Hydrate-phobic surfaces: fundamental studies in clathrate hydrate adhesion reduction

Clathrate hydrate formation and subsequent plugging of deep-sea oil and gas pipelines represent a significant bottleneck for deep-sea oil and gas operations. Current methods for hydrate mitigation are expensive and energy intensive, comprising chemical, thermal, or flow management techniques. In this paper, we present an alternate approach of using functionalized coatings to reduce hydrate adhesion to surfaces, ideally to a low enough level that hydrodynamic shear stresses can detach deposits and prevent plug formation. Systematic and quantitative studies of hydrate adhesion on smooth substrates with varying solid surface energies reveal a linear trend between hydrate adhesion strength and the practical work of adhesion (γ[superscript total][1 + cos θ[subscript rec]]) of a suitable probe liquid, that is, one with similar surface energy properties to those of the hydrate. A reduction in hydrate adhesion strength by more than a factor of four when compared to bare steel is achieved on surfaces characterized by low Lewis acid, Lewis base, and van der Waals contributions to surface free energy such that the practical work of adhesion is minimized. These fundamental studies provide a framework for the development of hydrate-phobic surfaces, and could lead to passive enhancement of flow assurance and prevention of blockages in deep-sea oil and gas operations.Massachusetts Institute of Technology. Energy Initiative (Chevron Corporation)Massachusetts Institute of Technology. Dept. of Mechanical EngineeringNational Research Council (U.S.) (Postdoctoral Fellowship

Polydispersity effects in poly(isoprene-b-styrene-b-ethylene oxide) triblock terpolymers

At time of publication all authors were at the University of Minnesota. Christopher Ellison is currently Asst. Professor at the University of Texas at Austin.Four hydroxyl-terminated poly (isoprene-b-styrene) diblock copolymers with comparable molecular weights and compositions (equivalent volume fractions of polyisoprene and polystyrene) but different polystyrene block polydispersity indices (Mw/Mn=1.06, 1.16, 1.31, 1.44) were synthesized by anionic polymerization using either sec-butyllithium or the functional organolithium 3-triisopropylsilyloxy-1-propyllithium. Poly (ethylene oxide) (PEO) blocks were grown from the end of each of these parent diblocks to yield four series of poly(isoprene-b-styrene-b-ethylene oxide) (ISO) triblock terpolymers that were used to interrogate the effects of varying the polydispersity of the middle bridged polystyrene block. In addition to the neat triblock samples, 13 multicomponent blends were prepared at four different compositions from the ISO materials containing a polystyrene segment with Mw/Mn=1.06; these blends were used to probe the effects of increasing the polydispersity of the terminal PEO block. The melt-phase behavior of all samples was characterized using small-angle X-ray scattering and dynamic mechanical spectroscopy. Numerous polydispersity-driven morphological transitions are reported, including transitions from lamellae to core-shell gyroid, from core-shell gyroid to hexagonally packed cylinders, and from network morphologies [either O70 (the orthorhombic Fddd network) or core-shell gyroid] to lamellae. Domain periodicities and order-disorder transition temperatures also vary with block polydispersities. Self-consistent field theory calculations were performed to supplement the experimental investigations and help elucidate the molecular factors underlying the polydispersity effects. The consequences of varying the polydispersity of the terminal PEO block are comparable to the polydispersity effects previously reported in AB diblock copolymers. Namely, domain periodicities increase with increasing polydispersity and domain interfaces tend to curve toward polydisperse blocks. The changes in phase behavior that are associated with variations in the polydispersity of the middle bridged polystyrene block, however, are not analogous to those reported in AB diblock copolymers, as increases in this middle block polydispersity are not always accompanied by (i) increased domain periodicities and (ii) a tendency for domain interfaces to curve toward the polydisperse domain. These results highlight the utility of polydispersity as a tool to tune the phase behavior of ABC block terpolymers.Chemical Engineerin

Exploiting Topographical Texture To Impart Icephobicity

Appropriately structured topographical features that are found in nature (e.g,, the lotus leaf) or that are produced synthetically (e.g., via lithography) can impart superhydrophobic properties to surfaces. Water beads up and readily rolls off of such surfaces, making them self-cleaning. Within the past few years, scientists and engineers have begun exploring the utility of these surfaces in mitigating the icing problem prevalent in the operation of critical infrastructure such as airplanes, ships, power lines, and telecommunications equipment. An article in this issue advances our fundamental knowledge in this area by examining the dynamic impact of water droplets on both smooth and topographically structured supercooled substrates. The results illustrate that, under at least some environmental conditions, superhydrophobic surfaces can minimize or even eliminate ice formation by repelling impinging water drops before they can freeze. Subsequent research will build on these results, possibly leading to the fabrication of commercially viable and durable icephobic surfaces that mitigate the icing problem under all environmental conditions.National Research Council (U.S.) (Postdoctoral Fellowship)United States. Air ForceUnited States. ArmyXerox Foundatio

Relationships between Water Wettability and Ice Adhesion

Ice formation and accretion may hinder the operation of many systems critical to national infrastructure, including airplanes, power lines, windmills, ships, and telecommunications equipment. Yet despite the pervasiveness of the icing problem, the fundamentals of ice adhesion have received relatively little attention in the scientific literature and it is not widely understood which attributes must be tuned to systematically design “icephobic” surfaces that are resistant to icing. Here we probe the relationships between advancing/receding water contact angles and the strength of ice adhesion to bare steel and twenty-one different test coatings (~200−300 nm thick) applied to the nominally smooth steel discs. Contact angles are measured using a commercially available goniometer, whereas the average strengths of ice adhesion are evaluated with a custom-built laboratory-scale adhesion apparatus. The coatings investigated comprise commercially available polymers and fluorinated polyhedral oligomeric silsesquioxane (fluorodecyl POSS), a low-surface-energy additive known to enhance liquid repellency. Ice adhesion strength correlates strongly with the practical work of adhesion required to remove a liquid water drop from each test surface (i.e., with the quantity [1 + cos θ[subscript rec]]), and the average strength of ice adhesion was reduced by as much as a factor of 4.2 when bare steel discs were coated with fluorodecyl POSS-containing materials. We argue that any further appreciable reduction in ice adhesion strength will require textured surfaces, as no known materials exhibit receding water contact angles on smooth/flat surfaces that are significantly above those reported here (i.e., the values of [1 + cos θ[subscript rec]] reported here have essentially reached a minimum for known materials).Air Force Research Laboratory (Wright-Patterson Air Force Base, Ohio). Propulsion DirectorateUnited States. Air Force Office of Scientific ResearchChevron CorporationMassachusetts Institute of Technology. Dept. of Mechanical Engineerin

Superoleophobic Surfaces through Control of Sprayed-on Stochastic Topography

The liquid repellency and surface topography characteristics of coatings comprising a sprayed-on mixture of fluoroalkyl-functional precipitated silica and a fluoropolymer binder were examined using contact and sliding angle analysis, electron microscopy, and image analysis for determination of fractal dimensionality. The coatings proved to be an especially useful class of liquid repellent materials due to their combination of simple and scalable deposition process, low surface energy, and the roughness characteristics of the aggregates. These characteristics interact in a unique way to prevent the buildup of binder in interstitial regions, preserving re-entrant curvature across multiple length scales, thereby enabling a wide range of liquid repellency, including superoleophobicity. In addition, rather than accumulating in the interstices, the binder becomes widely distributed across the surface of the aggregates, enabling a mechanism in which a simple shortage or excess of binder controls the extent of coating roughness at very small length scales, thereby controlling the extent of liquid repellence.United States. Air Force Office of Scientific ResearchJet Propulsion Laboratory (U.S.

Superoleophobic Surfaces through Control of Sprayed-on Stochastic Topography

The liquid repellency and surface topography characteristics of coatings comprising a sprayed-on mixture of fluoroalkyl-functional precipitated silica and a fluoropolymer binder were examined using contact and sliding angle analysis, electron microscopy, and image analysis for determination of fractal dimensionality. The coatings proved to be an especially useful class of liquid repellent materials due to their combination of simple and scalable deposition process, low surface energy, and the roughness characteristics of the aggregates. These characteristics interact in a unique way to prevent the buildup of binder in interstitial regions, preserving re-entrant curvature across multiple length scales, thereby enabling a wide range of liquid repellency, including superoleophobicity. In addition, rather than accumulating in the interstices, the binder becomes widely distributed across the surface of the aggregates, enabling a mechanism in which a simple shortage or excess of binder controls the extent of coating roughness at very small length scales, thereby controlling the extent of liquid repellence

Superoleophobic Surfaces through Control of Sprayed-on Stochastic Topography

The liquid repellency and surface topography characteristics of coatings comprising a sprayed-on mixture of fluoroalkyl-functional precipitated silica and a fluoropolymer binder were examined using contact and sliding angle analysis, electron microscopy, and image analysis for determination of fractal dimensionality. The coatings proved to be an especially useful class of liquid repellent materials due to their combination of simple and scalable deposition process, low surface energy, and the roughness characteristics of the aggregates. These characteristics interact in a unique way to prevent the buildup of binder in interstitial regions, preserving re-entrant curvature across multiple length scales, thereby enabling a wide range of liquid repellency, including superoleophobicity. In addition, rather than accumulating in the interstices, the binder becomes widely distributed across the surface of the aggregates, enabling a mechanism in which a simple shortage or excess of binder controls the extent of coating roughness at very small length scales, thereby controlling the extent of liquid repellence

Superoleophobic Surfaces through Control of Sprayed-on Stochastic Topography

The liquid repellency and surface topography characteristics of coatings comprising a sprayed-on mixture of fluoroalkyl-functional precipitated silica and a fluoropolymer binder were examined using contact and sliding angle analysis, electron microscopy, and image analysis for determination of fractal dimensionality. The coatings proved to be an especially useful class of liquid repellent materials due to their combination of simple and scalable deposition process, low surface energy, and the roughness characteristics of the aggregates. These characteristics interact in a unique way to prevent the buildup of binder in interstitial regions, preserving re-entrant curvature across multiple length scales, thereby enabling a wide range of liquid repellency, including superoleophobicity. In addition, rather than accumulating in the interstices, the binder becomes widely distributed across the surface of the aggregates, enabling a mechanism in which a simple shortage or excess of binder controls the extent of coating roughness at very small length scales, thereby controlling the extent of liquid repellence