Transcript Slide 1
Shining Synchrotron Light on Supercritical Fluids Alan J. Anderson St. Francis Xavier University The Hydrothermal Diamond Anvil Cell HDAC Hydrothermal Diamond Anvil Cell (HDAC) Different Diamond Anvil Configurations Re Gasket Sample Chamber Grooves Surface Profilometry Average depth 47.48 μm Volume 3.55 X 106 µm3 FIB Milling of Diamond Anvil HDAC Sample Chamber at 25 oC Aqueous solution 0.2 mm Vapor bubble 1000 Pressure (MPa) 800 600 400 200 Liquid 0 Vapor 0 100 200 300 400 500 600 Temperature (oC) 700 800 900 Synchrotron X-ray Micro- and Nanoprobes Canadian Light Source Inc. 4 2 0 18900 19000 19100 Energy (eV) 19200 Nuclear Resonant Inelastic X-ray Scattering X-ray Diffraction Angle-dispersive Energy-dispersive X-ray Raman X-ray Emission Spectroscopy Microdiffraction Synchrotron Mössbauer Spectroscopy X-ray Absorption Spectroscopy L-N2 L-He mK X-ray Magnetic Circular Dichroism Laser & Resistive heating Radial X-ray Diffraction Physics Astrophysics Geochemistry Chemistry Crystallography Mineral physics Biology Geophysics Materials science Solution in Sample Chamber @ 25 ºC Diamond Anvil Path of Fluorescence X-rays to the Detector Liquid Vapor Path of Incident X-rays 300 µm X-ray Fluorescence Imaging and Quantitative Analysis Map showing the distribution of Ta2O5 particles in 5% HF at 25 ºC (HDAC 116) Solid Ta2O5 Particles Map showing the distribution of Ta in 5% HF at 360°C (HDAC 116) 100 µm Ta Lα1 5 3.5x10 Ta2O5 Dissolved in 5% HF HDAC 116 @ 360°C (ρ = 0.566) 10,700 μg mL-1 Ta HDAC 110 @ 350°C (ρ = 0.575) 7,400 µg mL-1 Ta 5 3.0x10 5 Intensity 2.5x10 5 2.0x10 Ta Standard (1000 µg mL-1) HDAC 110 @ 360°C (ρ = 0.575) HDAC 116 @ 400°C (ρ = 0.504) 5 1.5x10 5 1.0x10 Ta Lβ1 4 5.0x10 Fe Kα1 Fe Kβ1 0.0 6 7 8 9 Energy (keV) 10 11 Time resolved analysis - Pb in aqueous fluid during interaction with partially metamict zircon (ZrSiO4) at 300 oC X-ray Absorption Spectroscopy XAS Resolving the local structure of metals in SCW X-ray Absorption Fine Structure (XAFS) TaCl5 in 2% HF Ta2O5 in 5% HF 3 Absorption Intensity (Arb. Units) 3 o o 400 C, 39.1 MPa 400 C, 29.1 MPa 2 2 o 350 C, 16.5 MPa o 360 C, 22.8 MPa 1 1 o 25 C, room pressure o 25 C, room pressure 9880 9900 9920 9940 9880 Energy (eV) 9900 9920 9940 400 °C 30 NF=9.1 F.T. Magnitude (Arb. Units) 25 20 MS 3.61 Å 15 2.01 Å 10 NCl=6.4 MS 3.57 Å 5 2.05 Å 0 0 2 R (Å) 4 Summary • Synchrotron – based techniques • Monitor SCW – material interaction • Resolve the local structure of aqueous metal complexes • Solubility of selected oxides Raman spectroscopy Raman system HDAC on the microscope Interferences in X-ray Emission Spectra Re L lines Ta L lines 7.0 7.5 8.0 8.5 9.0 9.5 10.0 Energy (keV) 10.5 11.0 11.5 12.0 12.5 Counts Sample Contamination from Re Gasket Energy (keV) ** Sample Contamination from Gasket Reaction with Diamond 500 500 1000 1000 1500 1500 2000 2000 2500 2500 * 3500 3500 2992.5 1285.3 (c) CH4 (c) (b) Intensity (a.u.) Intensity (a.u.) 1285.3 3000 3000 4000 4000 1388.1 1388.1 experiment # 2-11-08a VV 1283.9 1283.9 2918.2 1387.2 1387.2 2900 2900 29 (d) (d) LL 4125. 412 CO2 (V) CO 2 (V) 4000 experiment # 2-5-08b 1260 1280 1300 1320 1340 1360 1380 1400 1280 1300 1360 3000 1380 1400 29001260 2920 2940 1320 296013402980 3020 -1 Wavenumber ((cm Wavenumber cm-1 )) 4120 4120 X-ray Diffraction In situ XRD Wu et al. (1997) Dehydration & Rehydration of Montmorillonite Reversible changes in lattice dimensions