The present disclosure relates to fluid conveying apparatuses forming a channel through or along which fluid is conveyed, such as tubes, pipes, etc. More particularly, it relates to fluid conveying apparatuses with channel flow surfaces presenting minimal drag properties.
Tubes, pipes and a plethora of other channel-defining structures are commonly employed to convey or transfer fluid in a wide range of vastly different environments. For example, flexible, small diameter catheters are used to convey small volumes of medical liquids (e.g., blood), whereas rigid, large diameter pipes convey large volumes of other liquids such as water or oil. In these and many other end use applications, the particular channel-defining structure is conventionally designed to present as flat (smooth) a surface as possible to fluid flowing through the channel, under the assumption that a flat surface will generate minimal drag. As a point of reference, drag is the resistant force a fluid imposes on an object in either closed channel (internal flow) or open channel (external flow) conditions; the surface of the object along which the fluid flows directly affects drag (via skin friction).
More recently, efforts have been made, in the context of open channel flow, to design surfaces with reduced drag properties. Inspired by designs found throughout living nature, researchers have investigated some of the world's flora and fauna to solve fluid drag and other technical challenges. Examples include “low drag” surfaces of boats and swimsuits inspired by low drag shark skin. Also, “self-cleaning” windows inspired by the superhydrophobic and low adhesion lotus leaf have been devised. Self-cleaning occurs when contaminant particles are collected and removed from a surface by fluid flow.
Another, but not yet fully resolved, technological problem common place to fluid flow applications is fouling. Fouling can be generally categorized as biological fouling (“biofouling”) or inorganic fouling. Biofouling is the accumulation of unwanted biological matter, with biofilms created by microorganisms and macroscale biofouling created by macroorganisms. In addition to biofouling, inorganic fouling can occur as a result of deposits from corrosion, crystallization, suspended particles, oil, ice, etc. Furthermore, biologically induced corrosion is of concern. A low drag surface often equates to less fouling and energy conservation, which is important for many industries.
Many engineering applications can benefit from low drag and self-cleaning surfaces in the medical, marine, and industrial fields. As but one example, low drag is important for the oil transportation industry, where pipeline flow must overcome high drag (with Reynolds numbers reaching 1×105). Lower drag in pipelines reduces the required pumping energy and increases flow rates, which saves both time and money. Traditionally, drag is lowered using fluid additives or improving the pipeline interior smoothness with corrosion resistant epoxy coatings. By way of further example, self-cleaning can also be an important characteristic with oil transportation (and other) applications for preventing the unwanted deposition of oil by means of oil-resistant or superoleophobic properties.
As mentioned above, characteristics of certain flora and fauna have previously been found beneficial for, and incorporated into, various products. In the aquatic environment, fish (for example rainbow trout) exhibit low drag in water. It is surmised that their surface is covered with oriented scales that promote anisotropic flow from head to tail. Furthermore, the scales are mucous covered (lowering drag) and hinged (preventing motion in the opposite direction), which help navigate in fast moving currents. Fast swimming shark skin (for example Mako) also exhibits low drag in water. This is due to anisotropic flow characteristics of riblet microstructures aligned in the swimming direction as well as the control of vortices on the skin normally present in turbulent flow. The riblets lift and pin any vortices generated in the viscous layer. Lifting reduces the total shear stress since vortices contact just the small riblet tips, as opposed to the total surface area. Pinning reduces the cross-stream motion of a fluid and ejection of vortices from the viscous sublayer, which reduces energy loss. Lower drag increases fluid flow at the skin, reduces microorganism settlement time, promotes washing, and allows for faster predatory swimming.
In the ambient environment, lotus leaves (Nelumbo mucifera) have been found to promote self-cleaning with a superhydrophobic and low adhesion surface, due to a waxy hierarchical surface structure. It has been found that key features of the lotus leaf are a microscopically rough surface, consisting of a vast array of randomly distributed micropapillae (diameters on the order of 5-10 μm) that are covered with the waxy, branch-like nanostructures (average diameter on the order of about 125 nm). Water on these surfaces can form almost spherical droplets that do not adhere to the surface. On an incline, the water droplets move easily, collecting and removing contaminant particles. These characteristics have been collectively referred to as the lotus effect. As a point of reference, “superhydrophobic” is in reference to surfaces that have a water contact angle of at least about 150°; the lotus leaf surface structure can provide contact angles as high as 170°.
While many attempts have been made to implement shark skin or lotus effects onto or into the surfaces of various articles intended to interface with liquids in an open-channel manner, only limited research has been previously made into possible closed channel end use applications. Moreover, many other items in living nature, previously not fully understood, may implicate further advancements in one or more of fluid drag, self-cleaning, or anti-fouling. Therefore, a need exists for fluid conveying apparatuses presenting a fluid interface surface that builds upon the shark skin and lotus effects, and methods of manufacturing the same.
Some aspects of the present disclosure relate to a fluid conveying apparatus. The apparatus includes a wall structure forming a channel for conveying fluid. The channel is bounded by an interior face of the wall structure. A rice leaf-like textured surface is formed on the interior face. The textured surface includes a plurality of micropillars projecting from the interior face and arranged in a geometry akin to rice leaf micropapillae. In some embodiments, the textured surface is a replica of a rice leaf surface structure. In other embodiments, the micropillars are arranged to define a plurality of longitudinal grooves having a transverse sinusoidal pattern. In yet other embodiments, the micropillars are arranged in a substantially uniform micropattern, and have a diameter on the order of about 2 μm and a height on the order of about 4 μm. In related embodiments, the micropillars are arranged into longitudinal rows having a pitch distance on the order of 4 μm. In even further related embodiments, the rows of micropillars are further grouped into sets of rows (e.g., three rows per set), and a lateral spacing on the order of 8 μm is established between adjacent sets.
The rice leaf-like textured surfaces of the present disclosure can further include a nanostructured coating applied to each of the micropillars, creating a hierarchical structure. The nanostructured coating can assist in rendering the micropillars superhydrophobic in some embodiments, and mimics the waxy nanobumps of a native rice leaf. In other embodiments, the nanostructured coating is superoleophobic.
The hierarchical, rice leaf-like textured surfaces are uniquely configured to exhibit low drag, self-cleaning, and anti-fouling properties. It has surprisingly been found that the textured surfaces of the present disclosure are highly useful in various fluid interface environments, for example closed channel flow environments. Various liquids, for example water, experience the lotus effect when traversing the textured surfaces of the present disclosure, with the textured surface further facilitating anti-fouling actions, unlike known flora or fauna-inspired fluid interface constructions. Further, other high viscosity liquids, such as oil, also experience very minimal drag when interfacing with the textured surfaces of the present disclosure in, for example, closed channel flow conditions. Thus, the fluid conveying apparatuses of the present disclosure are highly useful in a plethora of end-use applications, for example closed channel liquid flow devices ranging from small diameter catheters to large diameter oil pipelines.
Other aspects in accordance with principles of the present disclosure are directed toward methods of manufacturing an apparatus for conveying fluid. The method includes forming a textured surface on an interior face of a wall structure, with the interior face bounding a channel in the wall structure. The textured surface is rice leaf-like, and includes a plurality of micropillars projecting from the interior face and arranged in a geometry akin to rice leaf micropapillae. With this construction, fluid flowing through the channel experiences minimal drag along the textured surface. In some embodiments, the textured surface is formed by mold (e.g., master molds created using standard photolithography techniques and soft-lithography) replicating a native rice leaf. In other embodiments, the textured surface is formed on an adhesive-backed sheet formed apart from the wall structure. With these embodiments, the sheet is adhered to the interior face to locate the textured surface along the channel. In yet other embodiments, a nanostructured coating is applied to the micropillars, creating a hierarchical structure.
In the present disclosure, “micro-scale” size is defined as a size in the range equal to or more than 1 μm and less than 100 μm. As used throughout the present disclosure, any term having the prefix “micro” is in reference to the micro-scale size unless stated otherwise. A “nano-scale” size is defined as a size in the range equal to or more than 1 nm and less than 1000 nm. As used throughout the present disclosure, any term having the prefix “nano” is in reference to the nano-scale size unless stated otherwise. A “hierarchical structure” or “hierarchical surface” comprises microstructures and nanostructures.
Aspects of the present disclosure are directed toward fluid conveying apparatuses having a fluid interface surface that incorporates a textured surface structure, in some embodiments a hierarchical textured surface, akin to a rice leaf as described in greater detail below. In more general terms, the fluid conveying apparatuses of the present disclosure can assume a multitude of different forms adapted for countless end-use applications. With this in mind,
The textured surface 28 mimics properties of the hierarchical surface of a rice leaf by including a plurality of micropillars (i.e., micro-scale sized pillars) 30 projecting from the interior face 26. In some embodiments, the textured surface 28 is a direct replica of the hierarchical surface of a rice leaf sample, with the replicated micropillars 30 being relatively randomly arranged in accordance with the micropapillae of the actual rice leaf sample being replicated. In other embodiments, the micropillars 30 are not directly molded from an actual rice leaf sample, and instead are formed and arranged in a micropatterned geometry described below. In either case, the micropillars 30 are generally cylindrical and are akin to the micropapillae (and corresponding micropattern) of rice leaves. The micropillars 30 can be rendered superhydrophobic with low adhesion via application of an optional nanostructured coating 32 that exhibits fluid interface properties akin to the epicuticular wax of rice leaves. The nanostructured coating 32 applies a plurality of nanoparticles 34 on each of the micropillars 30. In some embodiments, the nanoparticles 34 are silica particles, such as hydrophobosized silica nanoparticles, having a particle size on the order of 35-65 nm. In yet other embodiments, the rice leaf-like textured surfaces of the present disclosure consist of the micropillars 30 without the nanostructured coating 32, and thus are not necessarily hierarchical.
The micropillars 30 are, in some embodiments, substantially identical (e.g., dimensional parameters, such as diameter, do not vary by more than 10% across the micropillars 30). Each of the micropillars 30 can be substantially cylindrical, having or defining a height H and a diameter D. In some embodiments, the micropillars 30 have a substantially identical height H (e.g., variation in height H does not exceed 10% across the micropillars 30); in other embodiments, the micropillars 30 can have differing heights H.
With the one exemplary micropattern of
The lateral spacing L is greater than the pitch distance P. For example, the first and second sets 60a, 60b can each be described as having respective first-third rows 40a-40c, 40a′-40c′. The third row 40c of the first set 60a is immediately adjacent the first row 40a of the second set 60b. The center-to-center distance between laterally aligned ones of the micropillars 30 of the first set third row 40c and the second set first row 40a′ defines the lateral spacing L (e.g., the lateral distance between the identified micropillar 30c of the first set third row 40c and the identified micropillar 30d of the second set first row 40a′).
It has surprisingly been found that the micropillar diameter D, height H, and spacing (e.g., the pitch distance P) are all important characteristics for promoting low drag, self-cleaning and/or anti-fouling. It has been shown that for similar patterns that water droplets fully penetrated the area between the micropillars 30 (transitioning from Cassie-Baxter to Wenzel regimes) when:
(√{square root over (2)}P−D)2/R≧H (1)
where the known parameters are pitch (P), diameter (D), droplet radius (R), and uniform cylindrical micropillar height (H). It has surprisingly been found that that certain dimensional parameters most effectively mimic rice leaf structure geometry in the Cassie-Baxter regime. For example, in some embodiments, the micropillars 30 and corresponding micropattern have a diameter D in the range of 1-3 μm, for example 2 μm; a pitch spacing P of approximately 2D (e.g., in range of 2-6 μm, for example 4 μm); a height H in the range of 2-6 μm, for example 4 μm; and a lateral spacing L of approximately 2P (e.g., in the range of 4-12 μm, for example 8 μm). These geometries have surprisingly been found to encourage low drag, self-cleaning, and anti-fouling by ensuring superhydrophobicity, low adhesion, and anisotropic fluid control. Further, the selected pitch spacing P in accordance with some embodiments is selected to be smaller than the size of microbacteria. This configuration surprisingly deters microorganisms from colonizing at the interior face 26 (
Whether the textured surface 28 (
Returning to
The micropatterned micropillars 30 of the present disclosure can have substantially identical heights H as mentioned above. In other embodiments, dual (or other) height micropatterns can be employed. For example,
A related embodiment textured surface 28′ in accordance with principles of the present disclosure is shown in
The rice leaf-like textured surfaces 28 (
Returning to
In one embodiment, replica fabrication includes a two-step soft-lithography molding procedure, reflected in
In some embodiments, the above-described molding techniques (and other fabrication techniques known to one of skill) are employed to form the fluid conveying apparatus 20 (
A two-step molding process was used to fabricate replica rice leaf-like structure samples in accordance with principles of the present disclosure and from which sample closed channel fluid conveying apparatuses in accordance with principles of the present disclosure were constructed. Samples of rice leaf (Oryza sativa) were obtained. Using liquid platinum silicone (e.g., Smooth-On Dargon Skin 20), a negative mold was taken after cleaning the actual sample with deionized water and isopropyl alcohol. The liquid silicone ensured that details were accurately replicated and that air bubbles would rise away from the molding surface. With the silicone mold complete, a liquid urethane polymer (e.g., Smooth-On Smooth-Cast 305) was applied and cured, yielding a precise positive replica. Before casting the final positive replica as a channel-forming tube, two positive replicas were created to remove any contaminants remaining on the negative mold. A post-machining process was employed to ensure proper channel lengths.
Other replica structure samples were fabricated in a similar manner using actual butterfly wing (Blue Morpho didus), rainbow trout fish scales (Oncorhynchus mykiss) and Mako shark skin (Isurus oxyrinchus) samples.
Replicas were characterized and compared with actual samples to determine the accuracy of replication. Both scanning electron microscope (SEM, Hitachi S-4300) and optical profiler (Veeco Contour GT with Vision 64 software) images were taken, which provide evidence of surface replication success. Since fish scales and shark skin are naturally covered by mucous, the actual samples were cleaned and dehydrated prior to CA and CAH measurements (described below). Cleaning consisted of deionized water and isopropyl alcohol rinses followed by drying in a desiccator for 96 hours. Samples were then mounted with conductive paint and gold-coated prior to SEM imaging. Prior to optical profiler imaging, the samples were mounted on glass slides and then desiccator dried for 96 hours.
As described below, certain nanostructured coatings were applied to selected ones of the replica samples to provide superhydrophobicity or superoleophobicity to the replica surface. However, other ones of the replica samples did not receive a nanostructured coating, and are referred to as an “uncoated replica sample” in the testing explanations and analysis below.
In addition to the shark skin replica sample described above, laser etched riblet samples were prepared that were inspired by the dogfish shark Squalus acanthias. Multiple different laser etched riblet samples were prepared having different riblet dimension. The riblet dimensions of interest include thickness (t), valley widths (vs), spacing (s), gaps (g), lengths (L), and heights (h). Riblet dimensions were incrementally varied for each sample, implementing differing h/s and t/s values. In the riblet sample descriptions below, corresponding h/s and t/s values are parenthetically provided.
To mimic the fluid interface characteristics of the actual native samples with the cast urethane replicas, the surfaces of selected replica samples were made superhydrophobic with low adhesion by using a nanostructured coating to create a roughness-induced lotus effect. This was applied on selected samples based on preliminary performance in drag and self-cleaning experiments. Various experiments were conducted to ensure that the lotus effect was achieved without detrimentally affecting the sample micro/nanostructures. Deposition variables included the particle and binder solution concentrations as well as dip rates, with contact angle and microscope measurements evaluating their effects. This resulted in superhydrophobic coated rice leaf and shark skin replicas, where the coated rice leaf replica more accurately mimics the actual rice leaf hierarchical structure. Similar lotus effect coatings are known to exhibit low drag and self-cleaning properties.
For the superhydrophobic nanostructured coating, silica particles were selected as they are known to provide high durability and transparency, if desired. Replicas were dip-coated with a solution consisting of 50 nm (±15 nm) hydrophobized silica nanoparticles (by Evonik-Degussa Corporation, Parsippany, N.J.) combined with methylphenyl silicone resin (SR355S from Momentive) dissolved in tetrahydrofuran and isopropyl alcohol. As a point of reference, this superhydrophobic coating was found to be superoleophilic, with the resultant sample structures being referenced as “superhydrophobic” or “superhydrophobic (superoleophilic)” in the discussions below.
Selected ones of the laser etched riblet samples also received the superhydrophilic nanostructured coating described above. Using the laser etched riblet Shallow (0.16, 0.31) sample as a basis, new samples were created with total and partial coatings, which are referred to as Coated riblet (0.16, 0.31) and Valleys coated riblet (0.16, 0.31), respectively. The Valleys coated riblet sample simulated actual shark skin, where slippery mucous is present between the riblet tips in the so-called Valleys. Contact angle and microscope measurements ensured that the superoleophilicity was achieved without detrimentally affecting the sample micro/nanostructures.
To investigate the role of superoleophobicity, a superoleophobic coating was applied to other selected ones of the replica samples. To create the superoleophobic coating, a two-step, nanotechnology-based oleophobic coating available from UltraTech International, Inc. of Jacksonville, Fla. under the trade designation EverDry® SE 7.6.110 was applied. The base and top coats of the EverDry® system were individually applied with an internal mixing double action airbrush using laboratory air at 30 psi. As a point of reference, the so-created superoleophobic surfaces were also found to be superhydrophobic.
In the discussions below, reference to a “superhydrophobic” sample, a “superhydrophobic (superoleophilic)” sample, or more simply a “coated” sample refers to a replica or laser etched riblet sample coated with the superhydrophobic nanostructured coating above unless noted otherwise, whereas reference to a “superoleophobic” sample refers to a replica sample coated with the superoleophobic coating of this section.
Various ones of the uncoated replica and laser etched riblet samples, superhydrophobic samples, and superoleophobic samples were fabricated into closed channel fluid conveying apparatuses. The channels were formed to have a rectangular cross-sectional shape, and was inspired by hospital catheter tubes (3-5 mm diameter) commonly used in the healthcare industry to transport aqueous fluids. A rectangular sandwich design (i.e., two half sections that combine to define, when assembled, a complete closed rectangular channel) was selected, where the sample structure was applied to one side and then sandwiched together with the second channel section.
For water experiments, water was pumped from a reservoir to the elevated container (via the fill line), which then flowed down the supply line. To ensure a constant flow rate, the control valve and overflow line regulated the water level and the flow rate (thus Re number) was varied by changing the container elevation. The syringe pump delivered water flow at low velocities (0.04-0.09 m/s), while the elevated container provided higher velocity water flow (2-5 m/s).
For air flow experiments, laboratory air connected to an adjustable Omega FL-1478-G rotameter allowed for incremental variation of the flow velocity (4-33 m/s). The laboratory airflow velocity was calculated based on the rotameter reading and the channel cross-sectional area.
For oil experiments, white paraffin oil (Carolina CAS number 8012-95-1) was selected due to its low surface tension, chemical compatibility with samples, and low health hazard. This selection and criteria are similar to the oil used in the so-called Berlin oil channel. To achieve a wide range of constant flow rates, oil was pumped into the closed channels using the syringe pump and a miniature gear pump (Cole-Parmer EW-07012-30). The syringe pump provided oil flow at low velocities (0.02-0.14 m/s) whilst the gear pump provided oil flow for the high velocity (3.5-4.5 m/s). The high velocity oil flow rate was chosen to simulate conditions found in oil pipeline applications.
To maintain kinematic viscosity, fluid temperature was monitored with a CND DTQ450X digital thermometer, and held constant (18.5-21° C.). The pressure drop between the inlet and outlet was measured with an Omega PX26-005DV differential manometer (potted in RTV silicone). Data were collected at 10 Hertz for 30 seconds with a Vishay 2311 Laboratory Amplifier and a Measurement Computing USB-1208LS DAQ card. The system was calibrated prior to use with an Ametek RK-1600W6 pneumatic pressure system.
To confirm that the system was behaving properly (e.g., detecting possible leaks and misalignments), the measured value were compared to predicted pressure drop. This was done by comparing the flat experimental sample channel to the predicted values. It also allows for a baseline comparison when reporting pressure drop percentage values. Predicting pressure drop of a flat rectangular duct requires the use of the incompressible flow equations for straight uniform pipes. Since the Mach number is less than 0.3 for all experiments, incompressible flow equations may be used. The predicted pressure drop was calculated using the total channel cross-sectional area.
Pressure drop (Δp) between two points in a straight uniform closed channel with incompressible and fully developed flow is found with the Darcy-Weisbach formula:
where ρ is the fluid density, V is the flow velocity, f is the friction factor, L is the length between two points on a channel, and D is the hydraulic diameter. Flow velocity (V) is determined by dividing the volumetric flow rate by the channel cross-sectional area. In air experiments, the rotameter values were used with manufacture provided charts to determine the flow velocity.
The rectangular duct hydraulic diameter is:
where a is the width and b is the height.
The friction factor (f) for rectangular duct flow is:
where b/a≦1.
Eq. 4 shows that the friction factor is dependent on channel geometry and independent of the surface roughness. In order to account for roughness, friction factor values for pipes can also be found with the Moody chart.
Self-cleaning experiments were conducted by contaminating selected samples, employing a wash technique, and determining the percentage of particles removed. Depositing contaminated particles on tilted (45°) samples involved a glass contamination chamber (0.3 m diameter and 0.6 m high), as shown in
Wash experiments consisted of exposing the tilted (45°) sample to water droplets falling from a specified height and drip rate (total duration of 2 min using 10 μt, water at 18.5<temp.<19° C.). The syringe pump and tubing were positioned relative to the sample being tested as shown in
Wettability plays a significant role in self-cleaning, for instance as found in nature with the superhydrophobic lotus leaf of superhydrophilic pitcher plant. With the lotus effect, a high contact angle (CA) coupled with low contact angle hysteresis (CAH) repels many liquids and may remove contaminant particles. With the pitcher plant effect, a thin surface water film encourages the shearing effect that may also remove contaminant particles. To understand the effects of wettability, the apparent contact angle (CA) and contact angle hysteresis (CAH) were measured for selected actual, uncoated replica and coated replica samples. CAH is the difference between the advancing (downhill side) and receding (uphill side) contact angles, which is lower for Cassie-Baxter (droplet sitting on top of asperities) and higher for Wenzel (droplet penetrating gaps between asperities) regimes. Various CA and CAH measurement tests were performed with water and air droplets; and for completeness oil droplet CA was measured under water for selected samples.
Water droplet measurements were taken with an automated goniometer (Rame-Hart model 290-F4) that gently deposited 5 μL, (approximately 1 mm diameter) water droplets onto the sample surfaces. Similar sized oil droplets were deposited using a microliter syringe (Hamilton model 701 with volume of 10 μL). For both water droplet and oil droplet testing, CAH was determined by tilting the sample until the droplet began to move (up to 90°), and subtracting the advancing and receding contact angles.
Measuring oil droplet CA under water at the solid-water-oil interface is useful when considering self-cleaning efficiency of underwater surfaces contacting oil, or vice versa, where superoleophobicity may repel contaminants. Clean surfaces encourage low drag, so therefore self-cleaning is necessary for underwater applications where oil contaminants are present.
Since fish scales and shark skin are naturally covered by mucous, the actual samples were cleaned and dehydrated prior to CA and CAH measurements. Cleaning consisted of deionized water and isopropyl alcohol rinses followed by drying in a desiccator for 96 hours. It was found that dried shark skin soaks in the water droplet before the CA or CAH can be measured. It was not necessary that the rice leaf or butterfly wing actual samples be subjected to washing or dehydrating preparation.
To characterize the actual and replica samples, an SEM and an optical profiler were employed for a qualitative and quantitative comparison and understanding of the relevant mechanisms, as shown in
SEM images in
Optical profiler images in
Information was gathered from SEM and optical profiler images at different magnifications to measure features of interest as summarized in Table 1 below. The x, y, and x-spacing dimensions were determined from SEM images by estimations based on the scale bars, with the exception of the rice leaf grooves and fish scales that were determined with the optical profiler. The z-dimensions and peak radiuses were estimated from optical profiler cross-sectional height maps, using objective zooms ranging from 5× to 100×.
sativa
Morpho
didius)
mykiss)
oxyrinchus)
To understand the drag effects of replicas with water, oil, and air flow, the results of a series of the pressure drop experiment described above are presented below. In many of the graphs discussed, one plot shows the predicted pressure drop for a flat rectangular channel using Eqn. 2 to estimate pressure drop for a milled channel. In order to account for milled channel surface roughness, friction factor values from the Moody chart were selected based on the roughness value ε=0.0025 mm. Additionally, many of the plots show the milled channel control sample for comparison, and percentage pressure drops are calculated from the control samples.
Results: Pressure Drop with Water Flow
The top rows of
The bottom rows show superhydrophobic coated and uncoated rice and shark skin replicas and results indicate that the coating offers improvement. The greatest benefit is shown in higher flow velocity conditions. In laminar water flow, the maximum pressure drop reduction of 26% was found with the superhydrophobic flat sample. In turbulent water flow, maximum pressure drop reduction is shown with superhydrophobic coated rice leaf and shark skin replicas at 26% and 29%; and uncoated at 17% and 19%, respectively. These values compare to other rectangular duct experiments conducted with micro-sized pillar photolithography samples, which yielded pressure drop reductions in laminar and turbulent flows. It has been surmised that the superhydrophobic rice leaf replica sample benefits from anisotropic flow and low adhesion, which leads to lower drag. In addition, the superhydrophobic shark skin replica benefits from the shark skin effect combined with low adhesion, which also leads to low drag.
Results: Pressure Drop with Oil Flow
The oil flow pressure drop test results for the replica samples are shown in
The top rows of
At the high and low velocities, the superoleophobic rice leaf and shark skin replica samples provide drag reduction, due to anisotropic flow and low adhesion. In addition, the superhydrophobic (superoleophilic) rice leaf replica sample provided drag reduction due to the thin film effect described below.
In general, the greatest benefit is shown in high velocity conditions. It is surmised that this is due to the formation of a thin oil film at the boundary layer interface, thus increasing the slip length. It is further surmised that the replica of rice leaf morphology retains a thin oil film where oil fully penetrates the microstructures at the boundary layer to reduce drag, thus benefiting from the Wenzel state. This drag reducing state is amplified with the nanostructured coating that further increases the oleophilicity. The coated shark skin replica does not perform as well as the coated rice leaf replica, which is likely due to the absence of the thin oil film. It is surmised that oil is not trapped as speculated in the rice leaf, due to the riblets oriented in the flow direction. Rice leaf micropapillae are oriented such that oil remains stationary in between the micropapillae. With low Reynolds numbers, turbulent vortices are not formed and thus the shark skin effect is not present in these experiments. In high velocity (4.3 m s−1), maximum pressure drop reduction is shown with superhydrophobic (superoleophilic) and superoleophilic coated rice leaf and butterfly wing replica samples at 10% and 6%, respectively.
The pressure drop test results for the laser etched riblet samples are presented in
Results: Pressure Drop with Air Flow
With air, the achievable velocity range was higher as compared to water or oil, and the higher Reynolds numbers show continued pressure drop reduction (until expected plateauing). When comparing fish scales and shark skin replica results of
Developing a nondimensional pressure drop expression allows one to estimate pressure drops for various fluids. This can be accomplished by combining Eqs. 2-4 and a dimensioness Reynolds number
Solving for the nondimensional pressure drop as a function of Reynolds number yields:
where G is the fluid property and channel dimension parameter. Eqn. 5 shows that pressure drop is directly proportional to velocity and nondimensional pressure drop is proportional to the Reynolds number. It allows one to effectively compare and study different fluids.
As expected, the superhydrophobic and superoleophobic coated samples outperformed the uncoated replicas and more particles were removed at higher versus lower velocities. The coatings amplify the self-cleaning abilities of the replicas, and it is surmised that the droplets are able to roll and collect the particles after impact. Furthermore, the coated samples exhibit the lower adhesion forces, suggesting that the particles are easier to remove versus uncoated. Self-cleaning is demonstrated with superhydrophobic coated rice leaf and shark skin replica samples at 95% and 98% contaminant removal, respectively, as compared to uncoated replica samples at 85% and 79%, respectively. The superoleophobic coated replica samples performed similarly. For comparison, the flat control sample showed a 70% contaminant removal.
Combining the lotus leaf and shark skin effects is evident with the coated rice leaf and shark skin replica samples, which improves the self-cleaning efficiency.
Results: Wettability with Water Droplets
To understand the impact of water droplet apparent contact angle (θ) and thus wettability on drag and self-cleaning, a series of experiments were conducted with the actual, uncoated, and coated samples using water droplets as described above. Exemplary images and corresponding determined apparent contact angle (θ) of water droplets for several of the actual samples are summarized in
When comparing pressure drop results with wettability, there is not a direct correlation, since the shark skin replica exhibits a lower contact angle but also higher pressure drop reduction. When combining the lotus effect with the shark skin effect, as demonstrated by coating the rice leaf and shark skin replicas, the new superhydrophobic surface provides benefit, which provides the greatest pressure drop reduction.
As a point of reference, contact angle and adhesion are important attributes for low drag and self-cleaning and can be estimated with Cassie-Baxter and Wenzel equations. Close examination of the solid-air-liquid interface reveals that the Wenzel regime does not contain an air pocket unlike the Cassie-Baxter regime. This difference, due at least in part to surface roughness, influences the surface wettability since the air pocket affords a larger contact angle θ and smaller CAH. Eqn (6) below describes the Wenzel equation where θ=contact angle, θ0=contact angle of the droplet on the flat surface, Rf=roughness factor, AF=flat projected area, and ASL=solid-liquid surface area, whereas Eqn (7) below describes the Cassie-Baxter equation with fLA=fractional flat liquid-air contact area.
Wenzel: cos θ=Rf cos θ0 (6)
where Rf=ASF/AF.
Cassie-Baxter: cos θ=Rf cos θ0−fLA(Rf cos θ0+1) (7)
Using optical profiler height map images (1.2×0.096 mm), the values of Rf and fLA were obtained for several samples. The Rf value was estimated with optical profiler software by measuring the solid-liquid surface area and dividing by the flat projected area. The fLA value was estimated with SPIP software by adjusting the asperity height threshold to remove the upper 25% of the peaks and measuring the remaining projected flat surface area. Using the so-obtained roughness factor and fractional liquid-air contact area measurements, the contact angles for the replica rice leaf, butterfly wing, fish scales, and shark skin were then estimated. Table 2 shows the values of Rf and fLA from actual samples, along with a comparison to measured and predicted contact angles for each replica. Such a comparison aids in the understanding of Wenzel or Cassie-Baxter regimes for a water droplet on replica surfaces.
didius)
mykiss)
oxyrinchus)
aIndicates the Wenzel regime.
bIndicates the Cassie-Baxter regime.
The measured and predicted values correlate with the Cassie-Baxter for rice leaf and butterfly wing replicas; and Wenzel for fish scales and shark skin. This coincides with living nature, since the rice leaf and butterfly wing are found in the ambient environment (can exhibit air pockets), whereas fish scales and shark skin are designed for the marine environment (cannot exhibit air pockets).
Results: Wettability with Oil Droplets
Similar experiments were conducted with oil droplets in air and underwater. Contact angle measurements at the solid-air-oil interface are relevant for closed channel oil drag reduction, whereas measurements at the solid-water-oil interface are relevant for self-cleaning of underwater surfaces and vice-versa. Exemplary images, corresponding determined contact angle (θ) and conceptual mechanisms of oil droplets for several of the actual samples underwater are summarized in
The contact angles suggest oleophobic behavior except in the case of replica butterfly wing and superhydrophobic (superoleophilic) coated samples. The superhydrophobic coating is oleophilic at the solid-water-oil interface, and the superoleophobic coating is superoleophobic at the solid-air-oil interface. Oleophobicity is expected to be a function of surface tension. To begin, when a water droplet is placed on a surface in air, the solid-air-water interface forms the static contact angle of the droplet. The equation for the contact angle of a water droplet (ΘW) in air is predicted by Young's equation:
where γSA, γSW, and γWA are the surface tensions of the solid-air, solid-water, and water-air interfaces, respectively. Eqn (8) predicts that hydrophilicity is possible when γSA>γSW.
However, the equation for the contact angle of an oil droplet (Θ0) in air is predicted by Young's equation:
where γSA, γSO, and γOA are the surface tensions of the solid-air, solid-oil, and oil-air interfaces, respectively. Eqn (9) predicts that oleophilicity in air is possible when γSA>γSO where the surface energy of a solid surface must be higher than the surface tension of the oil.
Furthermore, the equation for the contact angle of an oil droplet (ΘOW) in water is predicted by Young's equation:
where γSW, γSO, and γOW are the surface tensions of the solid-water, solid-oil, and oil-water interfaces, respectively. Eqn (10) predicts that oleophobicity underwater (at the solid-water-oil interface) is possible when γSO>γSW. Further, it is believed that the surface tension of the solid-oil interface (γSO) is lower than the solid-air interface (γSA), therefore as predicted by Eqn 9 the result is oleophilicity.
The results of the apparent contact angle (CA) of water droplets and oil droplets (in air and underwater) for the various samples described above are presented in tabulated form in
When comparing the actual to replica samples there is a noticeable difference. In the case of rice leaf and butterfly wing samples, the contact angle difference between the actual and replica samples is significant. Conversely, the difference between the actual and replica fish scales and shark skin samples is lower. It is surmised that this is due to the different mechanisms at work and how the replicas differ from the actual samples. The greatest difference was found with oil droplets. For instance, the actual rice leaf is superoleophilic at the solid-water-oil interface whereas the replica rice leaf is oleophobic at the same interface. This is due to the lack of hierarchical structures on the replica that are present on the actual rice leaf. Once the nanostructured coating is applied to the replica rice leaf, the contact angle nears the contact angle of the actual rice leaf. Furthermore, the oil is unable to penetrate the replica butterfly wing as in the case of the actual sample, and a 71° (versus 0°) contact angle at the solid-water-oil interface was seen. Contact angles were lower for the replica fish scales and shark skin compared to the actual ones, presumably due to the absence of an oil-repellent water layer.
Results: Wettability comparison with laser etched riblets
Additional contact angle with oil droplet testing was performed on selected ones of the laser etched riblet samples. Contact angle measurements were taken at the solid-air-oil and for completeness also at the solid-water-oil interfaces, with images and results summarized. Contact angle measurements at the solid-air-oil interface are relevant for closed channel oil drag reduction, whereas measurements at the solid-water-oil interface are relevant for self-cleaning of underwater surfaces contacting oil, or vice versa. It is surmised that the high contact angle of oil droplets underwater encourages self-cleaning efficiency, which leads to lower drag in environments where contaminants may be present. Measurements were taken in both the streamwise and transverse flow directions, with the maximum values reported. For instance, rice leaf and continuous sawtooth riblet samples show a lower apparent contact angle when viewed in the streamwise compared to the transverse direction, since the droplets are pinned between the longitudinal grooves.
A summary of apparent contact angle data for several actual, replica, coated replica and laser etched riblet sample at both the solid-air-oil (
When comparing the drag results with wettability, there does not appear to be a direct correlation, although high CA coupled with low CAH provides superior self-cleaning. For instance, it was determined that drag reduction is possible with both sup erhydrophobic/oleophobic as well as superoleophilic surfaces, and superhydrophobic/oleophobic surfaces provide superior self-cleaning. Drag reduction mechanisms differ for the various fluids under investigation with considerations given to liquid repellency, low adhesion, and anisotropic flow. In the case of water flow, superhydrophobicity and low adhesion provide the greater drag reduction. However in oil flow, the superoleophilic surfaces provide drag reduction with the thin film effect whereas superoleophobic surfaces perform similarly due to liquid repellency and low adhesion. Therefore, lower drag is achieved when appropriate wettability is coupled with the appropriate surface morphology, which can promote anisotropic flow, liquid repellency, low adhesion, control of turbulent vortices, and/or produce the thin oil film.
Low drag and self-cleaning are desirable properties, and it is important to understand the mechanisms at work to replicate living nature. Conceptual modeling of each sample is shown in
Using the experimental and modeling information, the novel bioinspired self-cleaning low-drag surfaces of the present disclosure are highly viable by combining shark skin and lotus leaf effects into a rice leaf and butterfly wing model effect. The rice leaf surface was surprisingly found to be desirable due to its self-cleaning and low drag properties, as well as relatively simple two-dimensional cylindrical pillar geometry. The rice leaf and butterfly wing effect is successfully designed into a fluid flow interface surface using a uniform micropattern of optionally superhydrophobic low adhesion cylindrical pillars arranged in longitudinal rows. This surface structure will work well with water, oil, and air flow in laminar and turbulent regimes.
For the first time it has been surprisingly discovered that rice leaves and butterfly wings combine the desirable shark skin (anisotropic flow leading to low drag) and lotus (superhydrophobic and self-cleaning) effects, creating the rice leaf and butterfly wing effect. These unique surfaces exhibit anisotropic flow, water repellency, self-cleaning, and low adhesion properties, which is believed to promote low drag, self-cleaning, and anti-fouling. It is surmised that the sinusoidal grooves in rice leaf or the aligned shingle-like scales in butterfly wings provide anisotropic flow leading to low drag. Hierarchical structures consisting of micropapillae superimposed by waxy nanobumps in rice leaves or microgrooves on top of shingle like scale structures in butterfly wings provide superhydrophobicity and low adhesion.
It has surprisingly been found that the lotus effect nanostructured coating applied to the rice leaf and shark skin replicas produced the rice leaf and butterfly wing effect, where the coated rice leaf replica closely mimics the actual rice leaf. It has surprisingly further been found that rice leaf and butterfly wing effect samples show reduced drag, increased contact angle, and improved self-cleaning efficiency. The greatest drag reduction benefit is demonstrated in turbulent flow, where the maximum pressure drop reduction occurs with Superhydrophobic coated rice leaf and shark skin replicas at 26% and 29%; and uncoated at 17% and 19%, respectively. A 10% pressure drop reduction using both the superoleophilic and superoleophobic rice leaf replica samples in laminar oil flow. The greatest self-cleaning is shown with the lotus effect coated samples, where the maximum contaminant removal occurs with superhydrophobic coated rice leaf and shark skin replicas at 95% and 98%; and uncoated at 85% and 79%, respectively.
A correlation was found with the laser etched riblet samples. It was observed that the coating seems to enhance drag reduction at the low velocity with riblets but provides negligible benefit at the high velocity. At low velocity, the Coated and Valleys laser etched riblet coated samples show a noticeable drag reduction compared to their uncoated counterpart. Furthermore, it was found that the coating can increase drag, as in the case of the coated shark skin replica, where a slight increase in drag was observed. Comparing coated to uncoated, drag reduction improvement by coating the shallow laser etched riblet sample (4% reduction for coated vs. 1% increase for uncoated) was observed. From this, it is surmised that lower drag is achieved when superoleophilicity is coupled with the appropriate surface morphology to produce what is likely the thin oil film at the surface. Drag was also reduced using the butterfly wing replica and the laser etched riblet Narrow (0.38, 0.38) samples, with pressure drop reductions of 6% and 9%, respectively. The remaining samples—fish scales, shark skin and various laser etched riblet samples—either exhibited negligible differences or drag increase compared to the flat control. It is surmised that such surfaces do not form the thin oil film and thus the increased wetted surface area translates into higher friction/drag. Since the oil flow is laminar in each experiment, the shark skin effect was not present due to the lack of turbulent vortices.
In addition to low drag, it is surmised that an increased flow rate at the surface encourages self-cleaning by reducing the opportunity for contaminants to settle. Incidentally, it was determined that actual fish scale and shark skin samples are superoleophobic at the solid-water-oil interface. It is surmised that bioinspired surfaces based on actual fish scale and shark skin can promote self-cleaning in applications where oil is contaminating water, or vice versa.
Developing a new low drag and self-cleaning surface model inspired by rice leaves is achieved. Drag can be reduced by appropriate micro/nanostructures that provide a thin oil film at the solid-liquid interface. Such bioinspired surfaces can be created using a uniform micropattern of cylindrical pillars arranged in a uniformly spaced pattern having superoleophilicity. The spacing of the rice leaf-inspired micropillars is, in some embodiments, slight smaller than many common microorganisms, which prevents microorganism attachment to the surface and thus colonization leading to a biofilm. This investigation has successfully developed and characterized new bioinspired low oil drag surfaces, confirming that the new rice leaf replica and rice leaf-like hierarchical textured surfaces of the present disclosure are highly viable for various medical, marine, and industrial applications.
Although the present disclosure has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes can be made in form and detail without departing from the spirit and scope of the present disclosure.
This invention was made with government support from the National Science Foundation, Grant Number CMMI-1000108. The government has certain rights in the invention.