Bulletin of the American Physical Society
APS March Meeting 2018
Volume 63, Number 1
Monday–Friday, March 5–9, 2018; Los Angeles, California
Session S38: Materials in Extremes: Synthesis of Novel Materials |
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Sponsoring Units: DCOMP GSCCM DMP Chair: Romain Perriot, Los Alamos National Laboratory Room: LACC 501A |
Thursday, March 8, 2018 11:15AM - 11:27AM |
S38.00001: Polymerization of CO2 at moderate P-T condition Minseob Kim, John Tse, Choong-Shik Yoo We report the formation of extended network polymers of singly bonded CO4 by catalytic oxidation reactions of CO2 at relatively low pressures, using Raman spectroscopy, X-ray diffraction, and visual observations. The results indicate that there are three different solid phases; a needle-like phase (NP), a rock-like phase (RP), and a transparent phase (TP), formed as temperature increases at 8 GPa. The spectral evidence indicates these transformations accompany the sp2 hybridized C=O in molecular CO2 to sp3 hybridized C-O single bonds. The diffraction data of the quenched RP at ambient temperature at 8 GPa indicates a layered tetragonal structure of CO4 tetrahedra with ρ=2.85g/cm3 – a similar density to that of extended CO2-V at the same pressure. |
Thursday, March 8, 2018 11:27AM - 11:39AM |
S38.00002: X-ray and pressure induced synthesis of a novel material: doped polymeric carbon monoxide. Michael Pravica, Egor Evlyukhin, David Goldberger, Petrika Cifligu, Blake Harris We report the x-ray and pressure induced synthesis of a novel material: stable doped solid carbon monoxide (p-CO) via hard x-ray irradiation of strontium oxalate (and other oxalate salts) at ambient conditions and high pressure. We also show via mid- and far- infrared (IR) techniques that CO2 produced via x-ray photochemistry remained trapped within the recovered sample for period of over one year in contrast to pure p-CO which decomposes in days. Our results demonstrate that p-CO doped with carbonates (as verified with IR and Extended X-ray Absorption Fine Structure spectroscopies) is relatively stable, enabling longer term and practical use of this novel material for CO2 storage or as a novel electrical/optical material. |
Thursday, March 8, 2018 11:39AM - 11:51AM |
S38.00003: Copolymerization of dense CO and N2 to extended CON network structure Choong-Shik Yoo, Young Jay Ryu, Minseob Kim, Jinhyuk Lim, Iskander Batyrev CO and N2 are isoelectronic, which have similar melting temperatures, phase transitions, and crystal structures at low pressures and undergo similar chemical transformations to extended network structures at high pressures. In this study, we have investigated chemical transformations of CO-N2 mixtures over a wide range of composition and pressure, using laser-heated diamond anvil cells, Raman spectroscopy, X-ray diffraction and inelastic X-ray Raman scattering. The results show strong evidences for the formation of all singly bonded, extended CON network structures at 30-50 GPa, highlighting a catalytic role of CO in the synthesis of high energy density, nitrogen-rich polymers well below 100 GPa. |
Thursday, March 8, 2018 11:51AM - 12:03PM |
S38.00004: Hydronitrogen oxides at high pressures Brad Steele, Ivan Oleynik Hydrogen-rich materials have been identified as potential high temperature superconductors following the discovery of record-high Tc in the hydrogen sulfide system at high pressures near 200 GPa. Water-ice H2O is chemically similar to hydrogen sulfide but is an insulator below 1 TPa. It has been recently suggested that substitution of nitrogen for oxygen into the crystal lattice phase X of water-ice might result in induced superconductivity of water/ice. In order to determine whether the proposed compounds are chemically stable, and if not, whether other hydronitrogen oxide superconductors exist, the ternary HxNyOz crystal structure search is performed at high pressures. The ternary H-N-O phase diagram is constructed and the several stable and metastable HNO compounds are found. The chemical pathways involving pressure-induced deprotonation of suitable hydronitrogen hydrades are considered. The electronic and vibrational properties of these new compounds are analyzed and their potential for observation of superconductivity of these hydronitrogen oxides is discussed. |
Thursday, March 8, 2018 12:03PM - 12:15PM |
S38.00005: Predicted Stabilities of High-Density P-N and H-N Extended Solids: A Combined Modeling and Experimental Study Iskander Batyrev, Shawn Coleman, Jennifer Ciezak-Jenkins, Elissaios Stavrou, Joseph Zaug Evolutionary structural search simulations were conducted to search for stable P-N and H-N network-type structures. Density functional theory-based calculations with SCAN functional of relevant high-pressure systems formed the basis for our approach. High-density covalently bonded structures were created in silico using variable and fixed concentration methods. Rank sorting of the most promising (viable) systems is initially based on thermodynamic stability assessments and direct comparison with our measured experimental X-ray diffraction (XRD) patterns. The high pressure stability of predicted systems was finally estimated from convex-hull plot at 0 K. Temperature effect on the stable structures were calculated using temperature dependent effective potential method (TDEP). XRD patterns were calculated using a virtual diffraction algorithm that computes kinematic diffraction intensities in three-dimensional reciprocal space. Direct computation of structure factors enables implementation of distinct atomic scattering factors for each atomic constituent. Evolution (or pressure dependence) of Raman spectra and elastic constants at high pressure were calculated and compared with experiment for the P-N extended solids. |
Thursday, March 8, 2018 12:15PM - 12:27PM |
S38.00006: Carbon Condensation During High Explosive Detonations: Traversing the Carbon Phase Diagram by Varying Material and Detonation Geometry Joshua Hammons, Michael Bagge-Hansen, Michael Nielsen, William Shaw, Lisa Lauderbach, Ralph Hodgin, Sorin Bastea, Tony Van Buuren, Matt Cowan, Daniel Orlikowski, Laurence Fried, Chadd May, Jan Ilavsky, Nicholas Sinclair, Trevor Willey Explosive detonations produce a variety of different carbon nanomaterials that include detonation nanodiamond, carbon onions and other graphitic or amorphous phases. Understanding how these different nano-polymorphs form has challenged the scientific community. In this study, we varied the high-explosive material and the detonation geometry (i.e., cylindrical charge initiated at one end, vs. initiated at both ends) to change the temperatures and pressures attained during detonation and therefore the carbon nano-condensate phase and morphology. A characterization of these nanoscale phases, during detonation, was performed using synchrotron X-rays, as well as ex-situ TEM imaging and theoretical simulations. Due to the rapid detonation velocities ( ~ 8 mm/μs), the X-ray approach pushes the limits of synchrotron experimentation and requires careful considerations and challenges that are also presented. We compare our results of generated carbon morphologies to the heat of detonation and the detonation geometry of different high-explosive materials. |
Thursday, March 8, 2018 12:27PM - 12:39PM |
S38.00007: Carbon Chemistry and Formation of Hierarchical Nanocarbons under Extreme Conditions Produced by High Explosive Detonations Millicent Firestone, Bryan Ringstrand, Matthew Janish, Rick Gustavsen The study of solid carbon (nanocarbons) nucleation and growth from detonating HE is limited, given the difficulty in direct evaluation of chemical reactions behind the shock front. The lack of information on chemical reactions occurring behind the shock front restricts the controlled and reproducible synthesis of carbon materials via detonations. Beyond nanoscience, researchers in the shock physics community are also intrigued by carbon condensation and the reactions occurring behind the detonation front. Insights and ultimately mechanisms regarding the chemistry occurring post-detonation is needed for more accurate predication of HE performance, simulation refinement, and intent. In prior work the primary (carbon) nanoparticle morphology and hybridization states was obtained through multi-scale characterization on unpurified soot. Here, a facile, benign separation protocol is described. The fractionated soot is characterization by SAXS, WAXS, and TEM. This protocol is carried out on products recovered from a colliding wave TATB-based HE detonation. This work is a first step in developing a generally applicable isolation and purification protocol for the recovery of nanocarbons formed by detonations, allowing for verification of organic reactions occurring behind the shock front. |
Thursday, March 8, 2018 12:39PM - 12:51PM |
S38.00008: Synthesis and characterization of molecularly doped nanodiamond at high pressure and high temperature conditions Matthew Crane, Abbie Ganas, Rhonda Stroud, E. James Davis, Peter Pauzauskie The ability to optically initialize, manipulate, and read out the spin of defects in diamond has enabled multifunctional applications in quantum computing, sensing, and cryptography. However, the rational doping of nanodiamond has remained a challenge due to diffusion limitations and diamond’s metastable lattice. |
Thursday, March 8, 2018 12:51PM - 1:03PM |
S38.00009: Mechanochemical Synthesis of Semiconducting Diamonds Matthew Kroonblawd, Nir Goldman We predict a mechanochemical synthetic route to obtain semiconducting diamonds through rapid uniaxial compression of graphite. Ensembles of quantum molecular dynamics simulations reveal that a subset of products formed from initially perfect graphite crystals exhibit significant disorder and partial band gap closure. Seeding atomic vacancies in graphite is shown to significantly bias toward forming semiconducting products. We identify a strong correlation between gap closure and disordered configurations that informs which kinds of structural defects are associated with formation of the semiconducting material. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. |
Thursday, March 8, 2018 1:03PM - 1:15PM |
S38.00010: Mechanochemical Synthesis of Carbon and Carbon Nitride Nanothread Single Crystals Xiang Li, Maria Baldini, Tao Wang, Bo Chen, En-shi Xu, Brian Vermilyea, Vincent Crespi, R Hoffmann, Jamie Molaison, Christopher Tulk, Malcolm Guthrie, Stanislav Sinogeikin, John Badding A new type of 1D sp3 carbon nanomaterial, carbon nanothreads, was recently reported (Nat. Mater., 2015). Modeling suggests “diamond” nanothreads may uniquely combine extreme strength with flexibility and resilience. They are synthesized by compressing benzene slowly in Paris-Edinburgh (PE) cell. After optimizing the synthetic conditions, we now report the synthesis of single crystals of these nanothreads in both PE and diamond anvil cells (JACS, 2017); their single crystal nature allows them to exfoliate into fibers. Exfoliation into individual threads that might be assembled into functional materials may be possible. We also synthesized carbon nitride nanothreads from pyridine by the same kinetically controlled approach. Tuning the chemical composition by the methods of organic chemistry allows for flexible design of properties such as bandgap, solubility etc. We investigated the composition and structure of these diamond and carbon nitride nanothread crystals by NMR, x-ray diffraction, XPS, and vibrational spectroscopies. Synthesis of a large new family of carbon nanomaterials by the slow compression methods used for the synthesis of benzene nanothreads appears plausible. |
Thursday, March 8, 2018 1:15PM - 1:27PM |
S38.00011: Identifying Nanothread Structures with Experimental and Calculated Nuclear Magnetic Resonance Spectra Tao Wang, Pu Duan, En-shi Xu, Brian Vermilyea, Bo Chen, R Hoffmann, Xiang Li, John Badding, Klaus Schmidt-Rohr, Vincent Crespi Well-ordered packed one-dimensional, mainly sp3, carbon nanomaterials, known as nanothreads, have recently been synthesized by slowly compressing and decompressing crystalline, solid benzene from high pressure. The atomic structure of these threads has been determined only in part. We calculated the 13C NMR chemical shifts, chemical shielding tensors and anisotropy of several axially ordered and disordered partially (degree-4) and fully (degree-6) saturated nanothreads within density functional theory and compared systematically with the experimental solid-state NMR spectra to assist in identifying the structures of the synthesized nanothreads. The results reveal that some degree-4 threads might contribute to the sp2 carbon component, and degree-6 threads with distinct carbon sites are plausible candidates of the one-dimensional carbon nanomaterial. We further narrowed down the subset of possible degree-4 and degree-6 candidates by analyzing the calculated and measured chemical shifts anisotropy and two-dimensional solid-state NMR spectra. |
Thursday, March 8, 2018 1:27PM - 1:39PM |
S38.00012: New Route to High-Energy Density Polymeric Nitrogen “t-N” via He-N Compounds Yinwei Li, Xiaolei Feng, Hanyu Liu, Simon Redfern, Jian Hao, Weiwei Lei, Dan Liu, Yanming Ma Polymeric forms of nitrogen, stabilized by compressing pure molecular nitrogen, have not yet been recovered to ambient conditions, precluding their practical application as high-energy density materials. Here, we highlight a possible route to the formation of a novel tetragonal polymeric nitrogen via He-N compounds at high pressures. By combining first-principles calculations with structure searching, we predict the existence of a new class of nitrogen-rich nitrides with a stoichiometry of HeN4 that are energetically stable (relative to a mixture of solid He and N2) above 8.5 GPa. HeN4 adopts a structure consisting of a polymeric channel-like nitrogen framework filled with linearly-arranged helium atoms at pressures above 95 GPa. The nitrogen framework persists to ambient pressure on decompression after the removal of helium atoms, forming a new pure polymeric nitrogen denoted as t-N. t-N is dynamically and mechanically stable at ambient pressure and has an estimated energy density of ~11.31 kJ/g, which marks it out as a remarkable high-energy density material. This expands the known polymeric forms of nitrogen and provides a new potential route to synthesise it. |
Thursday, March 8, 2018 1:39PM - 1:51PM |
S38.00013: High pressure crystal chemistry and compression behaviors of novel early transition-metal nitrides Masashi Hasegawa, Ken Niwa, Takurou Yamamoto, Kazuo Soda Transition-metal (TM) nitrides have attractive physical and chemical properties, such as superconductivity, peculiar magnetism, eminent hardness, distinguished catalytic capability etc. Accordingly, they have been studied from the viewpoints of not only fundamental sciences but also materials science and engineering. Particularly, nitrogen-rich TM nitrides are paid the most attention to now because the laser-heated diamond anvil cell (LH-DAC) is a powerful tool to synthesize novel metal nitrides at ultra-high pressures above dozens GPa ranges. We have reported synthesis, crystal chemistry and electronic structure of various kinds of novel late TM nitrides, such as FeN2, CoN2, FeN, CoN, RhN2, RuN2, IrN2, PtN2 etc. Recently, we have also succeeded in synthesizing novel early TM nitrides using LH-DAC. Especially, single crystals of a novel Cr-nitride have been grown in a supercritical nitrogen fluid and characterized by the synchrotron X-ray diffraction and Raman scattering measurements under both high and ambient pressures. First-principles calculation has been also carried out to evaluate and discuss the electronic structure of these nitrides above. This talk will systematically discuss about novel early TM nitrides as well as late TM ones. |
Thursday, March 8, 2018 1:51PM - 2:03PM |
S38.00014: New Metastable Nitrogen Rich Nitrides of Titanium Venkata Bhadram, Hanyu Liu, DuckYoung Kim, Enshi Xu, Tianshu Li, Stephan Lany, Timothy Strobel The high-pressure and temperature synthesis technique has previously been used for discovering many nitrogen-bearing compounds that exhibit unique properties like high hardness, superconductivity and elctrocatalytic activity etc. Here, we report our experimental discovery of two new compounds in Ti-N system; 1) TiN2 (titanium pernitride) and 2) Cubic-Ti3N4. Both the compounds were synthesized at pressures of a few tens of GPa and temperatures >2300K using diamond anvil cells (DACs) and characterized using in situ X-ray diffraction and Raman scattering. Our first principles calculations suggest that both the compounds exhibit distinct electronic and mechanical properties as compared to corresponding mononitride, TiN. The first non-noble metal pernitride,TiN2 exhibits crystal structure that consists of single-bonded nitrogen dimers (N–N dumbbells) and It is an ultraincompressible material (bulk modulus ~385 GPa). TiN2 is metallic and fully recoverable to ambient conditions and is stable in air. On the other hand Cubic-Ti3N4 is dynamically unstable below 5 GPa but it is the first known semiconducting nitride of titanium and exhibits a crystal structure with coordination numbers of Ti and N that are much higher than usual metal mononitrides with the rocksalt structure. |
Thursday, March 8, 2018 2:03PM - 2:15PM |
S38.00015: New group-14 element pernitrides synthesized at high pressure and temperature Ken NIWA, Hirokazu OGASAWARA, Tomoya Inagaki, Masashi HASEGAWA Recent development in high pressure technique allows successful synthesizing novel materials as well as experimental exploring the deep inside of the earth and the condensed matter physics. We have been focusing on the nitrides and recently succeeded in the synthesis of the last remaining platinum group element pernitrides (RhN2 and RuN2) and 3d transition metal nitrides (NiAs-type FeN and CoN2) under high pressure. Here, we would like to show new experimental results on the recent high-pressure synthesis of novel group-14 element pernitrides by using laser-heated diamond anvil cell and advanced characterization techniques of synchrotron radiation and Raman scattering etc. The direct nitridation of group-14 elements (Si, Ge and Sn) at 60 GPa resulted in the formation of pyrite-form of pernitrides, which is very interesting because the A3N4 (A=Si, Ge and Sn) have long time been known as the only nitrides of grou-14 elements so far. The synthesized pernitrides were quenched into ambient pressure and the quasi-single bonded nitrogen was evaluated based on the experimental data. We would like to discuss the details and crystal chemistry of group-14 element pernitrides. |
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