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Electro-responsivity of ionic liquid boundary layers in a polar solvent revealed by neutron reflectance
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science.
KTH, School of Industrial Engineering and Management (ITM), Machine Design (Dept.). (System and Component Design)
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Surface and Corrosion Science.
KTH, School of Industrial Engineering and Management (ITM), Machine Design (Dept.). (System and Component Design)
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2018 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 148, no 19, article id 193806Article in journal (Refereed) Published
Abstract [en]

Using neutron reflectivity, the electro-responsive structuring of the non-halogenated ionic liquid (IL) trihexyl(tetradecyl)phosphonium-bis(mandelato)borate, [P6,6,6,14][BMB], has been studied at a gold electrode surface in a polar solvent. For a 20% w/w IL mixture, contrast matched to the gold surface, distinct Kiessig fringes were observed for all potentials studied, indicative of a boundary layer of different composition to that of the bulk IL-solvent mixture. With applied potential, the amplitudes of the fringes from the gold-boundary layer interface varied systematically. These changes are attributable to the differing ratios of cations and anions in the boundary layer, leading to a greater or diminished contrast with the gold electrode, depending on the individual ion scattering length densities. Such electro-responsive changes were also evident in the reflectivities measured for the pure IL and a less concentrated (5% w/w) IL-solvent mixture at the same applied potentials, but gave rise to less pronounced changes. These measurements, therefore, demonstrate the enhanced sensitivity achieved by contrast matching the bulk solution and that the structure of the IL boundary layers formed in mixtures is strongly influenced by the bulk concentration. Together these results represent an important step in characterising IL boundary layers in IL-solvent mixtures and provide clear evidence of electro-responsive structuring of IL ions in their solutions with applied potential.

Place, publisher, year, edition, pages
American Institute of Physics (AIP), 2018. Vol. 148, no 19, article id 193806
Keywords [en]
Cross level, environmental management, interplay, spatial planning, strategic planning
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-222497DOI: 10.1063/1.5001551ISI: 000432853800010PubMedID: 30307199Scopus ID: 2-s2.0-85041289749OAI: oai:DiVA.org:kth-222497DiVA, id: diva2:1181941
Note

QC 20180212

Available from: 2018-02-12 Created: 2018-02-12 Last updated: 2024-04-02Bibliographically approved
In thesis
1. Sustainable Lubrication and Tribotronics enabled by Ionic Materials
Open this publication in new window or tab >>Sustainable Lubrication and Tribotronics enabled by Ionic Materials
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Developments in machine design play a crucial role in the global endeavor towards sustainability. The potential for energy conservation and emission reduction has pushed lubrication research to the forefront, with the lubricant considered to be a vital machine component. As a result of the need for high machine efficiency and longevity, as well as that of greener lubricants, ionic liquids (ILs) are gaining attention for lubrication applications, especially in combination with biodegradable oils. ILs also present a unique opportunity for developing active lubrication, tribotronic systems. To make them an industrially viable option, however, an in-depth understanding of IL lubrication behavior is required. In this doctoral work, investigations of the tribologically relevant ionic boundary films formed by non-halogenated ILs dispersed in a carrier medium (polar solvent or bio-oil) were conducted using a variety of tribological techniques and neutron reflectance. The effect of external actuation by electric potential on the extent, ionic composition, and tribological relevance of the interfacial boundary films was also studied. The results revealed that the ionic architecture and the condition of IL in the oil play an important role in defining the lubricity of the adsorbed boundary films. Clear electroresponsivity was also observed across methods, with the relative concentration of cations and anions in the interfacial film and the lubricating film thickness changing with the electric potential bias. It was established that the anions, playing an anchor role on the surface, are crucial for the formation of robust load-carrying boundary films. A methodology using electrochemical impedance spectroscopy was developed for measuring and characterizing the electric conductivity of complex lubricating greases with ionic and non-ionic additives. According to these measurements, the electrical characteristics of greases depend on the interactions of IL with the grease matrix. Overall, this work contributes towards the development of sustainable lubrication and tribotronic systems using ILs.

Abstract [sv]

Utvecklingen inom ämnesområdet maskinkonstruktion spelar en avgörande roll i den globala strävan mot hållbarhet. Potentialer för energibesparing och utsläppsminskningar har drivit på forskningen om smörjmedel och smörjmedlet anses idag vara ett viktigt maskinelement. Som ett resultat av behovet av hög verkningsgrad, lång livslängd samt miljövänligare smörjmedel, har jonvätskor (eng. Ionic Liquids) fått uppmärksamhet inom smörjtillämpningar, särskilt i kombination med biologiskt nedbrytbara oljor. Jonvätskor ger även en unik möjlighet att utveckla tribotroniska system för aktiv smörjning. För att göra dem industriellt gångbara krävs dock en djupgående förståelse för jonvätskors smörjegenskaper. Inom ramen för detta doktorandprojekt genomfördes undersökningar av de smörjfilmer som bildas i kontakters gränssnitt av icke-halogenerade jonvätskor dispergerade i ett polärt lösningsmedel eller en bioolja. En mängd olika tribologiska mätinstument, bland annat neutronreflektans, användes i projektet. Smörjfilmens egenskaper under inverkan av en extern aktivering via en elektrisk potential studerades även genom att mäta filmtjocklek, jonsammansättning samt tribologisk relevans i gränsskikten. Resultaten visade att den joniska arkitekturen och tillståndet för jonvätskan i oljan spelar en viktig roll för att definiera smörjförmågan hos de adsorberade gränsfilmerna. Tydliga reaktioner på en pålagd elektrisk potential observerades genom att mäta förändringar av den relativa koncentrationen av katjoner och anjoner i gränssnittsfilmen samt smörjfilmens tjocklek. Det konstaterades att anjonerna, som fungerar som ankare på ytan, är avgörande för bildandet av robusta lastbärande gränsfilmer. En metodik som använder elektrokemisk impedansspektroskopi utvecklades för att mäta och karakterisera den elektriska ledningsförmågan hos komplexa smörjfetter med joniska och icke-joniska tillsatser. Enligt dessa mätningar beror fetters elektriska egenskaper på interaktionen mellan jonvätskan och fettmatrisen. Sammantaget bidrar detta arbete till utvecklingen av hållbara smörjmedel samt tribotroniska system där jonvätskor används.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2022. p. 75
Series
TRITA-ITM-AVL ; 2022:9
Keywords
sustainable lubrication, ionic liquid, tribotronics, lubricating grease, neutron reflectance
National Category
Other Mechanical Engineering Mechanical Engineering Other Mechanical Engineering
Research subject
Machine Design
Identifiers
urn:nbn:se:kth:diva-310124 (URN)978-91-8040-189-0 (ISBN)
Public defence
2022-04-27, Sal F3, https://kth-se.zoom.us/j/68200171393?pwd=M0dDV3dMWEhDaHN6L3FpeFJ3UlphUT09, Lindstedtsvägen 26-28, Stockholm, 09:00 (English)
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Supervisors
Available from: 2022-04-05 Created: 2022-03-28 Last updated: 2025-02-14Bibliographically approved

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Pilkington, Georgia A.Bergendal, ErikReddy, Akepati BhaskarGlavatskih, SergeiRutland, Mark W.

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Pilkington, Georgia A.Harris, KathrynBergendal, ErikReddy, Akepati BhaskarGlavatskih, SergeiRutland, Mark W.
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