long-wavelength fluorescence excitation in N, N′-dimethylaminobenzonitrile liquid solutions

We have studied the properties of the emission, absorption, and excitation of dual fluorescence of N,N??-dimethylaminobenzonitrile in a set of solvents of different polarity under selective irradiation of solutions by light with different energies of quanta in the range of the long-wavelength absorption band. In all cases, dual fluorescence is observed, which is caused by emission from locally excited Franck-Condon and charge-transfer states. A change in the energy of excitation quanta has no effect on the position of the fluorescence bands; however, the intensity ratio between the bands noticeably changes in favor of the intensity of the long-wavelength band, which belongs to the charge-transfer state. To explain the observed effects, we involve data of quantum-mechanical calculations, which show that there is a considerable probability of occurrence in solutions of these systems of rotational isomers that differ in the orientation of the dimethylamino group with respect to benzonitrile. In the excited state, these rotamers have different charge-transfer reaction rates, which leads to a change in the intensity ratio of the observed fluorescence bands upon using the selective excitation.     

The influence of temperature on red-edge excitation effects in liquid solutions of N,N′-dimethylaminobenzonitrile

A systematic study of new photophysical and photochemical processes in solutions is continued by the example of a recently found phenomenon of redistribution of the intensities of two fluorescence bands of N,N′-Dimethylaminobenzonitrile (DMABN) in polar solutions at room temperatures under selective irradiation by light with different photon energies in the region of the long-wavelength absorption band. The effects observed are explained using data of quantum-mechanical calculations, which reveal that solutions of these systems are very likely to contain rotational isomers with different orientations of the dimethylamino group with respect to the plane of the benzonitrile residue. The excited-state charge transfer reactions in these rotamers occur in different ways and, hence, with different rates, because of which the intensity ratio of recorded fluorescence bands is different for different wavelengths of selective excitation. In this study, the influence of the temperature on the red-edge excitation effect observed in the fluorescence of DMABN solutions in acetonitrile is studied in the temperature range of 274–313 K using the previously used selective excitation method. It is found that these effects manifest themselves at any temperature within this range, but are especially strong at 313 K. The parameters of the dual fluorescence that are most sensitive for recording of the considered effects are determined, and the obtained temperature dependences are interpreted.     

Temperature range of the liquid–glass transition

It has been shown that the currently used method for calculating the temperature range of δT_g in the glass transition equation qτ_g = δT_g as the difference δT_g = (T₁₂–T₁₃) results in overestimated values, which is explained by the assumption of a constant activation energy of glass transition in deriving the calculation equation (T₁₂ and T₁₃ are the temperatures corresponding to the logarithmic viscosity values of logη = 12 and logη = 13). The methods for the evaluation of δT_g using the Williams–Landel–Ferry equation and the model of delocalized atoms are considered, the results of which are in satisfactory agreement with the product qτ_g (q is the cooling rate of the melt and τ_g is the structural relaxation time at the glass transition temperature). The calculation of τ_g for inorganic glasses and amorphous organic polymers is proposed.     

Electrical resistivity of liquid Sb–Zn alloys

Using the DC four-probe method, temperature dependence of the electrical resistivity (ρ???T) of Sb_{100? x} Zn _x (x?=?25,?40,?50,?57,?61,?80 at%) alloys was investigated in the temperature range of 500–860°C. The results showed that resistivity of each liquid alloy decreased non-linearly with temperature increasing above their liquidus (T _L) until reaching critical temperature, at which the resistivity–temperature coefficients dρ/dT–T converts from negative into positive. The phenomena of liquid phase transformation might relate with the dissociation of covalent bonds, chemical orders and associations in Sb–Zn melts.     

Electrical resistivity of liquid Bi–Sb alloys

The electrical resistivities of liquid Bi–Sb alloys have been measured by DC four-probe method within Bi-rich composition through a wide temperature range. The distinct anomaly of a hump shape was observed on resistivity–temperature (ρndash;T) curves for liquid Bi–Sb alloys on heating at the relatively high temperatures. These anomalies have revealed the temperature-induced liquid–liquid phase transition in Bi–Sb melts. The DSC results for BiSb20wt% alloy further prove the existence of liquid–liquid transition. Measuring the ρ–T curves first on heating and then on cooling we have found that on cooling the ρ–T curve remained linear. It means that the postulated liquid–liquid transition may be irreversible.     

Core-softened potentials,multiple liquid–liquid critical points,and density anomaly regions: An exact solution

The pressure versus temperature phase diagram of a system of particles interacting through a multiscale shoulder-like potential is exactly computed in one dimension. The N-shoulder potential exhibits N density anomaly regions in the phase diagram if the length scales can be connected by a convex curve. The result is analyzed in terms of the convexity of the Gibbs free energy.     

Modification of glass transition and liquid—liquid transition in PMMA doped with fluorescent dyes

PMMA doped with fluorescent dyes presents important modifications of thermally stimulated current spectra at high temperature. Glass and liquid-liquid transitions are no longer resolved and only one intense peak appears at 127°C. This peak cannot be resolved by the thermal sampling method. It has an Arrhenius behavior, and the plot of τ(1/T) shows the existence of a compensation phenomenon with a characteristic temperature which does not depend on the dye concentration. The modification is induced even if the dye concentration is as weak as some 10s of ppm. Thus it cannot be considered as a plasticization effect.     

Concentration dependence of thermodynamic,transport and surface properties in Ag–Cu liquid alloys

Thermodynamic, transport and surface properties of Ag–Cu liquid alloys have been investigated on the basis of a simple statistical model. The free energy of mixing, heat of mixing and entropy of mixing have been computed to understand the thermodynamic properties of Ag–Cu alloys in liquid state at 1,423 K. The concentration–concentration fluctuations in the long wavelength limit and the chemical short range order parameter have been determined to comprehend the microscopic and structural information of the alloy. The viscosity and surface tension of the alloy have been evaluated to analyze the transport and surface properties. The theoretical analysis reveals that the energy parameter is temperature dependent, and that Ag–Cu liquid alloy is a weakly interacting-phase separating system.     

Revisit of rotational motion of axial poly-atomics by molecular dynamics simulation and group theory: liquid benzene at 298, 365, 432, 498, 562 K

The paper reports quantitative physical aspects of the overall rotational motion of axially symmetric poly-atomics on the example of liquid benzene at five temperatures between 298 and 562?K on the basis of the group-theoretical approach proposed by B. Keller and F. Kneub?hl in Helv. Phys. Acta 45,1127 (1972), with a database generated by molecular dynamics simulation of ensemble-averaged orientational fluctuations. It is shown that (i) benzene rotates by a Markov process around an average, in-frame moving rotation axis and (ii) that numerous reported orientational correlation results that claim to display the rotational motion of the molecule, are nevertheless now to be considered irrelevant to their promulgated aim because their analyses omitted to account for the simultaneous inclination motion, as well as its particular time scale, of the average direction of the singular average molecular rotation axis of a benzene molecule.     

Prediction of the solid–liquid–liquid equilibria of linear and branched semi-crystalline poly-ethylene in solutions of diphenyl ether by Lattice Cluster Theory

ABSTRACT

Recently, Lattice Cluster Theory has been applied to predict liquid–liquid equilibria and solid–liquid equilibria of low and high molecular weight mixtures taking into account the molecular architecture and the nature of crystallinity of the respective component. Herein, an LCT-based theory is applied to calculate solid–liquid–liquid equilibrium of a polyethylene + diphenyl ether system, depending on branching and degree of crystallinity of the polymeric component. Understanding the role that branching number, branching type and degree of polymer crystallinity play in the behaviour of triple and triple critical points is focused on. Insight is given here into constitution and properties of triple and triple critical points in binary polymer solvent systems depending on the molecular architecture of both components, polymer and solvent respectively, and the semi-crystalline nature of the polymer.     

Study of solid–liquid interface in water dispersions of microcrystalline celluloses

Interaction on the solid–liquid surface in dispersions of microcrystalline cellulose (MCC) with various particle sizes has been studied by means of rheological methods. It was shown that the MCC dispersions possess shear-thinning rheological properties. An inversely proportional relationship between the average particle size of the MCC particles and the viscosity of the dispersions was discovered. This phenomenon is explained by the decrease of water mobility with increase in the specific surface of the MCC particles. Irreversible closing of the MCC pores reduces the viscosity of water dispersions. Addition of some water-soluble polymers leads to a considerable increase in viscosity due to formation of macromolecular net composed of solid particles.     

Post-deposition dynamics of multiple cluster aggregation on liquid surfaces

A comprehensive simulation model---deposition, diffusion, rotation and aggregation---is presented to demonstrate the post-deposition phenomena of multiple cluster growth on liquid surfaces, such as post-deposition nucleation, post-deposition growth and post-deposition coalescence. Emphasis is placed on the relaxations of monomer density, dimer density and cluster density as well as combined cluster-plus-monomer density with time after deposition ending. It is shown that post-deposition coalescence largely takes place after deposition due to the large mobility of clusters on liquid surfaces, while the post-deposition nucleation is only possible before the saturation cluster density is reached at the end of the deposition. The deposition flux and the moment of deposition ending play important roles in the post-deposition dynamics.     

Gas—liquid interfaces of room temperature ionic liquids

The structure of the gas-liquid surface of dimethylimidazolium chloride has been studied using atomistic simulation. We find that there is a region of enhanced density immediately below the interface in which the cations are oriented with their planes perpendicular to the surface and their dipoles in the surface plane. There is negligible segregation of cations and anions. The temperature dependence of the surface tension is predicted to be anomalously low or be reversed in sign. The vapour-liquid interfaces between mixtures of water and dimethylimidazolium chloride show similar regions of enhanced density and preferential orientation of the cations. Water molecules also show preferential orientation in the interface region and are preferentially adsorbed on the vapour side of the interface. The surface tension decreases with increase in the mole fraction of water.     

Modulation of charge transfer rate in (N,N′-dimethylamino)benzonitrile liquid solutions

We studied the properties of the emission, absorption and excitation of dual fluorescence of (N,N′?dimethylamino)benzonitrile in a polar aprotic solvent acetonitrile under selective irradiation of solutions by light with different energies of quanta to elucidate mechanisms of dual fluorescence arising in this solvent at different temperatures in the range 274–313 K. In all cases, dual fluorescence of the solute in acetonitrile was observed, which is caused by emission from locally excited Franck-Condon and charge-transfer states. A change in the energy of excitation quanta has a weak effect on the position of the fluorescence bands; however, the intensity ratio between the bands noticeably changes in favour of the intensity of the long-wavelength band at excitation in the range of the long-wavelength absorption band. An interesting and unusual fact is that solution heating is accompanied by essential growth of quantum yield of dual fluorescence at all wavelengths of the excitation. To explain the observed effects, the same dependences were measured and analysed for DMABN in neutral solvent n-hexane in the same conditions. We involve also the data of quantum-mechanical calculations, which show that there is a considerable probability of occurrence in solutions of DMABN rotational isomers with differing orientation of the dimethylamino group with respect to the benzonitrile. In the excited state, these have different charge-transfer rates, resulting in a modulation in the intensity ratio of the observed fluorescence bands with change excitation energy quanta on the red wing of the absorption band, doi: 10.1134/S0030400X12050219.