High-pressure phase behaviour of the binary system {CO2 + cis-decalin} from (292.75 to 373.75) K

The phase behaviour of the {CO₂ (1) + cis-decalin (2)} binary system has been experimentally studied at temperatures ranging from (292.75 to 373.75) K. Saturation pressures, ranging from (15.9 to 490.5) bar, were obtained using a variable volume high-pressure cell by visual observation of phase transitions at constant overall composition. For this system, no literature data are available and the results obtained in this study reveal the occurrence of vapor–liquid, liquid–liquid, and vapor–liquid–liquid phase transitions in the investigated temperature range. A total of 133 experimental points are reported including bubble points, dew points, liquid–liquid phase equilibria, and coordinates of the three-phase line. The experimental data can be reasonably predicted by the PPR78 model in which the temperature-dependent binary interaction parameter is calculated by a group contribution method.     

Synthesis and crystal structure of the high-pressure iron borate α-FeB2O4

The high-pressure iron borate α-FeB₂O₄ was synthesized under high-pressure and high-temperature conditions in a Walker-type multianvil apparatus at 7.5 GPa and 1100 °C. The monoclinic iron borate crystallizes with eight formula units in the space group P2₁/c with the lattice parameters a=715.2(2), b=744.5(2), c=862.3(2) pm, and β=94.71(3)°. The compound is built up exclusively from corner-sharing BO₄-tetrahedra, isotypic to the monoclinic phases β-SrGa₂O₄, CaAl₂O₄-II, and CaGa₂O₄. Additionally, the structure is closely related to the orthorhombic compound BaFe₂O₄. The structure consists of layers of six-membered rings, which are interconnected to a three-dimensional network. The iron cations are coordinated by six and seven oxygen atoms. Next to synthesis and crystal structure of the new high-pressure borate, structural coherences to other structure types are discussed.     

Phase transitions of LiAlO2 at high pressure and high temperature

This work presents a comprehensive study on phase transitions in LiAlO₂ system at high pressures and temperatures (0.5-5.0 GPa and 300-1873 K, respectively), as well as the phase stability for polymeric phases of LiAlO₂ in the studied P-T space by X-ray diffraction (XRD). Besides the previously described polymorphic hexagonal α-phase, orthorhombic β-phase and tetragonal δ-phase, a possible new phase of LiAlO₂ was observed after the tetragonal γ-LiAlO₂ sample was treated at 5.0 GPa and 389 K. The stable regimes of these high-pressure phases were defined through the observation of coexistence points of the polymeric phases. Our results revealed that LiAlO₂ could experience structural phase transitions from γ-LiAlO₂ to its polymorphs at lower pressures and temperatures compared to the reported results. Hexagonal α-LiAlO₂ with highly (003) preferential orientation was prepared at 5.0 GPa and 1873 K.     

High-pressure vapor–liquid and vapor–liquid–liquid equilibria in the carbon dioxide + 1-heptanol system

Vapor–liquid equilibria (VLE) and vapor–liquid–liquid equilibria (VLLE) data for the carbon dioxide + 1-heptanol system were measured at 293.15, 303.15, 313.15, 333.15 and 353.15 K. Phase behavior measurements were made in a high-pressure visual cell with variable volume, based on the static-analytic method. The pressure range under investigation was between 0.58 and 14.02 MPa. The Soave–Redlich–Kwong (SRK)-EOS coupled with Huron–Vidal (HV) mixing rules and a reduced UNIQUAC model, was used in a semi-predictive approach, in order to represent the complex phase behavior (critical curve, LLV line, isothermal VLE, LLE, and VLLE) of the system. The topology of phase behavior is qualitatively correct predicted.     

Crosslinking, thermal properties and relaxation behaviour of polyisoprene under high-pressure

The transient hot-wire method has been used to measure the thermal conductivity κ and heat capacity per unit volume ρc_p of untreated (virgin) and crosslinked cis-1,4-poly(isoprene) (PI) in the temperature range 160-513 K for pressures p up to 0.75 GPa. The results show that the crosslinking rate of the polymer chains becomes significant at ∼513 K on isobaric heating at 0.5 GPa changing PI into an elastomeric state within 4 h without the use of crosslinking agents. The crosslinked PI and untreated PI have about the same κ = 0.145 Wm⁻¹ K⁻¹ and c_p = 1.81 kJ kg⁻¹ K⁻¹ at 295 K and 20 MPa, but different relaxation behaviours. Two relaxation processes, corresponding to the segmental and normal modes, could be observed in both PI and crosslinked PI but these have a larger distribution of relaxation times and become arrested at higher temperatures (∼10 K) in the latter case. The arrest temperature for the segmental relaxation of untreated and crosslinked PI, for a relaxation time of ∼1 s, are described well by the empirical relations: T(p) = 209.4 (1 + 4.02 p)^0.31 and T(p) = 221.3 (1 + 2.33 p)^0.40 (p in GPa and T in K), respectively, which thus also reflects the pressure variations of the glass transition temperatures.     

Ultrastructural immunogold localization of major sperm protein (MSP) in spermatogenic cells of the nematode Acrobeles complexus (Nematoda,Rhabditida)

The nematode spermatozoa represent a highly modified (aberrant) type of male gametes that lack a flagellum but for which the process of spermatogenesis culminates in the production of a crawling spermatozoon on the basis of the cytoskeletal component known as “major sperm protein”, or MSP. MSP is also known as an important hormone triggering oocyte maturation and ovulation in the model nematode Caenorhabditis elegans, where this protein was first identified. However, direct evidence of MSP localization and of its fate in nematode spermatogenic cells is rare. In this study, the spermatogenesis and sperm structure in the rhabditid nematode Acrobeles complexus (Rhabditida: Tylenchina: Cephalobomorpha: Cephaloboidea: Cephalobidae) has been examined with electron microscopy. Morphological observations were followed by high-pressure freezing and freeze-substitution fixation which allows post-embedding immunogold localization of MSP in all stages of sperm development using antibodies raised for MSP of C. elegans. In spermatocytes, synthetic activity results in the development of specific cellular components, fibrous bodies (FB) and membranous organelles (MO), which appear as FB-MO complexes where the filamentous matter of FB has been MSP-labeled. The spermatids subdivide into a residual body with superfluous cytoplasm, and a main cell body which contains nucleus, mitochondria and FB-MO complexes. These complexes dissociate into individual components, MO and FB, with the MSP being localized in FB. Immature spermatozoa from testes are opaque cells where a centrally located nucleus is surrounded by mitochondria, MO and FB clustered together, the MSP still being localized only in FB. Cytoplasm of mature spermatozoa from spermatheca is segregated into external pseudopods lacking organelles and a central cluster of mitochondria with intact MO surrounding the central nucleus. The FB ultimately disappear, and the MSP labeling becomes concentrated in the filamentous content of pseudopods and cytoplasm of the main cell body. Although the spermatogenesis and sperm structure of A. complexus is similar to that of many other rhabditid nematodes, their intact MO makes the morphology of the mature spermatozoa distinct from the “rhabditid pattern” and may be considered as a synapomorphy. The MSP localization in spermatogenic cells of A. complexus also follows the “rhabditid pattern” described in C. elegans and Ascaris spp. Our results and techniques of MSP labeling of A. complexus spermatogeneous cells reveal new possibilities to elucidate different research questions on MSP localization in nematodes related to C. elegans. Furthermore, the laboratory-cultured A. complexus strains can be used as a new and fascinating model to study MO and MSP functions in nematode reproduction.     

High pressure Raman spectra of DL-lysine hydrochloride

DL-lysine hydrochloride crystals were studied by Raman spectroscopy under hydrostatic pressure using a diamond anvil cell from ambient pressure up to 9.8 GPa in the spectral range from 1150 to 40 cm⁻¹. Changes in the Raman spectrum were observed in all spectral regions analyzed. In particular, modifications in the lattice modes indicate that the crystal undergoes a phase transition. The classification of the vibrational modes, the behavior of their band wavenumber as a function of the pressure and the reversibility of the phase transitions are also discussed.     

Pressure and temperature variation of the depolarized light scattering spectra of the fragile glass-former liquid salol

The pressure and temperature dependences of the depolarized light scattering spectra of salol have been measured at isobaric condition P = 1 bar for T between 328 and 393 K, and at isothermal condition T = 343 K for P between 1 and 625 bar, i.e. outside the metastable liquid region. The experimental results for both the α- and β-relaxations can be well described by the Mode Coupling Theory. The independence of the power-law parameters a, and consequently b and γ, from the thermodynamic variables T and P is demonstrated.The critical temperature T _c at 1 bar and the critical pressure P _c at T = 343 K have been determined from the normal liquid state. Received 2 May 2000     

In situ Hochdruck- und Hochtemperatur-Untersuchungen an Siliciumsuboxiden mittels energiedispersiver Röntgenbeugung

In situ High-Pressure- and High-Temperature Studies of Siliconsuboxides via Energy Dispersive X-ray Diffraction The amorphous silicon compounds Si₂O₃, H₂Si₂O₄, HSiO_1.5, and SiO have been investigated under High-Pressure- and High-Temperature conditions in situ via energy dispersive X-ray diffraction with synchrotron radiation. The studies have been performed using the Multi Anvil High Pressure Device MAX-80, at HASYLAB, DESY-Hamburg, Germany. Except for SiO, at a pre-set pressure of 45 kbars the formation of Coesite was observed at heating. Commercially available SiO did not crystallize in any way, indicating that it seems not to consist of silicon(II)-oxide, but is in fact a mixture of silicon and silicondioxide, disproportionated on an atomic scale.     

Structure conditioned velocity statistics in a high pressure swirl flame

A piloted, partially premixed, liquid-fueled swirl burner is operated at high pressure (1 MPa). High-speed (6 KHz) stereoscopic PIV is used to investigate the characteristics of the stagnation line separating the pilot jet and the central recirculation zone (CRZ) with varying pilot-main ratio and global equivalence ratio. The mean curvature of the stagnation line displayed a large spatial scale pattern that was present for all operating conditions. All three components of velocity, in-plane shear, and swirling strength are conditioned upon the instantaneous stagnation line. Mean distributions of the velocity normal to the stagnation line show that velocity is oriented towards the CRZ when the stagnation line is found nearer the centerline of the combustor. The conditioned out-of-plane velocity (w) shows a distinct concentration of large mean and fluctuation RMS values towards the center of the measurement domain. Varying fuel flow does not significantly change this spatial structure, only the magnitudes of the w statistics. The in-plane shear stress was the largest for the pilot biased condition as a stronger shear layer develops. For the leanest flame, large fluctuation RMS values of shear stress were confined to a region where the pilot jet begins to interact more heavily with the main jet. Operating with less pilot fuel flow enhanced the mean conditional swirling strength indicating that the pilot shear layer was shedding more intense eddies. Disregarding spatial relations, a scatter plot of w, shear stress, and swirling strength displayed trends between the variables. The largest swirling strength values coincide with highest magnitude shear stresses and the widest range of w. These conditioned statistics highlight how certain aspects of the combustor flow field are invariant with fuel distribution. This is desirable for aeropropulsive combustors that must maintain stable ignition from a range of conditions from landing/take-off to cruise.