Browsing by Author "Maynard-Casely, HE"

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    Accurate H-atom parameters for the two polymorphs of L-histi­dine at 5, 105 and 295 K
    (International Union of Crystallography, 2021-10-01) Novelli, G; McMonagle, CJ; Kleemiss, F; Probert, MR; Puschmann, H; Grabowsky, S; Maynard-Casely, HE; McIntyre, GJ; Parsons, S
    The crystal structure of the monoclinic polymorph of the primary amino acid L-histi­dine has been determined for the first time by single-crystal neutron diffraction, while that of the orthorhombic polymorph has been reinvestigated with an untwinned crystal, improving the experimental precision and accuracy. For each polymorph, neutron diffraction data were collected at 5, 105 and 295 K. Single-crystal X-ray diffraction experiments were also performed at the same temperatures. The two polymorphs, whose crystal packing is interpreted by intermolecular interaction energies calculated using the Pixel method, show differences in the energy and geometry of the hydrogen bond formed along the c direction. Taking advantage of the X-ray diffraction data collected at 5 K, the precision and accuracy of the new Hirshfeld atom refinement method im­ple­mented in NoSpherA2 were probed choosing various settings of the functionals and basis sets, together with the use of explicit clusters of molecules and enhanced rigid-body restraints for H atoms. Equivalent atomic coordinates and aniso­tropic displacement parameters were com­pared and found to agree well with those obtained from the corresponding neutron structural models.© International Union of Crystallography
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    Carbon molecules in space: a thermal equation of state study of solid hexamethylenetetramine
    (Australian Institute of Physics, 2020-02-04) Novelli, G; McIntyre, GJ; Maynard-Casely, HE; Marshall, WG; Kamenev, KV; Parsons, S
    Properties such as compressibility, thermo-elasticity and the energy landscape remain unknown for many organic compounds under conditions encountered on extraterrestrial planets and moons and in space. In this study, a thermal Equation of State (EoS) for the crystalline solid hexamethylenetetramine was determined by neutron powder diffraction in the temperature and pressure ranges of 113-480 K and 0-5 GPa, respectively. The material was chosen as a molecular model for its high symmetry and its property of remaining in the same phase throughout the experimental conditions selected to simulate the planetary environments. Equations of States (EoSs) show how the thermodynamic variables of temperature (T), pressure (P) and volume (V) are inter-related. The ideal gas law, PV = nRT, is an example of an EoS which is used as a simple but effective model to explain the properties of gases. More complex EoSs, where the assumption of ideality is relaxed, can be applied to solids in order to describe how the geometry and energy transform when they experience dramatic changes in their environment. Such information acquires enormous importance in planetary materials science, where scientists are trying to understand the fate of carbon, the fourth most abundant element in our galaxy, in the context of the origin of life and planetary environments. Despite the large heterogeneity of galactic and interstellar regions, the organic chemistry of the universe seems to follow common pathways. Molecules of high astrobiological and astrophysical relevance such as amino acids, polyaromatic hydrocarbons, and N-heterocycles have been identified across the solar system, but how they behave under such varied conditions is a question yet to be answered. Key to our approach was the determination of how the internal energy (U), entropy (S) and the Gibbs free energy (G) vary with pressure not only computationally, but also, and for the first time, experimentally. A new method has been developed, able to transform directly variable-PT crystallographic data into thermodynamic information. Although it is quite common to model thermal expansion at ambient pressure with a VTEoS, and compression at ambient temperature using a PV-EoS, determinations of PVT-EoSs are much less common, particularly for organic materials. This paucity of PTV-EoSs reflects the difficulty of varying pressure and temperature simultaneously in crystallographic experiments, especially at reduced temperatures. The task was addressed in this study by the variable-temperature insert for the Paris-Edinburgh press available on the PEARL instrument at the ISIS Neutron Spallation Source (UK). The results were successfully combined with periodic DFT (Figure 1) and other semiempirical calculations, where pressure and temperature can be included at little time cost, enabling the stability profile of the material to be understood, right down to the level of individual intermolecular interactions.
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    Cation order and magnetic behaviour in mixed metal bismuth scheelite Bi3FeMo2O12
    (International Union of Crystallography, 2021-08-14) Saura-Múzquiz, M; Mullens, BG; Liu, J; Vogt, T; Maynard-Casely, HE; Avdeev, M; Kennedy, BJ
    The scheelites are a family of compounds with chemical formula ABO4, and a characteristic crystal structure consisting of AO8 dodecahedra and BO4 tetrahedra. This structure is flexible and can accommodate a large variety of cations with a range of atomic radii and valence combinations. Scheelite-type oxides, such as CaWO4, BiVO4 and NaLa(MoO4)2 have been extensively studied due to their diverse range of physical and electronic properties [1]. In particular, Bi3+ containing molybdates have been found to be efficient photocatalysts due to the strong repulsive force of the 6s2 lone pair of Bi3+, resulting in distortion of the BO4 tetrahedra and alteration of the band gap [2, 3]. In 1974 Bi3FeMo2O12 (BFMO) was reported as the first scheelite-type compound containing trivalent cations on the tetrahedral sites [4]. Interestingly, two different polymorphs of BFMO can be isolated by varying the synthesis conditions [5]. The tetragonal scheelitetype polymorph, described by space group I41/a with a = 5.32106(13) Å and c = 11.656(4) Å, can be prepared by a sol-gel route from aqueous solution of the constituent ionic species and has a disordered arrangement of the Fe and Mo cations. When heated above 500 °C, a 2:1 ordering of the Mo and Fe cations occurs, which lowers the symmetry to monoclinic (C2/c). The corresponding superstructure has a tripling of the a axis (a = 16.9110 (3) Å, b = 11.6489(2) Å, c= 5.25630(9) Å, β = 107.1395(11)°). The two structures are illustrated in Figure 1. In the present study, both polymorphs of BFMO were synthesized and their structure and magnetic properties characterized using a combination of powder diffraction, microscopy and magnetometry techniques. In situ neutron powder diffraction (NPD) measurements of the structural evolution of disordered tetragonal BFMO with increasing temperature showed that no amorphization takes place prior to the formation of the ordered monoclinic phase. The lack of a structural break-down, despite the substantial cation movement required in such a transformation, suggests that a certain degree of local cation order exists in the “disordered” tetragonal phase, facilitating the direct conversion to the fully ordered monoclinic structure. Instead of the expected amorphization and recrystallization, the conversion takes place via a 1st order phase transition, with the tetragonal polymorph exhibiting negative thermal expansion prior to its conversion into the monoclinic structure. Zero-field-cooled/field-cooled and field-dependent magnetization curves of the monoclinic structure revealed the existence of a magnetic transition below 15 K. The long-range nature of the low temperature magnetic structure in the monoclinic polymorph was verified by high-resolution NPD data, which revealed the emergence of an incommensurate magnetic structure. There is no evidence for long-range magnetic order in the tetragonal polymorph. This is, to the best of our knowledge, the first study of the phase transition mechanism and magnetic properties of this complex system and represents a milestone in the structural understanding and targeted design of Bi3+ containing molybdates as efficient photocatalysts. © 2021 The Authors
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    Cation order in mixed metal bismuth scheelite Bi3FeMo2O12
    (Australian Institute of Nuclear Science and Engineering (AINSE), 2020-11-11) Saura-Múzquiz, M; Gaza, M; Maynard-Casely, HE; Kennedy, BJ
    The scheelites are a family of compounds with chemical formula AB O4 where A and B can represent a variety of different cations. The highly versatile scheelite crystal structure consists of A O8 dodecahedra and B O4 tetrahedra and gives rise to a variety of interesting properties depending on the combination of cations.1 Scheelite-type oxides including CaWO4, BiVO4 and NaLa(MoO4)2 have been extensively studied for applications exploiting some of these properties including luminescence, ferroelectricity, ionic conductivity and photocatalytic activity. In particular, Bi3+ containing molybdates are efficient photocatalysts2, 3 due to the strong repulsive force of the 6s2 lone pair of Bi3+, resulting in distortion of the B O4 tetrahedra and alteration of the band gap. The compound of interest in the present study, Bi3FeMo2O12 (BFMO), was reported by Sleight et al. in 1974 as the first scheelite type compound containing trivalent cations on the tetrahedral site.4 Notably, two different polymorphs of BFMO can be isolated.5 The ideal tetragonal scheelite-type structure in space group I 41/ a (#88) can be prepared by a wet chemical route from aqueous solution of the constituent elements. Jeitschko et al. reported in 1975 that, when the tetragonal scheelite structure is heated above 600 C° for ~10 h, a 2:1 ordering of the Mo and Fe cations occurs, which lowers the symmetry to monoclinic in space group C 2/ c (#15), and gives rise to a tripling of the a axis. Here, phase pure BFMO in the disordered tetragonal structure was synthesized by a wet chemical route. The conversion from the disordered tetragonal to the ordered monoclinic structure was examined by in situ neutron powder diffraction in order to understand the temperature dependence of the phase transition and cation order in the mixed metal bismuth scheelite. The study shows no amorphization prior to the formation of the ordered monoclinic phase. Given the substantial cation movement involved in such a transformation, the lack of structural break-down suggests that a certain degree of local cation order may already exist in the tetragonal phase, facilitating the conversion into a fully ordered monoclinic structure. This hypothesis is further supported by an opening in the field-dependent magnetization curve of the tetragonal phase at 1.8 K. © The authors.
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    Characterising new planetary materials with neutron diffraction
    (Australian Institute of Nuclear Science and Engineering, 2016-11-29) Maynard-Casely, HE; Brand, HEA; Cable, ML; Hodyss, RP
    There’s a lot of hydrogen in the outer solar system; locked up with water on the icy Galilean moons of Jupiter, within the small organic molecules that rain down on Saturn’s moons Titan or even in an elusive metallic form within the centers of the gas giants. The intrinsic hydrogen-domination of planetary ices, makes studying these materials with laboratory powder diffraction very challenging. Insights into their crystalline phase behavior and the extraction of a number of thermal and mechanical properties is often only accessible with high-flux synchrotron x-ray diffraction or with neutron diffraction. Here, we will present how both the ECHIDNA and WOMBAT instruments at ACNS have been used to gain insights into new materials that have be found to exist under planetary conditions.
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    Color centers in NaCl single crystals induced by pulsed intense relativistic electron beams to simulate radiation bursts in Europa
    (IOP Publishing, 2019-03-26) Toba, R; Kikuchi, K; Imada, G; Thorogood, GJ; Hayashi, N; Maynard-Casely, HE; Suematsu, H; Nakayama, T; Suzuki, T; Niihara, K
    To simulate the burst irradiation environment of Europa, single crystals of NaCl were irradiated by pulsed intense relativistic electron beams (PIREBs) with a peak energy of 6 MeV, a current of −800 A, and a pulse width of 70 ns. After irradiation, the optical absorption of the samples was measured, and results indicated that the irradiation induced F- and F2-centers. The density of F-centers was estimated to be 8.9 × 1016 cm−3 from 1 shot of PIREB irradiation with 6 MeV. The absorbed energy to form F-centers by PIREB was comparable but slightly higher than those induced by conventional direct current accelerators. The effect of pulsed heating, which should be taken into account for the detection of NaCl on Europa, is discussed. © 2019 The Japan Society of Applied Physics
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    Consequences of long-term water exposure for bulk crystal structure and surface composition/chemistry of nickel-rich layered oxide materials for Li-ion batteries
    (Elsevier, 2020-06-10) Andersen, HL; Cheung, EA; Avdeev, M; Maynard-Casely, HE; Abraham, DP; Sharma, N
    Water exposure of layered nickel-rich transition metal oxide electrodes, widely used in high-energy lithium-ion batteries, has detrimental effects on the electrochemical performance, which complicates electrode handling and prevents implementation of environmentally benign aqueous processing procedures. Elucidating the degradation mechanisms in play may help rationally mitigate/circumvent key challenges. Here, the bulk structural consequences of long-term (>2.5 years) deuterated water (D2O) exposure of intercalation materials with compositions LixNi0.5Co0.2Mn0.3O2 (NCM523) and LixNi0.8Co0.1Mn0.1O2 (NCM811) are studied by neutron powder diffraction (NPD). Detailed inspection of the NPD data reveals gradual formation of a secondary crystalline phase in all exposed samples, not previously reported for this system. This unknown phase forms faster in liquid- compared to vapor-exposed compounds. Structural modelling of the NPD data shows a stable level of Li/Ni anti-site defects and does not indicate any significant changes in lattice parameters or hydrogen-lithium (D+/Li+) exchange in the structure. Consequently, the secondary phase formation must take place via transformation rather than modification of the parent material. X-ray photoelectron spectroscopy data indicate formation of LiHCO3/Li2CO3 at the surface and a Li-deficient oxide in the sub-surface region of the pristine compounds, and the presence of adsorbed water and transition metal hydroxides at the exposed sample surfaces. © 2020 Elsevier B.V.
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    Copper(II) coordination polymers of imdc− (H2imdc+ = the 1,3-bis(carboxymethyl)imidazolium cation): unusual sheet interpenetration and an unexpected single crystal-to-single crystal transformation
    (Royal Society of Chemistry, 2013-10-08) Abrahams, BF; Maynard-Casely, HE; Robson, R; White, KF
    The monoanion of 1,3-bis(carboxymethyl)imidazolium (H2imdc+) combines with Cu(II) to produce an undulating 2D coordination polymer of composition [Cu2(imdc)2(CH3OH)2](BF4)2·(CH3OH)(H2O) (1) in which copper acetate-like dimers, linked by imdc− ligands, act as 4-connecting centres. Cationic sheets stack on top of each other in an A, B, A, B… fashion and produce a structure that contains channels running parallel to the plane of network. Tetrafluoroborate anions are located in channels between sheets. Upon removal of coordinated and noncoordinated solvent molecules a single crystal-to-single crystal transformation occurs to yield a similar compound but with BF4 − anions now coordinated. CO2 isotherms measured at 258 and 273 K show only modest uptake of CO2 but provide an indication that the sheets move apart at elevated pressures in order to accommodate the guest molecules. A compound of composition [Cu3(OH)2(imdc)2]·SiF6·2H2O·2MeOH (3), which possesses a 3D network, is formed by the combination of copper(II) acetate, copper(II) hexafluorosilicate and Himdc. In this structure infinite parallel Cu3(OH)2 chains are linked by bridging imdc− ligands to form channels that have an approximately triangular cross-section. These channels are occupied by SiF6 2− anions in addition to solvent molecules. When copper(II) acetate is combined with Himdc in the appropriate ratio, a 1D coordination polymer of composition Cu(imdc)2 (4) is formed in which pairs of imdc− anions bridge Cu(II) centres. When the reaction is performed in the presence of NaBF4 a minor crystalline product with tetragonal symmetry is isolated in addition to the 1D coordination polymer. This compound of composition Cu2(imdc)4NaBF4·7H2O (5) consists of 2D Cu(imdc)2 networks and features an unusual mode of interpenetration. © 2013, The Royal Society of Chemistry.
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    The crystal structure of methane B at 8 GPa—an α-Mn arrangement of molecules
    (AIP Scitation, 2014-12-18) Maynard-Casely, HE; Lundegaard, LF; Loa, I; McMahon, MI; Gregoryanz, E; Nelmes, RJ; Loveday, JS
    From a combination of powder and single-crystal synchrotron x-ray diffraction data we have determined the carbon substructure of phase B of methane at a pressure of ∼8 GPa. We find this substructure to be cubic with space group I4 ¯ 3m I4¯3m and 58 molecules in the unit cell. The unit cell has a lattice parameter a = 11.911(1) Å at 8.3(2) GPa, which is a factor of √2 larger than had previously been proposed by Umemoto et al. [J. Phys.: Condens. Matter14, 10675 (2002)]. The substructure as now solved is not related to any close-packed arrangement, contrary to previous proposals. Surprisingly, the arrangement of the carbon atoms is isostructural with that of α-manganese at ambient conditions. © 2014, AIP Publishing LLC.
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    Crystallography at ANSTO’s jewel, the OPAL reactor
    (Australian Institute of Physics, 2014-09-01) Maynard-Casely, HE; McIntyre, GJ
    Australian neutron scattering leapt into the 21st century with the start up of the OPAL reactor at ANSTO in 2006. The major part of the initial success has been in crystallography, carrying on the excellent tradition established since the late 1950s at the HIFAR reactor. The combination of state-of-the-art instrumentation, support facilities, expert scientific staff, and enthusiastic users of OPAL has yielded an impressive series of scientific results, as well as a fledgling industrial programme, and has trained numerous students who are now highly respected ambassadors for neutron scattering. Here we give an overview of highlights in crystallography that have come from the capabilities offered by and around OPAL, and hint at further developments in the field. © 2014 Australian Institute of Physics Inc.
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    Current high-pressure capabilities at ACNS and future plans
    (Australian Institute of Nuclear Science and Engineering (AINSE), 2020-11-11) Maynard-Casely, HE; Booth, N; Shumack, A; Baldwin, C; White, R; Rule, KC; McIntyre, GJ; Novelli, G
    High-pressure (>1 Kbar) is a marvellous variable, which can reveal mechanical properties, structural transitions and exotic behaviours. This pairs very well with neutron scattering, where the highly penetrating nature of neutron beams is idea for accessing sample within complex sample environments. The Australian Centre for Neutron Scattering (ACNS) has developed a number of capabilities for high-pressure experiments, mainly revolving around the use of our Paris-Edinburgh press but more recently with miniature diamond-anvil cells. Some of these, such as our ability to compress radioactive samples as well as combining high-pressure and high-electric fields are unique in the world. Here we review the high pressure capabilities at ACNS, and outline some directions for capabilities and measurements.
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    Effect of high pressure on the crystal structures of polymorphs of l-histidine
    (American Chemical Society, 2020-11-06) Novelli, G; Maynard-Casely, HE; McIntyre, GJ; Warren, MR; Parsons, S
    The effect of pressure on the crystal structures of the two ambient-pressure polymorphs of the amino acid l-histidine has been investigated. Single-crystal diffraction measurements, up to 6.60 GPa for the orthorhombic form I (P212121) and 6.85 GPa for the monoclinic form II (P21), show their crystal structures undergo isosymmetric single-crystal-to-single-crystal first-order phase transitions at 4.5 and 3.1 GPa to forms I′ and II′, respectively. Although the similarity in crystal packing and intermolecular interaction energies between the polymorphs is remarkable at ambient conditions, the manner in which each polymorph responds to pressure is different. Form II is found to be more compressible than form I, with bulk moduli of 11.6(6) GPa and 14.0(5) GPa, respectively. The order of compressibility follows the densities of the polymorphs at ambient conditions (1.450 and 1.439 g cm–3 for phases I and II, respectively). The difference is also related to the space-group symmetry, the softer monoclinic form having more degrees of freedom available to accommodate the change in pressure. In the orthorhombic form, the imidazole-based hydrogen atom involved in the H-bond along the c-direction swaps the acceptor oxygen atom at the transition to phase I′; the same swap occurs just after the phase transition in the monoclinic form and is also preceded by a bifurcation. Concurrently, the H-bond and the long-range electrostatic interaction along the b-direction form a three-centered H-bond at the I to I′ transition, while they swap their character during the II to II′ transition. The structural data were interpreted using periodic-density-functional theory, symmetry-adapted perturbation theory, and semiempirical Pixel calculations, which indicate that the transition is driven by minimization of volume, the intermolecular interactions generally being destabilized by the phase transitions. Nevertheless, volume calculations are used to show that networks of intermolecular contacts in both phases are very much less compressible than the interstitial void spaces, having bulk moduli similar to moderately hard metals. The volumes of the networks actually expand over the course of both phase transitions, with the overall unit-cell-volume decrease occurring through larger compression of interstitial void space. © 2020 American Chemical Society
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    The effect of sterically active ligand substituents on gas adsorption within a family of 3D Zn-based coordination polymers
    (American Chemical Society, 2020-06-09) Abrahams, BF; Babarao, R; Dharma, AD; Holmes, JL; Hudson, TA; Maynard-Casely, HE; McGain, F; Robson, R; Waite, KF
    An investigation of the adsorption properties of two structurally related, 3D coordination polymers of composition Zn(2-Mehba) and Zn(2,6-Me2hba) (2-Mehba = the dianion of 2-methyl-4-hydroxybenzoic acid and 2,6-Me2hba = the dianion of 2,6-dimethyl-4-hydroxybenzoic acid) is presented. A common feature of these structures are parallel channels that are able to accommodate appropriately sized guest molecules. The structures differ with respect to the steric congestion within the channels arising from methyl groups appended to the bridging ligands of the network. The host network, Zn(2-Mehba), is able to take up appreciable quantities of H2 (77 K) and CO2 and CH4 (298 K) in a reversible manner. In regard to the adsorption of N2 by Zn(2-Mehba), there appears to be an unusual temperature dependence for the uptake of the gas such that when the temperature is increased from 77 to 298 K the uptake of N2 increases. The relatively narrow channels of Zn(2,6-Me2hba) are too small to allow the uptake of N2 and CH4, but H2 molecules can be adsorbed. A pronounced step at elevated pressures in CO2 and N2O isotherms for Zn(2,6-Me2hba) is noted. Calculations indicate that rotation of phenolate rings leads to a change in the available intraframework space during CO2 dosing. © 2020 American Chemical Society
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    Exploration of organic minerals on Saturn's moon Titan
    (International Union of Crystallography, 2021-08-14) Maynard-Casely, HE; Hodyss, R; Vu, TH; Malaska, MJ; Choukroun, M; Cable, ML; Runčevski, t
    Titan, the largest moon of Saturn, has been revealed by the Cassini-Huygens mission to be a fascinating and quite Earth-like world. Among the parallels to Earth, which includes the lakes, seas, fluvial and pluvial features on its surface, is an inventory of organic minerals [1]. However, where on Earth these organic minerals are only found in niche environments, on Titan they are likely to be the dominant surface-shaping materials. Titan’s organic minerals are formed primarily from photochemistry induced by UV radiation and charged particles from Saturn’s magnetosphere, which cause molecular nitrogen and methane (the primary components of the upper atmosphere) to generate into various CHN-containing species that deposit onto the surface [2]. Despite the ubiquity of these organic minerals upon the surface, it is difficult to understand their influence on the landscape and as, in some cases, even their crystal structure is unknown let alone wider physical properties[3]. Hence we have undertaken an experimental program to address this, and are currently focusing on the missing crystal structure and physical property understanding of a number of molecular solids and co-crystals that are likely to be organic minerals upon Titan. Using a combination of neutron diffraction, Xray diffraction and Raman scattering we have studied molecular solids including ethane, acrylonitrile, acetonitrile, butadiene and propyne, and explored what co-crystal form from the inventory of Titan’s molecules. This contribution will report highlights from these investigations. © The Authors
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    Exploring Jupiter's icy moons with old techniques and big facilities - new insights on sulfuric acid hydrate
    (Australian Institute of Physics, 2014-02-07) Maynard-Casely, HE; Avdeev, M; Wallwork, KS; Brand, HEA
    Sulfuric acid hydrates have been proposed to be abundant on the surface of Europa, and hence would be important planetary-forming materials for this moon and its companions Ganymede and Callisto. Understanding of the surface features and subsurface of these moons could be advanced by firmer knowledge of the icy materials that comprise them, insight into which can be drawn from firmer knowledge of physical properties and phase behaviour of the candidate materials. We wish to present results from a study that started with the question ‘What form of sulfuric acid hydrate would form on the surface of Europa?’, with this study undertaken with in situ powder diffraction at Australian Synchrotron and ANSTO. We have used the Powder Diffraction beamline at Australian synchrotron and the Echidna (High-resolution neutron powder diffraction) instrument of the Australian Nuclear Science and Technology Organization, to obtain a number of new insights into the crystalline phases formed from H2SO4/H2O mixtures. These instruments have enabled the discovery a new water-rich sulfuric acid hydrate form, improved structural characterisation of existing forms and charting of the phase diagram of this fundamental binary system. This has revealed exciting potential for understanding more about the surface of Europa from space, perhaps even providing a window into its past.
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    Exploring Jupiter's icy moons with old techniques and big facilities-new insights on sulfuric acid hydrates
    (American Geophysical Union, 2013-12-13) Maynard-Casely, HE; Avdeev, M; Brand, HEA; Wallwork, KS
    Sulfuric acid hydrates have been proposed to be abundant on the surface of Europa [1], and hence would be important planetary forming materials for this moon and its companions Ganymede and Callisto. Understanding of the surface features and subsurface of these moons could be advanced by firmer knowledge of the icy materials that comprise them [2], insight into which can be drawn from firmer knowledge of physical properties and phase behaviour of the candidate materials. We wish to present results from a study that started with the question ';What form of sulfuric acid hydrate would form on the surface of Europa'. The intrinsic hydrogen-domination of planetary ices, makes studying these materials with laboratory powder diffraction very challenging. Insights into their crystalline phase behavior and the extraction of a number of thermal and mechanical properties is often only accessible with high-flux synchrotron x-ray diffraction and utilization of the large scattering cross section with neutron diffraction. We have used the Powder Diffraction beamline at Australian synchrotron [4] and the Echidna (High-resolution neutron powder diffraction) instrument of the Australian Nuclear Science and Technology Organization, [5] to obtain an number of new insights into the crystalline phases formed from sulfruic acid and water mixtures. These instruments have enabled the discovery a new water-rich sulfuric acid hydrate form [6], improved structural characterisation of existing forms [7] and a charting the phase diagram of this fundamental binary system [8]. This has revealed exciting potential for understanding more about the surface of Europa from space, perhaps even providing a window into its past.[1] Carlson, R.W., R.E. Johnson, and M.S. Anderson, Science, 1999. 286(5437): p. 97-99. [2] Fortes, A.D. and M. Choukroun. Space Sci Rev, 2010. 153(1-4): p. 185-218. [3] Blake, D., et al., Space Sci Rev,, 2012. 170(1-4): p. 341-399. [4] Wallwork, K.S., Kennedy B. J. and Wang, D., AIP Conf Proc, 2007. 879: p. 879-882. [5] Liss, K.D., et al., Phys B-Cond Mat, 2006. 385-86: p. 1010-1012. [6] Maynard-Casely, H.E., K.S. Wallwork, and M. Avdeev, (In review). [7] Maynard-Casely, H.E., H.E.A. Brand, and K.S. Wallwork, J.of App.Cryst, 2012. 45: p.1198-1207. [8] Maynard-Casely, H.E., K.S. Wallwork, and H.E.A. Brand, (In Preparation). Stages of the crystal structure determination of sulfruic acid octahydrate a) the oxygen and sulfur postions were determined from the synchrotron x-ray data b) Once neutron diffraction data was collected Fourier difference methods were used to locate hydrogen positions to determine c) the full structure of sulfuric acid octahydrate.
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    Hydrates under pressure - new insights from sulfuric acid hydrates
    (Australian Institute of Physics, 2016-02-04) Maynard-Casely, HE; Hattori, T; Sano-Furukawa, A; Machida, S; Komatsu, K
    Hydrates are a rich and diverse class of materials that display a wide range of structures and properties – a feature that is only exaggerated when they are subjected to high-pressures. Consequently, these have implications on our understanding of many outer solar system bodies, where hydrates are amongst the dominant materials found there. For Europa and Ganymede, two moons under intense investigation from past and future space missions, their surfaces seen to be mostly water-ice and hydrates. Despite the apparent ‘simplicity’ of these materials, we still observe very complex geological formations on these moons – including subduction. Hence, we need to understand the transformations of candidate surface materials under a range of pressure/temperature conditions in order to accurately explain the formations on these icy surfaces. One hydrate candidate material for the surfaces of these moons are sulfuric acid hydrates, formed from radiolytic sulfur (from Io) reacting with the surface ice. Sulfuric acid hydrates have already been established to have a complex phase diagram with composition. We have now used the Mito cell at the PLANET instrument to undertake the first investigation of the high-pressure behaviour of the water rich sulfuric acid hydrates. Compressing at 100 K and 180 K we see that the hemitriskaidekahydrate becomes the stable water-rich hydrate and observe some interesting relaxation behaviour in this material at pressure, which could have significant consequences for the interiors of Ganymede.
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    Hydrogen cyanide and butadiene as cryominerals on the surface of Titan
    (American Geophysical Union (AGU), 2021-12-17) Hodyss, RP; Vu, TH; Maynard-Casely, HE; Cable, ML; Malaska, MJ; Choukroun, M
    The Cassini-Huygens mission has revealed a wide variety of Earth-like landforms on Titan’s surface: plains, mountains, plateaux, dunes, lakes, seas and rivers. Titan’s surface appears to be constructed from organic materials and ice, rather than rocks and minerals that make up Earth’s surface. At a surface temperature of ~92 K, non-covalent interactions such as hydrogen bonding and van der Waals forces are sufficiently strong to enable stable interactions among these organic molecules, which form an entirely new class of cryogenic organic minerals (naturally occurring compounds with a specific composition). Photochemical models, partially validated by Huygens surface measurements and Cassini spacecraft measurements as well as Earth-based observations, allow us to make an initial guess for the composition of Titan’s surface. Simple organic molecules like acetylene, hydrogen cyanide, acetonitrile, etc. in their solid form are expected to be important constituents of the surface. However, many of their crystal structures and properties in solid state, at Titan relevant temperatures, are ambiguous. It is highly likely that crystalline polymorphs of some of these molecules are yet to be discovered. The crystal structure of a solid material is one of its most fundamental properties, and is necessary for understanding of intermolecular interactions and for prediction of mechanical and chemical properties – such as the ability to support deep valleys, high canyon walls, and resistance to erosion. We will present new data on the crystal structure and physical properties of two molecules thought to be present in significant quantities on Titan’s surface: hydrogen cyanide and butadiene. We have used Raman spectroscopy and cryogenic powder X-ray diffraction to better understand the phase behavior and structure of these materials under Titan conditions. While hydrogen cyanide is known to undergo a phase transition at ~170 K, the behavior of butadiene at low temperature has not been explored in detail. Our data indicates a new monoclinic structure for butadiene, and a possible new structure for HCN at low temperature. We will also present the implications of these results for Titan’s geology and evolution.
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    In situ studies of structural changes in DME synthesis catalyst with synchrotron powder diffraction
    (Elsevier, 2014-09-22) Kabir, KB; Maynard-Casely, HE; Bhattacharya, S
    Structural changes in a bi-functional dimethyl ether synthesis catalyst (CuO-ZnO-Al2O3-MgO + γ-Al2O3, BFC), a methanol synthesis catalyst (CuO-ZnO-Al2O3-MgO, MSC) and a methanol dehydration catalyst (γ-Al2O3, MDC), were studied using X-ray synchrotron powder diffraction. The catalysts were first reduced in 10% H2/He and then treated in a gas containing CO, H2 and CO2. Measurements were taken at temperatures between 50 °C and 500 °C. These measurements were complemented by ex-situ techniques—thermogravimetry (TG) and scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDS). The X-ray diffraction (XRD) results showed that the copper oxide phase, present in methanol synthesis and bi-functional catalysts, reduced to form Cu0 after reduction. No further chemical changes were observed for these catalysts. γ-Al2O3 was resistant to structural and chemical changes. The copper crystallite sizes of the methanol and bi-functional catalysts were found to increase with temperature. The extent of deactivation was higher for CuO-ZnO-Al2O3-MgO + γ-Al2O3 compared to CuO-ZnO-Al2O3-MgO. © 2014, Elsevier B.V.
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    Investigating carbon molecules with pressure-volume-temperature equations of state
    (Australian Nuclear Science and Technology Organisation, 2019-09-03) Novelli, G; McIntyre, GJ; Maynard-Casely, HE; Funnell, NP; Marshall, WG; Kamenev, KV; Parsons, S
    We are interested in intermolecular interactions which determine thermodynamic stability in crystalline solids and their response to changes in the external conditions. In no area is this information of more importance than in planetary materials science, where scientists are trying to understand the fate of carbon in the context of the origin of life and/or the varied planetary surfaces observed. Molecules of high astrobiological and astrophysical relevance, such as amino acids (1), polyaromatic hydrocarbons, and N-heterocycles (2), have been identified across the Universe but how they behave under such varying conditions is a question yet to be answered. Key to our approach is the determination of the internal-energy, entropy and the Gibbs free energy - not only computationally but also, and for the first time, experimentally. We have developed a new method that transforms variable-pressure (P)-temperature (T) crystallographic data into thermodynamic information. Equations of State (EoSs) are the models of choice to fit these data, describing how pressure, temperature, and volume (V) are inter related in solid phases. Although it is quite common to model thermal expansion at ambient pressure with a VT equation of state (EoS), and compression at ambient temperature using a PV-EoS, determinations of PVT-EoSs are much less common, particularly for molecular materials (3). The paucity of PVT-EoSs reflects the difficulty in varying pressure and temperature simultaneously in crystallographic experiments, especially at reduced temperatures. These difficulties are addressed by the variable temperature insert for the Paris-Edinburgh press available on the PEARL instrument at the ISIS Neutron Spallation Source (4) and by the cryofurnace for the Merrill-Bassett cell available on the KOALA instrument at the ANSTO OPAL reactor (5). The results can then be combined with Periodic DFT and other semi-empirical calculations, where pressure and temperature can be included at little time cost, enabling the stability profile of a material to be understood, right down to the level of individual intermolecular interactions. Many classes of structure-directing intermolecular interactions involve hydrogen atoms: hydrogen bonds are an obvious example, but hydrogens can also be involved in dispersion and electrostatic interactions. The responses of different kind of crystalline organics containing these interactions, such as hexamethylenetetramine, naphthalene, histidine, and alanine are to be studied using powder and single-crystal neutron diffraction up to 5 GPa and between 105-480 K. We are specifically using neutron diffraction for the experiments because of its sensitivity to locate hydrogen atoms. Additionally, the penetrating nature of neutron radiation means that complete, high-quality data can be obtained for samples in elaborate extreme-conditions environments.