Benzophenone glass, supercooled liquid, and crystals: elastic properties and phase transitions.

The elastic properties of glass α- and ß-modifications of benzophenone (C6H5)2CO are determined for the first time by the ultrasonic method at high pressures up to 1 GPa and in the temperature range of 77 K< T < 293 K. Four states of benzophenone are experimentally observed in the investigated temperature range of 77-293 K: glass, supercooled liquid, and α- and ß-crystalline phases. The boundaries of phase transitions during isobaric heating are determined. The bulk and shear moduli B and G, Poisson's ratio σ, and density ρ are calculated. Glassy benzophenone has much lower elastic moduli than the α-modification at 77 K (the shear modulus G of glass is about half the value for the crystal). The crystalline α-modification demonstrates a strong softening of both moduli with an increase in the temperature in the range of 77-293 K. Heating of glass leads to the formation of a very viscous supercooled liquid, which crystallizes into the metastable ß-modification. A further increase in the temperature leads to a monotropic phase transition ß â†’ α.

Ultrasonic study of 1-X adamantane (X = F, Cl, Br) compounds at high pressure and at order-disorder transitions.

We present an ultrasonic study of the elastic properties of 1-X adamantane (X = F, Cl, Br) during order-disorder and order-quasi-order transitions at various temperatures (77-305 K) and high pressures (up to 1 GPa). On the basis of our ultrasonic experiments, we studied for the first time the high-temperature (HT) Fm3m, medium-temperature (MT) P42/nmc, and low-temperature (LT) P421c phases of 1-fluoroadamantane at high pressures. The elastic properties of these phases at pressures up to 1 GPa at T = 293 and 77 K, as well as at isobaric heating from 77 to 293 K, have been determined. The boundaries of the HT → MT → LT phase transitions have been evaluated, which makes it possible to extend the phase diagram of 1-fluoroadamantane to higher pressures. We have confirmed that the MT → LT transition is a second-order phase transition because it is not accompanied by volume jumps but is manifested in anomalies of the elastic properties and ultrasound transmission both in high-pressure experiments and under isobaric heating. The comparison of the elastic properties of 1-X adamantanes (X = H, F, Cl, Br) has indicated a monotonic dependence at low pressures: the bulk modulus is the highest for adamantane and decreases with an increase of the atomic number of the halogen substitute (from fluorine to bromine).

Phase transitions in 1-bromoadamantane compared to 1-chloroadamantane: similarities and unique features.

The elastic properties of 1-chloroadamantane and 1-Bromoadamantane in order-disorder and order-quasi-order phase transitions at temperatures in the range of 77-305 K and high pressures up to 1.1 GPa are studied by the ultrasonic method. The elastic moduli of halogenated adamantanes clearly indicate these transitions, demonstrating high capabilities of the ultrasonic method. Our ultrasonic studies have detected for the first time the λ-anomaly of the elastic properties and, thereby, have confirmed that the phase transition from the orientationally ordered to quasi-ordered phase (M → O) in 1-bromoadamantane is a weak first-order phase transition having some properties of a second-order phase transition. The pressure derivatives of the elastic moduli of 1-chloroadamantane and 1-bromoadamantane in the orientationally ordered phase at 77 K are dB/dP ≈ 8, which allows using the Lennard-Jones potential to theoretically describe this phase.

Comparative study of the elastic properties of adamantane and 1-chloroadamantane at high pressure and different temperatures and at order-disorder transitions.

We present a comparative ultrasonic study of the elastic properties of adamantane and 1-chloroadamantane at high pressure (up to 1.4 GPa) and different temperatures (77-293 K) and at order-disorder transitions. The ultrasonic method provides complementary pictures of the order-disorder transitions in diamondoids under pressure. The equation of state of adamantane and 1-chloroadamantane was determined up to 1.4 GPa from ultrasonic measurements of bulk modulus and is in good accordance with the previous equations developed from volumetric data. We measured the bulk and shear moduli and Poisson's ratio of adamantane and 1-chloroadamantane up to 1.4 GPa. The behaviors of elastic moduli are different for adamantane and 1-chloroadamantane. This indicates that the substitution of one hydrogen atom for chlorine significantly reduces both elastic moduli, particularly the shear modulus (≈30%). Although the pressure dependences of the bulk modulus B are almost linear and its pressure derivatives for adamantane and 1-chloroadamantane are close to each other (B' ≈ 10-12), a jump is hardly observed on the pressure dependence B(P) for adamantane at the transition from the plastic to ordered phase, whereas the pressure dependence of the bulk modulus for 1-chloroadamantane exhibits a jump of almost 17%. The experimental dependences of the bulk modulus and relative changes in the volume for both materials clearly demonstrate that the compressibility of 1-chloroadamantane is much higher for both phases. The Poisson coefficient calculated from our experimental data is larger for 1-chloroadamantane, having lower both bulk and shear moduli.

Vivid Manifestation of Nonergodicity in Glassy Propylene Carbonate at High Pressures.

As glasses are nonergodic systems, their properties should depend not only on external macroparameters, such as P and T, but also on the time of observation and thermobaric history. In this work, comparative ultrasonic studies of two groups of molecular propylene carbonate glasses obtained by quenching from a liquid at pressures of 0.1 and 1 GPa have been performed. Although the difference in the densities of the different groups of glasses is small (3-5%), they have significantly different elastic properties: the difference in the respective bulk moduli is 10-20%, and the difference in the respective shear moduli is 35-40% (!). This is due to the "closure of nanopores" in the glass obtained at 1 GPa. The pressure and temperature derivatives of the elastic moduli for these groups of glasses are also noticeably different. The glass-transition temperatures of glasses from different groups differ by 3-4 K. The character of absorption of ultrasound waves near the glass-transition temperature also differs for different groups of glasses. The differences in the behaviors of these groups of glasses disappear gradually above the glass-transition temperature, in the region of a liquid phase. Glasses with a wide diversity of physical properties can be obtained using various paths on the (T,P) diagram.