X-Ray Diamond Anvil Cell Facility at NSLS: 2008 Progress Report

1. X-Ray Diamond Anvil Cell Facility at NSLS: 2008 Progress Report Thomas Duffy Dept. of Geosciences Princeton University Beamline Management Team: D. Weidner (Stony Brook), T. Duffy (Princeton), M. Rivers (Chicago), J. Chen (FIU), A. Goncharov (CIW), L. Ehm (Stony Brook), C. Kao (BNL) Beamline Scientists: Jingzhu Hu, Quanzhong Guo 2008 COMPRES Annual Meeting – Colorado Springs

2. Current High-Pressure Program at the National Synchrotron Light Source X17B2, X17B3, X17C, U2A Single crystals and powder x-ray diffraction, infrared spectroscopy Diamond Cells and Multi-anvil devices X17 Superconducting wiggler, U2 bending magnet 200 users from 50 institutions annually ~45 publications per year (6% of NSLS total) Main support through Consortium for Materials Property Research in Earth Sciences (COMPRES) with additional funding from Carnegie/DOE Alliance Center, NSF-EAR, and DOD.

3. X17 DAC (X17C, X17B3) Strategic Plan • Provide a state-of-the-art community facility for high-pressure mineral physics research • Develop and enhance key and unique features of the NSLS DAC facility -- Energy dispersive Diffraction -- New laser heating capabilities -- Combined X-ray and IR studies -- High quality support lab --High-pressure community at NSLS 3. Lay groundwork to develop a high-pressure program at NSLS-II that will be world-class and take advantage of the unique features of this new machine

4. X-Ray Diamond Anvil Cell Research at NSLS: X17C X17C -- One of longest-running high-pressure synchrotron beamlines in the world Side station on a superconducting wiggler beamline Main techniques: Energy and angle dispersive diffraction on single crystals and polycrystals to ultrahigh pressures, Studies of: equation of state, phase transitions, structure refinements, yield strength, amorphization, texturing, compressibility, and other properties New techniques pioneered on the beamline in recent years: development of rotational diamond anvil cell, applications of synthetic and designer anvils, gem anvil cells, and radial x-ray diffraction techniques Materials studied: metals. oxides, silicates, nitrides, manganites, clathrates, nanocrystals, microinclusions Sample preparation facility: diamond cell equipment, stereomicroscope, microdrills, gas loading, ruby fluorescence spectrometer Supported by NSF Earth Science through COMPRES

5. Angle-dispersive x-ray diffraction experiments at X17C Monochromator Sagittally bent Si Laue crystals Beam energy tunable 20 keV to 40 keV Focusing mirror K-B mirror Primary beam size 0.150 mm x 0.160 mm Focus beam size 0.025 mm x 0.020 mm Detector MARCCD Energy-dispersive x-ray diffraction experiments at X17C White beam energy ramge 20 keV to100 keV Focusing mirror K-B mirror Primary beam size 0.060 mm x 0.070 mm Focus beam size 0.025 mm x 0.020 mm Detector Ge detector

6. X-Ray Diamond Anvil Cell Research at NSLS: X17B3 Main techniques: Energy and angle dispersive diffraction on single crystals and polycrystals to ultrahigh pressures; laser heating to 4000 K. Studies of: equation of state, phase transitions, structure refinements, yield strength, amorphization, melting, texturing, thermal expansivity, compressibility, liquid and glass structure and other properties New techniques pioneered on the beamline in recent years: Development of x-ray focusing devices, monochromators High energy total x-ray scattering of melts and glasses. sample detector slits Materials studied: metals. oxides, silicates, nitrides, manganites, clathrates, nanocrystals, microinclusions

7. Angle-dispersive x-ray diffraction experiments at X17B3 Monochromator Sagittally bent Si Laue crystals Beam energies 30 keV / 80 keV Focusing mirror K-B mirror (for 30 KeV) Primary beam size .100 mm x .150 mm at 2mrad Focus beam size 25 um x 25 um Detector Mar345 Energy-dispersive x-ray diffraction experiments at X17B3 White beam energy 20 keV to100 keV Focusing mirror K-B mirror Primary beam size .100 mm x .180 mm at 2mrad Focus beam size 8um x 8um Detector Ge detector

8. Operations Summary • Contributing user agreement with NSLS: 50% general user time and 50% contributing user (COMPRES) time (25% for users, 25% for development). • X-17C operates 100% of time: • ~81 days beamtime per cycle (G+C users) • X-17B3 operates 33% time dedicated, 33% parasitic with X-17B2. • ~ 54 days beamtime per cycle (G+C users) • All beamtime allocated by proposals submitted to NSLS General User System • Beamlines are running with only 1 staff person for each station. • 2008 Beamtime Usage Statistics for X17 DAC (X17C+X17B3): • May-August 2008: 20 proposals requesting 114 days of beamtime • Sept-Dec 2008: 24 proposals requesting 152 days of beamtime

9. X17C X17B3

10. X17 Selected Publications -- 2008 High Pressure Phase Transitions and Compressibilities of Er2Zr2O7 and Ho2Zr2O7 F. Zhang et al., Appl. Phys. Lett., 92: 011909 (2008) Phase Stability and Pressure Dependence of Defect Formation in Gd2Ti2O7 and Gd2Zr2O7 Pyrochlore Zhang et al.,Phys. Rev. Lett.,100: 045503 (2008) Osmium Metal Studied under High Pressure and Nonhydrostatic Stress M Weinberger et al., Phys. Rev. Lett., 100: 045506 (2008) Irraditation-Induced Stabilization of Zircon (ZrSiO4) at High Pressure Lang et al. Earth Planet Sci. Lett., 269: 291 (2008) Garnet Yield Strength at High Pressures and Implications for Upper Mantle and Transition Zone Rheology, Kavner, J. Geophys. Res., 112: B12207 (2008) In Situ High-Pressure X-ray Diffraction Study of H2O Ice VII M Somayazulu, et al,, J. Chem. Phys., 128: 064510 (2008) Premier Publication as defined by NSLS

11. Deformation of the Lower-Mantle Ferropericlase (Mg,Fe)O across the Electronic Spin Transition Beamline: X17C Category of Researcher: GU and CU Technique: EDXD Researchers & affiliations: J. Lin, LLNL H. R. Wenk, Berkeley S. Speziale, Potsdam J. Shu, CIW T. S. Duffy, Princeton Publication:Deformation of the lower-mantle ferropericlase across the electronic spin transition, submitted to Nature, 2008. Motivation: To understand the effect of an Fe spin transition on the texture, stress, and strength of ferropericlase under lower-mantle pressures, We have deformed [(Mg0.83,Fe0.17)O] under nonhydrostatic condition in a diamond anvil cell up to 81 GPa using energy-dispersive radial X-ray diffraction techniques. Results: We observe unexpectedly lower stress and strength of ferropericlase, together with active slip systems and high elastic anisotropy. These results indicate that ferropericlase would play more dominant roles in the deformation and seismic anisotropy of the lower mantle, including subducting slabs, than what is expected by studying the high-spin ferropericlase. Figure 1 Figure: Inverse pole figures of the compression direction for (Mg0.83,Fe0.17)O at high pressures in equal area projection.

12. Phase Transitions in Alkaline Earth Fluorides CaF2 and SrF2 to 95 GPa Beamline:X17B3 Category of Researcher: CU Technique: ADXD Laser Heating Researchers & affiliations: S. Dorfmann, F. Jiang, Z. Mao, and T. Duffy all: Princeton U Publication: S. Dorfmann et al., EOS Trans. AGU, 2007 Motivation: Results: The alkaline earth fluorides (MgF2, CaF2, SrF2, BaF2) exhibit extensive polymorphism at high pressures. They serve as a model system for understanding highly coordinated structures and phase transition pathways in other AX2 compounds such as SiO2. CaF2 and SrF2 transform to a hexagonal Ni2In-type structure at 84 and 36 GPa, respectively, following laser heating. This work represents the first synthesis and characterization of the Ni2In-type phase for these compositions. Figure 1 Pressure-volume data on SrF2. The Ni2In-type and cotunnite-type phases are fitted to a Birch-Murnaghan equation of state. On decompression, SrF2 passes through an intermediate orthorhombic phase at 28 GPa before returning to cotunnite structure at 22 GPa. This transition is analogous to the isosymmetric phase transition to the Co2Si-type structure reported in PbF2 by Haines et al. (1998). This is the first report of Co2Si structure in an alkaline earth fluoride.

13. Structure of liquid Gallium at high pressure Motivation: Results: Beamline:X17B3 Category of Researcher: CU Technique: X-ray total scattering Researchers & affiliations: T. Yu1, L. Ehm1,4, J. Chen1,2 S. Luo3, and Q. Guo1 1Stony Brook University 2Florida Int. University 3Los Alamos National Lab. 4NSLS Publication: This project received the "Best Poster" Award at 2007 NSLS User's Meeting. Yu et al., in preparation, 2008 Gallium shows many polymorphic phase transitions as a function of pressure and temperature. Furthermore, gallium belongs to the ice-type elements the density of the liquid phase exceeds the density of the stable crystalline phase Ga-I by ~3%. Hence, gallium melts at RT upon application of pressure. Figure 1 Raw data of solid gallium and the liquid phase of gallium. Non-uniform com-pression of the <Ga-Ga> distances. This compression behavior of liquid-Gallium can not easily be explained by a hard sphere model of the liquid. Figure 2 Normalized structure factor S(Q) at 1.32 GPa. Figure 3 Pressure dependence of thePair Distribution Function of liquid Gallium. Compression behavior and the presents of a shoulder on the first diffraction maximum in S(Q) suggest a local ordering in liquid Gallium.

14. Major Developments at X17 DAC -- 2008 1. Personnel and management New management team (Duffy, Weidner co-PI) Lars Ehm (SBU/BNL staff member) New beamline scientists in 2008 Integration of high-pressure activities at NSLS 2. Beamline Developments New laser heating system (Goncharov, PI) New dedicated area detector 3. Planning for transition to NSLS-II in 2015

15. Staffing Jingzhu Hu and Quanzhong Guo will retire on 9/30/08. Jingzhu has been beamline scientist at X17C for 18 years. She is 2008 winner of the NSLS Community Service Award. Quanzhong Guo has been beamline scientist at X17B3 for 10 years. The high-pressure community is very grateful for their years of dedicated service. On-going search for new beamline scientists Search committee: Duffy, Ehm, Weidner “Over the last 15 years, every single time I have been at X17C, Jingzhu has given 100 percent of herself to help ensure that my experiments worked. She seemed to live at the synchrotron. When problems that I couldn’t deal with popped up, whether at 9 a.m. or 9 p.m., Jingzhu was there to help us overcome them.” -- From an anonymous nomination letter for Jingzhu Hu for the NSLS community service award

16. X17B3 Upgrade: New Laser Heating System for Diamond Anvil Experiments

17. X17B3 Upgrade: New Area Detector Rayonix SX-165 CCD detector -- 165 mm active area, 2048 x 2048 pixels --Previous generation (MarCCD) is standard for high-P synchrotron experiments -- fast readout time (2.5 s) for in situ laser heating - millisecond partial readout time will allow for studies on a time scale not previously available in high P-T science.

18. High-Pressure Community Outreach Efforts and Planning Feb. 25-26, 2006 “NSLS X-Ray High Pressure Research Workshop: Current operation and vision into NSLS II (sponsored by COMPRES and MPI) (46 attendees) Report prepared by J. Chen et al. July 17-18, 2007 High-pressure discussion session at “NSLS-II Users Workshop” (28 attendees). “High Pressure Needs at NSLS-II Synchrotron” prepared by D. Weidner et al. January 17-18, 2008 “Materials at High Pressure” breakout session during the Workshop on “The NSLS-II Powder Diffraction Project Beamline” and “Materials Science Engineering Strategic Planning for NSLS and NSLS-II (34 attendees). White paper prepared by Lars Ehm et al. March 2008 Letter of Interest (LOI) submitted for high-pressure superconducting wiggler beamline at NSLS-II May 21, 2008 Workshop on “Future Directions in High-Pressure Research” at NSLS Users’ Meeting

20. d 25m 20mm Monochomatic beam Two crystals of 0.76 mm thick, with surfaces corresponding to the (001) planes, are bent sagittally to 1 m radius. Used in the Laue (transmission) mode. Silicon 111 reflection was used with asymmetry angle of 35.3 degrees. The monochromatic beam is higher 20 mm than incident white beam. The distance of two crystals d depends on the X-ray energy. At 30 keV d = 160mm. At 40 keV d = 200 mm. The bent Laue crystals provides high energy-resolution beam with a flux one order of magnitude greater than that of a flat-crystal monochromator, Sagittal focusing was not used at X17C due to short distance between monochromator and sample Z. Zhong, et. al., Acta. Cryst. A 59 (2003)

21. Experiment Setup in X17C Hutch Z Y Motorized X, Y, Z stages X Manual adjusting X, Y stages Rotating w stage X17B beam pipe Photo diode Monochromator Beam stop Vertical beam focusing mirror Ion chamber Si (100) DAC Horizontal beam focusing mirror 2q arm X-ray window Beam stop Clean up slit Beam slit MARCCD Goniometor q, 2q stages microscope