We use transmission optical microscopy to observe cyclopentane hydrate growth in sub-mm, open glass capillaries, mimicking cylindrical pores. The capillary is initially loaded with water and the guest fluid (cyclopentane) and thus possesses three menisci, that between water and cyclopentane (CP) in the middle and two menisci with the vapors at the ends. At temperatures T below the equilibrium temperature T ≈ 7 °C, the hydrate nucleates on the water-CP meniscus, rapidly coating it with an immobile, polycrystalline crust. Continued movement of the other two menisci provides insights into hydrate growth mechanisms, via the consumption and displacement of the fluids. On water-wet glass, the subsequent growth consists of a hydrate "halo" creeping with an underlying water layer on the glass on the CP side of the meniscus. Symmetrically, on CP-wet glass (silane-treated), a halo and a CP layer grow on the water side of the interface. No halo is observed on intermediate wet glass. The halo consists of an array of large monocrystals, over a thick water layer at low supercooling (ΔT = T - T below 5 K), and a finer, polycrystalline texture over a thinner water layer at higher ΔT. Furthermore, the velocity varies as ΔT, with α ≈ 2.7, making the early stages of growth very similar to gas hydrate crusts growing over water-guest interfaces. Beyond a length in the millimeter range, the halo and its water layer abruptly decelerate and thin down to submicron thickness. The halo passes through the meniscus with the vapor without slowing down or change of texture. A model of the mass balance of the fluids helps rationalize all of these observations.
Growth of gas hydrates as fast-growing polycrystalline crusts at interfaces between water and guest phases is well documented, but the mechanisms of hydrate growth on solid substrates are much less known. We report here on cyclopentane (CP) hydrate spreading on glass (fused silica) under CP. As seen for methane hydrate by Beltrán and Servio (Cryst. Growth Des.20101043394347), CP hydrate grows on glass as a “halo” radiating from the contact line of a “primary” drop. Complementary optical microscopies at micron resolution here allow identification of the mechanisms of halo growth and melting. We conclude that forms of water on the substrate control halo spreading, namely, a precursor film near the contact line and a breath figure (dew) condensed from the CP (halo spreading at ≤2 μm s–1 at T ≈ 0 °C or subcooling ∼7 °C), and “leap-frogging” (at ∼10 μm s–1) over “secondary” drops left behind by melting a previous halo. Halo thickening, about 5 nm s–1, is attributed to water condensation, either incorporation of water dissolved in CP (like ablimation) or settling of water “fog” from the CP. Halos spread slower on untreated, compared to hydrophilic, glass, an effect attributed to the quantity of water present on the substrate; a similar trend is noted when the CP phase is not pre-equilibrated with water prior to the experiment. No hydrate halo was detected on hydrophobized (silane-treated) glass, where the breath figure is absent.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.