Infrared Spectra of Crystalline,Glassy and Liquid Methanol at High Pressures

Abstract

Mid-infrared spectra in the range 400–1800 cm^?1 of methanol samples in diamond anvil cells at ambient temperature and pressures up to 11 GPa are reported. The freezing pressure is confirmed to be 3.6 GPa, and the spectra of the resulting metastable glass are very similar to those of the liquid. When maintained at high pressure, the glass spontaneously transforms to an ordered crystalline phase which is stable over the range 3.6 to 11 GPa. Small changes in peak wavenumbers for 14 internal modes as a function of pressure are observed, indicating that distortion of the molecules is minimal. A slight decrease for the C-O-H bending mode is attributed to charge transfer from the molecular 0-H bond to the strengthening intermolecular hydrogen bond.     

Comparison of the Raman pressure shift and the Raman temperature shift of benzene and diamond with the ruby soale

Abstract

In order to serve as substitute for the pressure ruby scale at high temperature, the breathing mode of bemsens (990 cm^?1) and the first order Raman mode of diamond (1333 cm^?1) have been studied as a function of pressure and temperature in the range of 0–15 GPa and 25–400°C. The diamond and bensene Raman frequency shifts are shoft to be of valuable use as a pressure scale at high temperature. A further advantage of bensene is to remain a suitable pressure transmitting medium up to 350°C and 15 GP.     

Pressure induced metallization of the antiferromagnetic-insulator CoI

Abstract

High pressure electrical measurements were conducted in the antiferromagnetic insulator CoI, using a miniature Diamond Anvil Cell (DAC). The existence of a Mott Transition predicted from high pressure ¹²⁹I Mgssbauer Spectroscopy (MS)¹ has been verified. At about 8 GPa the system becomes metal1ic as evidenced by the temperature behavior of the conductivity. The conductivity at room temperature, however, still increases with increasing pressure, leveling off at 11 GPa. The metallic behavior in the 8 -11 GPa is explained by coexistence of metallic and insulating clusters via a percolating process. Above 11 GPa the material is completely metallic. This mechanism is consistent with the MS findings.     

Phase transitions in poly(ethylene oxide) and polystyrene at high pressure

Abstract

The temperature and enthalpy of melting for poly(ethy1ene oxide) have, for the first time, been studied as a fuction of pressure up to 1 GPa by means of differential scanning calorimetry. The initial increase of the temperature of melting with increasing pressure is 64 K/GPa, whereas the enthalpy decreases by 40% in the 1 GPa pressure range. Using Clausius-Clapeyrons equation the volume change on melting is estimated to be 1.5 cm³/mol. The glass transition temperature T_g for polystyrene has also been studied by the same technique for pressures up to 0.1 GPa. The measurements show that T_g increases with increasing pressure by 250 K/GPa.     

SrB4O7:Sm2+: an optical sensor reflecting non-hydrostatic pressure at high-temperature and/or high pressure in a diamond anvil cell

A systematic investigation on the fluorescent spectra of SrB₄O₇:Sm²⁺ was performed in detail at high-temperature up to 623?K and/or high pressure up to 23.2?GPa with different pressure-transmitting media (PTMs), respectively. Combined with experiment data of previous research, the change of the ⁷D₀–⁵F₀ line (0–0 line) full width at half maximum (FWHM) of SrB₄O₇:Sm²⁺ under different pressure environments was specifically discussed. The results indicate that the FWHM of 0–0 line is sensitive to the non-hydrostatic pressure environment in 2-propanol, and methanol and ethanol mixture (ME) PTMs at ambient temperature. The first-order and the second-order derivation of the temperature dependence of 0–0 line FWHM at ambient pressure are 1.48(±0.21)?×?10^?4?nm/K and 9.63(±0.63)?×?10^?7?nm²/K² below 623?K. The 0–0 line FWHM is also sensitive to the non-hydrostatic pressure environment in ME at high-temperature and high pressure simultaneous, the non-hydrostatic transition pressures are 9.6?GPa at 323?K, 11.0?GPa at 373?K, 14.4?GPa at 423?K, respectively. SrB₄O₇:Sm²⁺ is recommended as an optical sensor to reflect the change of pressure environment in liquid media at high-temperature and/or high pressure.     

Thermal equation of state of goethite (α-FeOOH)

ABSTRACT

The pressure–volume–temperature (P–V–T) equation of state (EoS) of natural goethite (α-FeOOH) has been determined by an X-ray diffraction study using synchrotron radiation. Fitting the volume data to the third-order Birch–Murnaghan EoS yielded an isothermal bulk modulus, B₀ of 85.9(15)?GPa, and a pressure derivative of the bulk modulus, B′, of 12.6(8). The temperature derivative of the bulk modulus, (?B/?T)_P, was –0.022(9)?GPa?K^?1. The thermal expansion coefficient α₀ was determined to be 4.0(5)?×?10^?5?K^?1.     

High-precision measurements of the compressibility and the electrical resistivity of bulk <Emphasis Type="Italic">g</Emphasis>-As<Subscript>2</Subscript>Te<Subscript>3</Subscript> glasses at a hydrostatic pressure up to 8.5 GPa

High-precision studies of the volume and the electrical resistivity of g-As₂Te₃ glasses at a high hydrostatic pressure up to 8.5 GPa at room temperature are performed. The glasses exhibit elastic behavior in compression only at a pressure up to 1 GPa, and a diffuse structural transformation and inelastic density relaxation (logarithmic in time) begin at higher pressures. When the pressure increases further, the relaxation rate passes through a sharp maximum at 2.5 GPa, which is accompanied by softening the relaxing bulk modulus, and then decreases, being noticeable up to the maximum pressure. When pressure is relieved, an unusual inflection point is observed in the baric dependence of the bulk modulus near 4 GPa. The polyamorphic transformation is only partly reversible and the residual densification after pressure release is 2%. In compression, the electrical resistivity of the g-As₂Te₃ glasses decreases exponentially with increasing pressure (at a pressure up to 2 GPa); then, it decreases faster by almost three orders of magnitude in the pressure range 2–3.5 GPa. At a pressure of 5 GPa, the electrical resistivity reaches 10^–3 Ω cm, which is characteristic of a metallic state; this resistivity continues to decrease with increasing pressure and reaches 1.7 × 10^–4 Ω cm at 8.1 GPa. The reverse metal–semiconductor transition occurs at a pressure of 3 GPa when pressure is relieved. When the pressure is decreased to atmospheric pressure, the electrical resistivity of the glasses is below the initial pressure by two–three orders of magnitude. Under normal conditions, both the volume and the electrical resistivity relax to quasi-equilibrium values in several months. Comparative structural and Raman spectroscopy investigations demonstrate that the glasses subjected to high pressure have the maximum chemical order. The glasses with a higher order have a lower electrical resistivity. The polyamorphism in the As₂Te₃ glasses is caused by both structural changes and chemical ordering. The g-As₂Te₃ compound is the first example of glasses, where the reversible metallization under pressure has been studied under hydrostatic conditions.     

Xanes and raman spectroscopy under pressure of bromobenzene

Abstract

The behaviour of bromobenzene (BBe) compressed in a diamond anvill cell up to 30 GPa was studied by XANES and Raman spectroscopy. The liquid-solid transition and a solid-solid transition were observed at 0.9 GPa and 9 GPa respectively. Above 24 GPa, an irreversible transformation occurs to a solid orange-yellow compound which can be recovered at zero pressure. The polymerization mechanism, in connection with the occurence of Br-bonded Sp² and Sp³ carbons in the solid compound, is discussed.     

White-beam X-ray diffraction and radiography studies on high-boron-containing borosilicate glass at high pressures

ABSTRACT

Multi-angle energy-dispersive X-ray diffraction studies and white-beam X-ray radiography were conducted with a cylindrically shaped (1?mm diameter and 0.7?mm high) high-boron-content borosilicate glass sample (17.6% B₂O₃) to a pressure of 13.7?GPa using a Paris-Edinburgh (PE) press at Beamline 16-BM-B, HPCAT of the Advanced Photon Source. The measured structure factor S(q) to large q?=?19 Å^?1 is used to determine information about the internuclear bond distances between various species of atoms within the glass sample. Sample pressure was determined with gold as a pressure standard. The sample height as measured by radiography showed an overall uniaxial compression of 22.5% at 13.7?GPa with 10.6% permanent compaction after decompression to ambient conditions. The reduced pair distribution function G(r) was extracted and Si–O, O–O and Si–Si bond distances were measured as a function of pressure. Raman spectroscopy of the pressure recovered sample as compared to starting material showed blue-shift and changes in intensity and widths of Raman bands associated with silicate and four-coordinated boron.     

Pressure induced phase transition in n-type InP at low temperature studied by photoluminescence

Abstract

Low temperature (5 K) photoluminescence of n-type InP has been studied in the 0–12 GPa range. The luminescence band energy follows the pressure dependence of the band gap, provided effective mass variations are taken into account. No evidence of a direct to indirect gap crossover has been observed up to the phase transition pressure (10.3 GPa). The phase transition is uncompleted at 12 GPa     

Phase transitions and equations of state at multimegabar pressures

Abstract

Review of phase transitions and equations of state at multimegabar pressures (100–300 GPa) is presented. Energy dispersive x-ray diffraction techniques in conjunction with synchrotron radiation sources are used. Besides several transition metals, Pt to 282 GPa, Re to 251 GPa, W to 209 GPa, and Fe to 255 GPa, the special focus is on Group IVA elements and isoelectronic III-V compounds. At high pressure, the isoelectronic materials are isostructural and exhibit similar equation of state.     

Long time relaxation effect of liquid castor oil under high pressure conditions

Abstract

The relaxation times of Liquid castor oil have been investigated by observing the scattered light of a He-Ne gas laser during the slow or rapid application of pressure up to 0.7 GPa at 293 K. For the application of pressure above 0.36 GPa the strong increase of the scattered light intensity approximately by a factor of 10² has been observed 12 hours after an application of pressure. This pressure effect is also observed for subsequent pressure cycles, i.e., the pressure effect is reversible. Experimental results are interpreted according to a model of a liquid of long rod molecules.     

Calibration of the R ruby fluorescence lines in the pressure range [0-1 GPa] and the temperature range [250-300 K]

Abstract

The pressure range [&1 GPa] and the temperature range [250–300 K] are commonly used in many science fields like biology, agro-chemistry, pharmacology, or geology. In this paper, the calibration of the ruby R lines of fluorescence is performed in these pressure and temperature ranges, using the melting curve of pure water. The linear shifts of ruby peaks are equal to ?0.140cm^?1/K and ?0.768cm^?1/kbar with R₁, and to ?0.137cm^?1/K and ?0.779 cm^?1/kbar with R₂. The accuracy of pressure measurements can be as good as ± 10MPa if the temperature is known with ±0.5 K. Such a precision is achieved if: (1) the position of each peak is determined using an inversion method; (2) daily shifts of the spectrometer are corrected before each acquisition; (3) peak positions of each ruby are known at ambient pressure and temperature.     

In-situ X-ray diffraction study on β-CrOOH at high pressure and high-temperature

ABSTRACT

High pressure hydrous phases with distorted rutile-type structure have attracted much interest as potential water reservoirs in the Earth’s mantle. An in-situ X-ray diffraction study of β-CrOOH was performed at high pressures of up to 6.2?GPa and high-temperatures of up to 700?K in order to clarify the temperature effect on compression behaviors of β-CrOOH. The P-V-T data fitted to a Birch–Murnaghan equation of state yielded the following results: isothermal bulk modulus K_T0?=?191(4)?GPa, temperature derivative (?K_T/?T)_P?=??0.04(2)?GPa?K^?1, and volumetric thermal expansion coefficient α?=?3.3(2)?×?10^?5?K^?1. In this study, at 300?K, the a-axis became less compressible at pressures above 1–2?GPa. We found that the pressure where the slopes of a/b and a/c ratios turned positive increased with temperature. This is the first experimental study indicating the temperature dependence of the change in the axial compressibility in distorted rutile-type M³⁺OOH.     

Distribution of light alkanes in the reaction of graphite hydrogenation at pressure of 0.1–7.8 GPa and temperatures of 1000–1350°C

ABSTRACT

We studied the effect of pressure and temperature on the hydrocarbon (HC) chain length distribution and total amount of HCs in the reaction of direct graphite hydrogenation at pressures of 0.1–7.8?GPa and temperatures of 1000–1350°C. An increase in pressure was found to lead both to an increase in the absolute yield of HCs due to direct graphite hydrogenation and to chain elongation of HC products. Light alkanes predominate among HCs in the entire studied range of P–T parameters. However, their concentration in quenched fluids increases as pressure is elevated, from less than 10?rel.% at 0.1?GPa to more than 40–50?rel.% at P?≥?3.8?GPa. Methane is actually the only light alkane among reaction products at 0.1?GPa and 1000°C, while it is a minor component at 7.8?GPa and 1350°C. The most stable alkane at pressures above 3.8?GPa is ethane (C₂H₆).     

High hydrostatic pressure ESR manostats

Abstract

Two high pressure X-band ESR resonators for sensitive measurements are described. Both systems have 100 kHz internal modulation coils and can cooperate with any standard ESR spectrometer. These cavities operate in two different temperature and pressure ranges: 77–400 K, up to 0.8 GPa and liquid helium temperature range, up to 1 GPa, respectively. Additionally, the cavity operating in the 77–400 K temperature range enables Photo-ESR measurements to be carried out.     

High-pressure X-ray diffraction study of the δ-phase in the uranium-neptunium binary system

Abstract

High pressure X-ray diffraction studies were performed at room temperature on a uranium-neptunium binary alloy (U_{0, 40} Np_0.60) using a diamond anvil cell in an energy dispersive facility. The sample maintained its simple cubic phase up to 62 GPa (highest pressure reached in This experiment). The bulk modulus and its pressure derivative were determined to be B₀ = 82 (2) GPa and B₀′ = 9.4 (1.3), from the experimental data in the pressure range 0–20 GPa. The present results are compared with those obtained by the same techniques used for uranium and neptunium.     

Pressure dependence of crystal structure and molecular packing in anthracene

Anthracene molecular crystal has been investigated up to a pressure of 10.5 GPa at room temperature using variable shape variable size Monte Carlo simulations in an isothermal–isobaric ensemble. We have reported various structural quantities, such as cell parameters and unit cell volume, as a function of pressure and compared them with the experimental results [J. Chem. Phys. 119, 1078 (2003)]. The pressure dependence of angles θ, δ and χ which describe the relative packing of molecules in the crystal has been calculated. We report that anthracene molecular crystal does not exhibit any first order phase transition up to a pressure of 10.5 GPa which is consistent with the experimental observations by Oehzelt et al. [Phys. Rev. B 66, 174104 (2002)]. The calculated equation of state (EOS) has been fitted to a Murnaghan-type EOS with good agreement. The calculated bulk modulus and the pressure derivative of bulk modulus are 8.2 GPa and 8.9 respectively which are in agreement with the experimentally calculated values.     

High pressure study of the 2D polymeric phase of C60 by means of raman spectroscopy

Abstract

The effect of high hydrostatic pressure, up to 12GPa, on the intramolecular phonon frequencies and the material stability of the two-dimensional tetragonal Cm polymer has been studied by means of Raman spectroscopy in the spectral range of the radial intramolecular modes (200-800cm^?1). A number of new Raman modes appear in the spectrum for pressures ～ 1.4 and ～ 5.0 GPa. The pressure coefficients for the majority of the phonon modes exhibit changes to lower values at P=4.0 GPa, which may be related to a structural modification of the 2D polymer to a more isotropic phase. The peculiarities observed in the Raman spectra are reversible and the material is stable in the pressure region investigated.     

High-pressure phase transitions in UP1-xSx

Abstract

High-pressure X-ray diffraction using synchrotron radiation has been performed on UP_1-x -S_x (X=0.1; 0.25; 0.4) up to 53 GPa UP_1-x S_x is a solid solution with a B1 (NaCl) structure. For all compositions a second order phase transition is observed around 10 GPa to a distorted B1 structure of rhombohedral symmetry. For UP_1-x S_x with x 0.25 a second phase transition is observed, which takes place in the region of 35 GPa This phase transition occurs when the nearest U-U distance reaches the Hill limit of 330–340 pm. The high-pressure phase seems to have orthorhombic or even monoclinic symmetry. It has some similarities to the high pressure phase of UP. UP^1-x S_x 4 shows only weak indications for an additional phase at 53 GPa. In conclusion, we observe that the second phase transition and the bulk modulus B, in UP shift to higher pressure, when phosphorus is replaced by sulfur.