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At least 397 records · Page 22

X-Ray Diffraction and Electron Microscopy Studies of the Size Effects on Pressure-Induced Phase Transitions in CdS Nanocrystals

In recent years, investigations of the phase transition behavior of semiconducting nanoparticles under high pressure has attracted increasing attention due to their potential applications in sensors, electronics, and optics. However, current understanding of how the size of nanoparticles influences this pressure-dependent property is somewhat lacking. In particular, phase behaviors of semiconducting CdS nanoparticles under high pressure have not been extensively reported. Therefore, in this work, CdS nanoparticles of different sizes are used as a model system to investigate particle size effects on high-pressure-induced phase transition behaviors. In particular, 7.5, 10.6, and 39.7 nm spherical CdS nanoparticles are synthesized and subjected to controlled high pressures up to 15 GPa in a diamond anvil cell. Analysis of all three nanoparticles using in-situ synchrotron wide-angle X-ray scattering (WAXS) data shows that phase transitions from wurtzite to rocksalt occur at higher pressures than for bulk material. Bulk modulus calculations not only show that the wurtzite CdS nanomaterial is more compressible than rocksalt, but also that the compressibility of CdS nanoparticles depends on their particle size. Furthermore, sintering of spherical nanoparticles into nanorods was observed for the 7.5 nm CdS nanoparticles. Our results provide new insights into the fundamental properties of nanoparticles under high pressure that will inform designs of new nanomaterial structures for emerging applications.

Meng, Lingyao↗

Pressure-Induced Isostructural Phase Transition and Correlation of FeAs Coordination with the Superconducting Properties of 111-Type Na1-xFeAs

The effect of pressure on the crystalline structure and superconducting transition temperature (T{sub c}) of the 111-type Na{sub 1-x}FeAs system using in situ high-pressure synchrotron X-ray powder diffraction and diamond anvil cell techniques is studied. A pressure-induced tetragonal to tetragonal isostructural phase transition was found. The systematic evolution of the FeAs{sub 4} tetrahedron as a function of pressure based on Rietveld refinements on the powder X-ray diffraction patterns was obtained. The nonmonotonic T{sub c}(P) behavior of Na{sub 1-x}FeAs is found to correlate with the anomalies of the distance between the anion (As) and the iron layer as well as the bond angle of As-Fe-As for the two tetragonal phases. This behavior provides the key structural information in understanding the origin of the pressure dependence of T{sub c} for 111-type iron pnictide superconductors. A pressure-induced structural phase transition is also observed at 20 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm

Oxalyl chloride, (ClCO){sub 2}, has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO){sub 2} and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV/vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11 discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, {Phi}({lambda}), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO){sub 2} has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl){sub 2}+ hv{yields} ClCO*+ Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO*{yields} Cl + CO (3a), {yields} ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M {yields} Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO){sub 2}. {Phi}(193 nm) was found to be 2.07 {+-} 0.37 independent of bath gas pressure (25.8-105.7 Torr, N{sub 2}), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO){sub 2} is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 {+-} 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 {+-} 0.26 independent of bath gas pressure (15-70 Torr, N{sub 2}). {Phi}(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N{sub 2}). The low-pressure limit of the total Cl atom quantum yield, {Phi}{sub 0}(351 nm), was 2.05 {+-} 0.24. As part of this work, rate coefficients for the thermal decomposition of ClCO were measured between 253 and 298 K at total pressures between 13 and 128 Torr (He and N{sub 2} bath gases). The N{sub 2} bath gas results were combined with the data reported in Nicovich et al. [J. Chem. Phys. 92, 3539-3544 (1990)] to yield k{sub 4}(T, N{sub 2}) = (4.7 {+-} 0.7) Multiplication-Sign 10{sup -10} exp [-(2987 {+-} 16)/T] cm{sup 3} molecule{sup -1} s{sup -1}, while the He bath gas data fit yielded k{sub 4}(T, He) = (2.3 {+-} 2.1) Multiplication-Sign 10{sup -10} exp [-(2886 {+-} 218)/T] cm{sup 3} molecule{sup -1} s{sup -1}. The quoted uncertainties are at the 2{sigma} level from the precision of the fit. In addition, the room temperature rate coefficient for the Cl + ClNO reaction was measured in this work to be (1.03 {+-} 0.10) Multiplication-Sign 10{sup -10} cm{sup 3} molecule{sup -1} s{sup -1}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into Controls of Mineralogy and Pore Structure on the Density of Methane Adsorption Phase in Shales under Supercritical Conditions

With gradually increasing enhancing population and industrialization, exploitation of shale gas is enhancing in the world to satisfy the growing demand for energy worldwide. To exploit shale gas efficiently, accurate assessment of shale gas in place (GIP) is necessary for determining production strategies. Unlike free and dissolved gas, adsorbed gas contributes to the shale GIP up to 85% due to the well-developed surface area and micropores. Measured excess adsorption of methane (up to over 95% of subsurface shale gas) is often corrected to absolute adsorption to obtain the actual amount of adsorption under supercritical (or geological) conditions. During the correction, adsorption phase density (APD) is critical. However, the APD of subsurface shale gas and the effects of shale properties (e.g., mineralogy and pore structure) on APD remain poorly understood. A series of high-pressure methane adsorption isotherms (HPMAI) on Caney Shales were collected and analyzed in conjunction with other United States and Chinese shales from the literature at 35–125 °C and up to 15 MPa. Here, a three-layer Ono–Kondo (OK3) model is utilized to derive the temperature- and pressure-dependent APD coupling low-pressure nitrogen adsorption isotherms (LPNAI) and HPMAI. X-ray diffraction and organic geochemistry are combined to reveal the mineralogy. Brunauer–Emmett–Teller, Barrett–Joyner–Halenda, and Horvath–Kawazoe analyses via LPNAI are used to investigate the pore structures. Results show that APD increases with organic matter (OM) proxied by total organic carbon and decreases with clay minerals and the sum of quartz and feldspar. OM dramatically contributes to the APD as multiple-layer adsorption exists, and the APD for OM could be 1.4–8.5 times that for clay minerals. Other inorganic minerals contribute less to APD. The properties and constitution of the surface area instead of the volume fraction contribute to the APD in shales. APD does not show an obvious correlation with micropore volume, likely related to the ratio of micropore volume to the total pore volume. Here, we provide a significant and comprehensive study of petrological factors that impact the APD of subsurface shale gas, which will improve the estimation of supercritical adsorption and shale GIP under reservoir conditions. Also, the findings in this work can provide applications for subsurface carbon dioxide adsorption and storage.

58 GEOSCIENCES↗

A study of silver acetate under extreme conditions

With the aim of exploring chemical systems that may undergo metallization when irradiated with hard X-rays, we selected silver acetate (AgC 2 H 3 O 2 ) for the subject of this study. X-ray-induced decomposition of silver acetate under ambient and high-pressure conditions was observed in a diamond anvil cell (DAC), leading to the formation of metallic nanograins of silver at ambient pressure and 1.65 GPa. At 4 GPa, no decomposition was observed. The Avrami kinetics equation also provides information about novel structural formation at ambient pressure and 1.65 GPa. By modeling of the XRD data, it was found that the size of the silver nanocrystallites formed at 1.65 GPa pressure steadily increased to ∼5 nm after 600 min of X-ray irradiation as determined by applying the Scherrer equation to the diffraction peak widths. Time-resolved X-ray diffraction (XRD) revealed pressure-dependent kinetics, demonstrating that coupling pressure with irradiation enables controlled photochemical pathways in this model system. Concurrent with previous studies, the application of high pressure (HP) can be considered as a means of controlling X-ray synthetic photochemistry.

36 MATERIALS SCIENCE↗

Experimental and first-principles studies on the elastic properties of α-hafnium metal under pressure

Compressional and shear wave velocities of the α phase of hafnium have been measured up to 10.4 GPa at room temperature using ultrasonic interferometry in a multi-anvil apparatus. A finite strain equation of state analysis yielded K s0 = 110.4 (5) GPa, G 0 = 54.7(5) GPa,K s0 ' = 3.7 and G 0 ' = 0.6 for the elastic bulk and shear moduli and their pressure derivatives at ambient conditions. Complementary to the experimental data, the single crystal elastic constants, elastic anisotropy and the unit cell axial ratio c/a of α-hafnium at high pressures were investigated by Density Functional Theory (DFT) based first principles calculations. A c/a value of 1.605 is predicted for α-Hf at 40 GPa, which is in excellent agreement with previous experimental results. The low-pressure derivative of the shear modulus observed in our experimental data up to 10 GPa was found to originate from the elastic constant C44 which exhibits negligible pressure dependence within the current experimental pressure range. At higher pressures (>10 GPa), C 44 was predicted to soften and the shear wave velocity ν S trended to decrease with pressure, which can be interpreted as a precursor to the α-ω transition similar to that observed in other group IV elements (titanium and zirconium). Here, the acoustic velocities, bulk and shear moduli, and the acoustic Debye temperature (θ D = 240.1 K) determined from the current experiments were all compared well with those predicted by our theoretical DFT calculations.

36 MATERIALS SCIENCE↗

The effects of adiabatic and viscous heatings on plumes

The influences of viscous and adiabatic heatings on the transient development of plumes have been assessed by employing the time-dependent convection equations in the extended-Boussinesq limit. Both temperature-dependent and temperature- and pressure-dependent viscosities are employed. For constant thermal expansion of coefficient, the vigor of plume flows is diminished with larger magnitudes of the thermal expansivity. This effect is caused by the local domination of adiabatic decompression over viscous heating inside the developing plume for both the Cartesian and axisymmetric domains. For deep mantle flows a thermal expansivity decreasing with depth is required for thin plume structures to exist. Values of the thermal expansivity contrast, which can promote plume growth, are in accord with estimates from recent studies in seismic equation of state.

Zhao, Wuling↗

Power assist EVA glove development

Structural modeling of the EVA glove indicates that flexibility in the metacarpophalangeal (MCP) joint can be improved by selectively lowering the elasticity of the glove fabric. Two strategies are used to accomplish this. One method uses coil springs on the back of the glove to carry the tension in the glove skin due to pressurization. These springs carry the loads normally borne by the glove fabric, but are more easily deformed. An active system was also designed for the same purpose and uses gas filled bladders attached to the back of the EVA glove that change the dimensions of the back of the glove and allow the glove to bend at the MCP joint, thus providing greater flexibility at this joint. A threshold control scheme was devised to control the action of the joint actuators. Input to the controller was provided by thin resistive pressure sensors placed between the hand and the pressurized glove. The pressure sensors consist of a layer of polyester film that has a thin layer of ink screened on the surface. The resistivity of the ink is pressure dependent, so an extremely thin pressure sensor can be fabricated by covering the ink patch with another layer of polyester film and measuring the changing resistance of the ink with a bridge circuit. In order to sense the force between the hand and the glove at the MCP joint, a sensor was placed on the palmar face of the middle finger. The resultant signal was used by the controller to decide whether to fill or exhaust the bladder actuators on the back of the glove. The information from the sensor can also be used to evaluate the effectiveness of a given control scheme or glove design since the magnitude of the measured pressures gives some idea of the torque required to bend a glove finger at the MCP joint. Tests of this actuator, sensor, and control system were conducted in an 57.2 kPa glove box by performing a series of 90 degree finger bends with a glove without an MCP joint assembly, a glove with the coil spring assembly, and with the four fingered actuated glove. The tests of these three glove designs confirm the validity of the model.

Main, John A.↗

Turbulent Flame Speeds and NOx Kinetics of HHC Fuels with Contaminants and High Dilution Levels

This progress report documents the first year of the project, from October 1, 2010 through September 30, 2011. Laminar flame speeds and ignition delay times have been measured for hydrogen and various compositions of H 2 /CO (syngas) at elevated pressures and elevated temperatures. Two constant-volume cylindrical vessels were used to visualize the spherical growth of the flame through the use of a schlieren optical setup to measure the laminar flame speed of the mixture. Hydrogen experiments were performed at initial pressures up to 10 atm and initial temperatures up to 443 K. A syngas composition of 50/50 was chosen to demonstrate the effect of carbon monoxide on H 2 -O 2 chemical kinetics at standard temperature and pressures up to 10 atm. All atmospheric mixtures were diluted with standard air, while all elevated-pressure experiments were diluted with a He:O 2 of 7:1 to minimize hydrodynamic instabilities. The laminar flame speed measurements of hydrogen and syngas are compared to available literature data over a wide range of equivalence ratios where good agreement can be seen with several data sets. Additionally, an improved chemical kinetics model is shown for all conditions within the current study. The model and the data presented herein agree well, which demonstrates the continual, improved accuracy of the chemical kinetics model. A high-pressure shock tube was used to measure ignition delay times for several baseline compositions of syngas at three pressures across a wide range of temperatures. The compositions of syngas (H 2 /CO) presented in this study include 80/20, 50/50, 40/60, 20/80, and 10/90, all of which are compared to previously published ignition delay times from a hydrogen-oxygen mixture to demonstrate the effect of carbon monoxide addition. Generally, an increase in carbon monoxide increases the ignition delay time, but there does seem to be a pressure dependency. At low temperatures and pressures higher than about 12 atm, the ignition delay times appear to be indistinguishable with an increase in carbon monoxide. However, at high temperatures the composition of H 2 and CO has a strong influence on ignition delay times. Model agreement is good across the range of the study, particularly at the elevated pressures. Also an increase in carbon monoxide causes the activation energy of the mixture to decrease.

Petersen, Eric↗

Broadband Noise Predictions for an Airfoil in a Turbulent Stream

Loading noise is predicted from unsteady surface pressure measurements on a NACA 0015 airfoil immersed in grid-generated turbulence. The time-dependent pressure is obtained from an array of synchronized transducers on the airfoil surface. Far field noise is predicted by using the time-dependent surface pressure as input to Formulation 1A of Farassat, a solution of the Ffowcs Williams - Hawkings equation. Acoustic predictions are performed with and without the effects of airfoil surface curvature. Scaling rules are developed to compare the present far field predictions with acoustic measurements that are available in the literature.

Casper, J.↗

The effects of pressure on the nucleation rate of an undercooled liquid

The pressure dependence of the nucleation rate of an undercooled liquid is examined by analyzing the relationship between surface energy and external pressure. The dependence of the melt-crystal interfacial energy on the applied pressure is modeled, and the increase (decrease) in undercooling due to an applied pressure is described for substances which have positive (negative) values of delta-upsilon. A cavitation-nucleation argument is formulated along the lines of Hickling (1965) with attention given to the possibilities of negative and positive pulses about a bubble in the liquid.

Lee, Chun P.↗

High pressure powder X-ray diffraction of sillenites Bi{sub 12}MO{sub 20} (M=Si, Ge, Ti) and Bi{sub 4}Ti{sub 3}O{sub 12}

Powder X-ray diffraction experiments of sillenites Bi{sub 12}M O{sub 20} (M=Si, Ge, Ti) were performed with synchrotron radiation at the ESRF, Grenoble, at pressures up to 39 GPa (M=Si), 50 GPa (M=Ge), and 37 GPa (M=Ti), respectively. These three sillenites were investigated for the first time over such a large pressure range and they show no phase transition up to the highest pressures achieved. Birch–Murnaghan equations of state of third order were fitted to the pressure dependence of the lattice parameters. The resulting bulk moduli B{sub 0} and their pressure derivatives B′ are B{sub 0}=63(1)GPa with B′=6.6(3) (M=Si), B{sub 0}=63.0(5)GPa with B′=5.90(7) (M=Ge), and B{sub 0}=48(1)GPa with B′=9.4(5) (M=Ti). In the case of Bi{sub 12}SiO{sub 20} and Bi{sub 12}TiO{sub 20} the equation of state fits were restricted to pressures below 15 GPa, because the experimental data were affected by non-hydrostatic stress at higher pressures. The equation of state of neon was redetermined (V{sub 0}=11.7(6)cm{sup 3}/mol, B{sub 0}=5(1)GPa, B′=5.5(3)GPa) and its use as an internal pressure standard for diffraction experiments is discussed. A second cubic phase could be identified in our Bi{sub 12}TiO{sub 20} sample. This was attributed to eulytite-type Bi{sub 4}Ti{sub 3}O{sub 12}, which has B{sub 0}=50.9(8)GPa and B′=6.9(3). - Graphical abstract: X-ray diffraction at high pressure → Equation of state. - Highlights: • Powder X-ray diffraction experiments of sillenites were performed at high pressures. • Equations of state of sillenites Bi{sub 12}MO{sub 20} (M=Si, Ge, Ti) were determined. • The sillenite structure was shown to be stable at high hydrostatic pressure. • Sillenites are sensitive to non-hydrostatic pressure conditions in neon-loaded DACs. • An eulytite-type Bi{sub 4}Ti{sub 3}O{sub 12} phase was found to exist up to 10 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural phase transitions in SrTiO 3 nanoparticles

We present that pressure dependent structural measurements on monodispersed nanoscale SrTiO 3 samples with average diameters of 10 to ~80 nm were conducted to enhance the understanding of the structural phase diagram of nanoscale SrTiO 3 . A robust pressure independent polar structure was found in the 10 nm sample for pressures up to 13 GPa, while a size dependent cubic to tetragonal transition occurs (at P = P c ) for larger particle sizes. In conclusion, the results suggest that the growth of ~10 nm STO particles on substrates with significant lattice mismatch may maintain a polar state for a large range of strain values, possibly enabling device use.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Phase transitions in delafossite CuLaO{sub 2} at high pressures

Structural stability of a transparent conducting oxide CuLaO{sub 2} at high pressures is investigated using in-situ Raman spectroscopy, electrical resistance, and x-ray diffraction techniques. The present Raman investigations indicate a sequence of structural phase transitions at 1.8 GPa and 7 GPa. The compound remains in the first high pressure phase when pressure is released. Electrical resistance measurements carried out at high pressures confirm the second phase transition. These observations are further supported by powder x-ray diffraction at high pressures which also showed that a-axis is more compressible than c-axis in this compound. Fitting the pressure dependence of unit cell volume to 3{sup rd} order Birch-Murnaghan equation of state, zero pressure bulk modulus of CuLaO{sub 2} is determined to be 154(25) GPa. The vibrational properties in the ambient delafossite phase of CuLaO{sub 2} are investigated using ab-initio calculations of phonon frequencies to complement the Raman spectroscopic measurements. Temperature dependence of the Raman modes of CuLaO{sub 2} is investigated to estimate the anharmonicity of Raman modes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High pressure study of Ti[subscript 4]AlN[subscript 3] to 55 GPa

Using a synchrotron radiation source and a diamond anvil cell, we measured the pressure dependence of the lattice parameters of a polycrystalline Ti{sub 4}AlN{sub 3} sample up to a pressure of 55 GPa. No phase transformations were observed. As observed in Ti{sub 3}SiC{sub 2}, Ti{sub 3}Si{sub 0.5}Ge{sub 0.5}C{sub 2}, and Zr{sub 2}InC, the compressibility of Ti{sub 4}AlN{sub 3} along the c axis was larger than along the a axis which leads to a decrease in the c/a ratio with increasing pressure. The bulk modulus is 216 {+-} 2 GPa, with a pressure derivative of 3.84 {+-} 0.06.

43 PARTICLE ACCELERATORS↗

Local structure of solid Rb at megabar pressures

We have investigated the local and electronic structure of solid rubidium by means of x-ray absorption spectroscopy up to 101.0 GPa, thus doubling the maximum investigated experimental pressure. This study confirms the predicted stability of phase VI and was completed by the combination of two pivotal instrumental solutions. On one side, we made use of nanocrystalline diamond anvils, which, contrary to the more commonly used single crystal diamond anvils, do not generate sharp Bragg peaks (glitches) at specific energies that spoil the weak fine structure oscillations in the x-ray absorption cross section. Second, we exploited the performance of a state-of-the-art x-ray focussing device yielding a beam spot size of 5 × 5 μm{sup 2}, spatially stable over the entire energy scan. An advanced data analysis protocol was implemented to extract the pressure dependence of the structural parameters in phase VI of solid Rb from 51.2 GPa up to the highest pressure. A continuous reduction of the nearest neighbour distances was observed, reaching about 6% over the probed pressure range. We also discuss a phenomenological model based on the Einstein approximation to describe the pressure behaviour of the mean-square relative displacement. Within this simplified scheme, we estimate the Grüneisen parameter for this high pressure Rb phase to be in the 1.3–1.5 interval.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗