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Pressure-induced amorphization of noble gas clathrate hydrates
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).ORCID iD: 0000-0003-2296-4911
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Number of Authors: 92021 (English)In: Physical Review B, ISSN 2469-9950, E-ISSN 2469-9969, Vol. 103, no 6, article id 064205Article in journal (Refereed) Published
Abstract [en]

The high-pressure structural behavior of the noble gas (Ng) clathrate hydrates Ar center dot 6.5 H2O and Xe center dot 7.2 H2O featuring cubic structures II and I, respectively, was investigated by neutron powder diffraction (using the deuterated analogues) at 95 K. Both hydrates undergo pressure-induced amorphization (PIA), indicated by the disappearance of Bragg diffraction peaks, but at rather different pressures, at 1.4 and above 4.0 GPa, respectively. Amorphous Ar hydrate can be recovered to ambient pressure when annealed at >1.5 GPa and 170 K and is thermally stable up to 120 K. In contrast, it was impossible to retain amorphous Xe hydrate at pressures below 3 GPa. Molecular dynamics (MD) simulations were used to obtain general insight into PIA of Ng hydrates, from Ne to Xe. Without a guest species, both cubic clathrate structures amorphize at 1.2 GPa, which is very similar to hexagonal ice. Filling of large-sized H cages does not provide stability toward amorphization for structure II, whereas filled small-sized dodecahedral D cages shift PIA successively to higher pressures with increasing size of the Ng guest. For structure I, filling of both kinds of cages, large-sized T and small-sized D, acts to stabilize in a cooperative fashion. Xe hydrate represents a special case. In MD, disordering of the guest hydration structure is already seen at around 2.5 GPa. However, the different coordination numbers of the two types of guests in the crystalline cage structure are preserved, and the state is shown to produce a Bragg diffraction pattern. The experimentally observed diffraction up to 4 GPa is attributed to this semicrystalline state.

Place, publisher, year, edition, pages
2021. Vol. 103, no 6, article id 064205
Keywords [en]
Elastic modulus, Pressure effects
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:su:diva-192476DOI: 10.1103/PhysRevB.103.064205ISI: 000619132400002OAI: oai:DiVA.org:su-192476DiVA, id: diva2:1546332
Available from: 2021-04-21 Created: 2021-04-21 Last updated: 2023-02-03Bibliographically approved
In thesis
1. Pressure-Induced Amorphization and Distinct Amorphous States of Clathrate Hydrates
Open this publication in new window or tab >>Pressure-Induced Amorphization and Distinct Amorphous States of Clathrate Hydrates
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis summarizes a study on the pressure-induced amorphization (PIA) and structures of amorphous states of clathrate hydrates (CHs).

PIA involves the transition of a crystalline material into an amorphous solid in response of mechanical compression at temperatures well below the melting point. The first material observed to undergo PIA was hexagonal ice. More recently it was shown that compounds of water undergo the same phenomenon without decomposition, despite the presence of solutes. CHs, which are crystalline inclusion compounds consisting of water molecules encaging small guest species, undergo PIA at ca. 1–4 GPa below 145 K. The obtained amorphous CH phase can be further densified on isobaric heating at high pressure. This annealing step enables to retain an amorphous material on pressure release. There has been a significant amount of studies into the understanding of the nature of PIA and transformations between amorphous phases of pure ice. The aim of this thesis has been the understanding of the PIA in CHs and its relation to pure ice. New information on the nature of PIA and subsequent amorphous-amorphous transitions in CH systems were gained from structural studies and in situ neutron diffraction played pivotal role due to the sensitivity of neutrons to the light element hydrogen. Here a generalized understanding of the PIA in CHs and a clear image of amorphous CH structures are presented.

Abstract [sv]

Denna avhandling sammanfattar en studie om tryckinducerad amorfisering (TIA) av klatrathydrater (KH), samt strukturer av amorfa tillstånd där av.

TIA är övergången av ett kristallint material till ett amorft fast ämne som svar på mekanisk kompression vid temperaturer långt under smältpunkten. Det första materialet som observerades genomgå TIA var hexagonal is. Därefter har det visat sig att det finns strukturer av vatten som trots närvaron av lösta ämnen genomgår samma fenomen utan att strukturen bryts ned. KH:er är kristallina inneslutningskomplex som består av ett gitter av vattenmolekyler, vilka omsluter små gästmolekyler. Dessa strukturer genomgår TIA vid ca. 1–4 GPa vid temperaturer under 145 K. Den erhållna amorfa KH-fasen kan förtätas ytterligare vid isobarisk uppvärmning under högt tryck. Detta steg gör det möjligt att behålla ett amorft material vid tryckavlastning. Det har gjorts en betydande mängd studier av TIA:s natur och omvandlingar mellan amorfa faser av ren is. Syftet med denna avhandling har varit att förstå TIA i KH:er och dess relation till ren is. Ny information om karaktären hos TIA och efterföljande amorfa-amorfa övergångar i KH-system erhölls från strukturella studier, där in situ neutrondiffraktion spelade en avgörande roll tack vare neutronernas känslighet för det lätta elementet väte. Utifrån detta arbete presenteras här en generaliserad förståelse av TIA i KH samt en tydlig bild av amorfa KH-strukturer.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University, 2023. p. 78
Keywords
Clathrate Hydrates, Pressure-Induced Amorphization, Amorphous States, Glassy States, Ice, Neutron Diffraction, Klatrathydrater, Tryckinducerad Amorfisering, Amorfa tillstånd, Glasartade tillstånd, Is, Neutrondiffraktion
National Category
Condensed Matter Physics Materials Chemistry
Research subject
Physical Chemistry
Identifiers
urn:nbn:se:su:diva-214449 (URN)978-91-8014-186-4 (ISBN)978-91-8014-187-1 (ISBN)
Public defence
2023-03-31, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
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Available from: 2023-03-08 Created: 2023-02-03 Last updated: 2023-03-01Bibliographically approved

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B. Brant Carvalho, Paulo H.Lyubartsev, Alexander P.Häussermann, Ulrich

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