CARNEGIE/DOE ALLIANCE CENTER A Center of Excellence for High Pressure Science and Technology Supported by the Stewardship Science Academic Alliances Program of DOE/NNSA Year Six Annual Report December 2009 Russell J. Hemley, Director Ho-kwang Mao, Associate Director Stephen A. Gramsch, Coordinator Carnegie/DOE Alliance Center (CDAC): A CENTER OF EXCELLENCE FOR HIGH PRESSURE SCIENCE AND TECHNOLOGY YEAR SIX ANNUAL REPORT 1. Overview 1.1 CDAC in Year 6 – New Advances and Opportunities 1 1.2 Highlights from Year 6 4 Outreach and Training 4 Scientific Breakthroughs 6 Technique Developments 8 2. Scientific Progress 2.1 High P-T Phase Relations and Structures 10 Reversible Pressure-Induced Amorphization in Superconducting FeSe0.5Te0.5 10 Pressure-Induced Invar Phenomena 11 Progress in Understanding the Behavior of Dense Solid Hydrogen 12 Pressure-Induced Compound Formation in the Xe-H2 System 12 Intermolecular Interactions in the SiH4-H2 System at High Pressure 12 Phase Tranformations in Eu Metal at High Pressure 13 Polyamorphic Systems at High Pressure and Temperature 13 Liquid-Liquid Transition in Supercooled Silicon 14 Novel High-Pressure Phase of Elemental Boron 16 Effect of water on high-pressure phase transitions in MgSiO3 17 Exploring a New High Pressure Metallurgy 17 Melting Studies Using Simultaneous Diffraction and Laser Heating 18 Pressure-Induced Lattice Collapse in Fe1.05Te 19 Understanding Hydrogen Environments in Minerals 19 2.2 P-V-T EOS Measurements 20 Static Compression to Multimegabar Pressures 20 Structures and Phase Transitions in Transition Metal Oxides 20 Phase Transition and EOS of Y3Fe5O12 at High Pressures 22 Equations of State for Liquids and Amorphous Solids 23 High P-T EOS of Osmium 23 Equations of State for High Explosives 24 2.3 Phonons, Vibrational Thermodynamics and Elasticity 25 Understanding Invar Behavior at the Microscopic Level 25 Vibrational Entropy of Vacancies in Fe-Al 26 Elastic Properties from Powder Samples 26 Infrared Reflectivity Studies on Semiconductors 27 Elastic Moduli and Stregth of Nanocrystalline Cubic BC2N 28 EOS of Polymers by Brillouin Scattering 29 Pressure Tuning of Thermal Conductivity in a Layered Crystal 30 Thermal Conductivity Modeling of Dense Hydrogen Fluids 30 2.4 Plasticity, Yield Strength and Deformation 30 Deformation Measurements at High Pressure 30 Deformation in Hexagonal Metals 32 Microstructure Evolution at High Pressures 32 Uncovering the Role of Phase Transformations in Texture Changes 33 Residual Stress in Deformed Crystals 34 i 2.5 Electronic and Magnetic Structure and Dynamics 35 Amorphization and Superconductivity in Layered Fe-Based Materials 35 Magnetic Properties of Rare Earth Metals at High Pressure 37 Rare Earth-Iron Laves Phases at High Pressure and Temperature 37 Structural and Electronic Properties of Group IV Metals 38 Thermal Conductivity of Simple Oxides 39 Spin Transitions in Transition Metal Oxides 39 High-Pressure X-Ray Absorption Sepctroscopy of Fe2O3 40 Bigger, Better Diamond Single Crystals 40 Enhanced Magnetic Effects at High Pressure 41 Pressure Effects on the Properties of Relaxor Ferroelectrics 41 Metallization and Superconductivity in Group IVA Hydrides 42 Effects of Pressure-Induced Competition in Electronic Order 43 2.6 High P-T Chemistry 43 Special Properties of Bulk Metallic Glasses 44 Spectroscopy of Monolayers Under Extreme Conditions 44 Surface Chemistry and Spectroscopy 45 Aqueous Oxidation of Re Metal in Supercritical H2O-O2 Mixtures 46 Hydrogen Interactions with Polymerica B-N-H Compounds 47 Behavior of the NH3-BH3-H2 System at High Pressure 48 Boranes and Their Interactions with H2 Under Extreme Conditions 48 Hydrocarbon Condensation Reactions under Pressure 49 Recalibrating the Time Scale of Planet Formation 49 Can Pressure Modify the Rules for Alloy Formation? 50 3. Education, Training, and Outreach 3.1 CDAC Graduate Students and Post-doctoral Fellows 50 Student Publications 52 Student Presentations 54 3.2 Undergraduate Student Scholars 60 3.3 DC Area High School Outreach 61 3.4 CDAC Collaborators 62 3.5 Visitors to CDAC 71 3.6 2009 CDAC Winter Workshop 73 Posters Presented at the 2009 CDAC Winter Workshop 73 3.7 High Pressure Synchrotron Science Workshop 76 3.8 Carnegie CDAC Group Meetings 78 4. Technology Development 4.1 Technical Improvements at HPCAT 80 A Second Undulator on the Insertion Device Beamline 80 Beamline ID-D: X-Ray Spectroscopy 80 Beamline ID-B: Microfocused X-Ray Diffraction 81 Beamline 16-BM-D: High-Resolution Powder Diffraction 82 Beamline 16-BM-B: PE-Cell Development 82 4.2 Technical Improvements at HPCAT 83 Expanded Facilities 83 4.3 Infrastructure Development at Carnegie and Academic Nodes 83 Development of a Hybrid Optical-Mechanical Interferometer 83 Laser-Launched Flyer Plates 84 Development of Laser Heating Techniques 84 ii Automation of Laser Heating-Raman Spectroscopy Experiments 85 5. Interactions with NNSA/DP Laboratories 5.1 Overview 86 5.2 Beam Time for Experiments at HPCAT 87 5.3 Other Interactions 87 6. Management and Oversight 6.1 CDAC Organization and Staff 89 6.2 CDAC Oversight 90 7. Plans for Year 5 and Beyond 7.1 New Academic Partners 91 7.2 HPCAT Upgrade 91 7.2.1 High Brilliance: Undulator Source Upgrade by APS 92 7.2.2 High Heat Load and High Efficiency Beamline Optics 93 7.3 New Initiatives 93 7.3.1 HPSynC Science and Outreach 93 7.3.2 New Facilities and Projects 94 Appendix I CDAC Publications and Presentations for Year 6 96 A. CDAC Publications 96 B. CDAC Presentation 108 Appendix II CDAC Synchrotron Users/Experiments (APS and NSLS) for Year 5 125 A. HPCAT (APS) 125 B. U2A Infrared Beamline (NSLS) 137 References 140 On the Cover Clockwise from top left: 1) Crystalline SiH4(H2) 2 formed from a mixture of SiH4 and H2 at in a diamond anvil cell and separated from the surrounding fluid at 7 GPa. In this high pressure material, the H2 covalent bond weakens substantially, suggesting a pathway for dissociation and metallization of molecular hydrogen. 2) One of many types of diamond anvil cells in use at CDAC. Simple in design and powerful in application, such diamond-based devices allow measurements of structural, spectroscopic and transport properties of materials at extreme pressures up to several hundred gigapascals and temperatures close to 104 K.. 3) Target Chamber of the National Ignition Facility (NIF). CDAC personnel are participating the first materials science experiments carried out at NIF. Credit for this image is given to Lawrence Livermore National Security, LLC, Lawrence Livermore National Laboratory, and the Department of Energy under whose auspices this work was performed. 4) Calculated electron density of the high-pressure, incommensurate tl19 phase of sodium metal prior to the formation of its recently discovered dense insulating state. 5) CDAC Graduate Student Lowell Miyagi examines a sample in a diamond anvil cell. Miyagi, who received his PhD from the University of California – Berkeley in 2009, investigated the deformation mechanisms of materials at high pressures and temperatures for his dissertation research with Academic Partner Hans-Rudolf Wenk. iii 1. OVERVIEW Science is the foundation of our Nation’s security in the modern world. Indeed, the importance of science continues to grow with the numerous challenges we now face in maintaining the safety, security and reliability of our nuclear deterrent as the size of the stockpile is reduced. Moreover, that same fundamental knowledge is essential for nuclear forensics and the support of non-proliferation of nuclear weapons. In the absence of explosive nuclear testing, we must rely on accurate knowledge of the underlying physics, chemistry and materials science of the remarkable variety of components in the nuclear weapons complex. A key part of this broad scientific effort is an understanding of material behavior in extreme environments of pressure and temperature. The Carnegie-DOE Alliance Center (CDAC) is a vibrant partner working in support of the national security effort, through our work with stewardship science campaigns in the Department of Energy (DOE)/National Nuclear Security Administration (NNSA). As a Center of Excellence within the Stewardship Science Academic Alliances (SSAA) program, the primary scientific work of CDAC is high P-T materials science of interest to DOE/NNSA. Here we highlight progress from the first year of our second five-year phase of funding as part of the SSAA program in an evolving era of stockpile stewardship. 1.1 CDAC in Year 6—New Advances and Opportunities Since its founding, CDAC has been characterized by a remarkable diversity of scientific interests, and through our Center-like structure, CDAC continues to make a significant impact in scientific achievement, technique development, and student education and training. Academic 1 Partners in CDAC have been selcted from leading high-pressure programs in the United States representing chemistry, physics, materials science and geoscience departments, while CDAC Laboratory Partners come from the high-pressure groups at all three NNSA Labs. The scientific research carried out by CDAC groups is equally diverse, from investigating the equations of state, magnetic properties and phase transitions of rare earth and transition metals at high pressure and temperature to determining the high P-T vibrational properties of hydrogen and hydrogen-rich alloys and compounds. Increasingly important is chemical information at the atomic scale, and CDAC has made great strides in understanding how pressure affects chemical processes at interfaces and in bulk materials. Improved x-ray diffraction and analysis methods have enabled determinations of the elastic and rheological properties of a wide selection of polymeric materials and oxides, as well as the solution of structural models for polymers and bulk metallic glasses. Advancements in a variety of x-ray spectrosopic techniques have likewise resulted in new information on phonon dynamics at high pressures, along with new views on the evolution of chemical bonding and magnetism in an extensive array of materials with pressure.