While microstructured surfaces have been proven useful for altering properties including hydrophobicity, hydrophilicity, friction, feel, appearance, and electrical properties, the use of microstructured surfaces to combine enhanced properties on a surface has not been demonstrated. Typically, microstructures cause the surface in which they are applied to exhibit only physical properties associated with that particular microstructure. For example, microstructures which result in superhydrophobicity (the extreme water repelling ability of some natural surfaces such as the lotus leaf and synthetic surfaces that mimic natural surface structures) do not readily prevent fluids from being pressed into the microstructure thereby degrading the microstructures effect.
Even though superhydrophobic microstructures have been a popular area of research since the late 1990's, these surfaces have low pressure resistance. Therefore, mechanical pressing of droplets into the surface easily pushes the droplets into the microstructures which cause the droplets to become “stuck” due to contact line pinning. “Stuck” droplets cannot take advantage of the superhydrophobic properties of the underlying surface and the advantages of the superhydrophobic surface can be lost.
Larger microstructures, however, can physically block an intruding item that would otherwise press liquid into the smaller superhydrophobic structures preventing droplets from becoming “stuck”. However, such larger microstructures do not exhibit the desirable superhydrophobic properties of the smaller structures.
Therefore, it is an object of the present invention to provide a microstructure that included an arrangement of various microfeatures such as a smaller set to provide or modify physical properties of the surface such as causing superhydrophobic effects and larger microfeatures to block intruding items.
It is another object of the present invention to provide a microstructure that includes multiple set of microfeatures each exhibiting different physical properties when integrated onto a surface of an object.
The objects of the invention are achieved by providing a microstructure disposed on a surface carried by an object comprising: a first set of microfeatures carried by the object wherein the first set of microfeatures cause the surface of the object to exhibit properties selected from the group of: reduced friction, increased friction, increased heat transference, decreased condensation, increased condensation, liquid repellency, increased absorbance, increased capacitance, increase surface fluid storage, reduced boiling points of a substance in contact with the surface, increased boiling points of a substance in contact with the surface, reduced fluid drag, increased fluid drag, reduced sliding force, increased sliding force, reduced sliding force with applied lubrication, hydrophobic properties, hydrophilic properties, electrical properties, self-cleaning, reduction in hydrodynamic drag, reduction in aerodynamic drag, optical effects, prismatic effects, direction color effects, tactile effects, and any combination of these; and, a second stet of microfeatures carried by the surface wherein the second set of microfeatures is load bearing.
The invention can also include a method for manufacturing a microstructured manufacturing object comprising the steps of: fabricating a microstructured prototype having a first set of microfeatures that cause the surface of the object to have properties selected from a group of: reduced friction, increased friction, increased heat transference, decreased condensation, increased condensation, liquid repellency, increased absorbance, increased capacitance, increased surface fluid storage, reduced boiling points of a substance in contact with the surface, increased boiling points of a substance in contact with the surface, reduced fluid drag, increased fluid drag, reduced sliding force, increased sliding force, reduced sliding force with applied lubrication, hydrophobic properties, hydrophilic properties, electrical properties, self-cleaning, reduction in hydrodynamic drag, reduction in aerodynamic drag, optical effects, prismatic effects, direction color effects, tactile effects, and any combination of these, and, a second set of microfeatures carried by the surface wherein the second set of microfeatures is load bearing; creating a microstructured intermediate from the microstructured prototype so that the surface of the intermediate is a negative of the surface of the microstructured prototype; and, creating the microstructured manufacturing object from the microstructured intermediate.
The invention can also include a microstructure disposed on a surface carried by an object comprising: a first set of microfeatures carried by the object wherein the first set of microfeatures causes the surface of the object to exhibit physical properties differing from physical properties exhibited by a non-microstructured surface; and, a second set of microfeatures carried by the surface wherein the second set of microfeatures causes the surface of the object to exhibit physical properties differing from physical properties exhibited by the non-microstructured surface and by the first set of microfeatures.
In one embodiment, the microstructure can have a first set of microfeatures that has dimensions between 10 nm and 500 μm and said second set of microfeatures has dimensions between 10 nm and 500 μm. In one embodiment, the microstructure can have a first set of microfeatures that has dimensions between 10 nm and 1 μm and said second set of microfeatures has dimensions between 1 μm and 500 μm. In one embodiment, the dimensions of the first set of microfeatures is at least an order or magnitude smaller than that of the second set of microfeatures.
The height:width ratio of the first set of microfeatures is between 1:20 and 7:1. The microstructure can have a first set of microfeatures that have dimensions between 10 nm and 100 μm and the second set of microfeatures has dimensions 100 μm and larger. The spacing between the individual microfeatures can be variable.
The following specification is further understood in reference to the following drawings:
As
Three commonly used models describe different wetting states of a liquid drop resting on a solid: the Young relation, Wenzel relation, and Cassie-Baxter relation. In 1805, Thomas Young analyzed the interaction of a fluid droplet resting on a solid surface surrounded by a gas in
The force balance showed
where the contact angle of the droplet θ is shown on the left hand side of
If the solid surface is rough, and the liquid is in intimate contact with the solid asperities, the droplet is in the Wenzel state. If the liquid rests on the tops of the asperities, it is in the Cassie-Baxter state.
In 1936, Wenzel examined roughened surfaces and assumed that liquid was in intimate contact with solid asperities. Wenzel determined that when the liquid moves a differential distance dx the liquid experiences a change of surface energy dE=r(γSL=γSV)dx+γLVdx cos θ where r is the ratio of the actual area to the projected area. Because equilibrium implies dE/dx=0, the increased solid area interacting with the liquid will change θ to θW as
cos θW=r cos θ (2).
If we assume that the liquid is suspended on the tops of the asperities and denote φ to be the area fraction of the solid that the liquid touches, such a liquid that moves a differential distance dx experiences a change of surface energy dE=φ(γSL−γSV)dx+(1−φ)γLVdx+γLVdx cos θCB. At equilibrium we can solve for the Cassie-Baxter equation:
cos θCB=φ(cos θ+1)−1 (3).
Liquid in the Cassie-Baxter state is more mobile than in the Wenzel state, and so the Cassie-Baxter state is often the desired state for superhydrophobic applications. We can predict whether the Wenzel or Cassie-Baxter state should exist by calculating the new contact angle with both equations. By a minimization of free energy argument, the relation that predicts the smaller new contact angle is the state most likely to exist. Stated mathematically, for the Cassie-Baxter state to exist, the following inequality must be true:
To understand the interplay of surface chemistry and the geometric parameters involved in achieving the Cassie-Baxter state on flat microstructured surfaces, we used equation 4 to predict the pillar heights that cause a transition between the Wenzel and Cassie-Baxter states for a given original contact angle, microstructure diameter, pitch, and height.
When increasing the microstructure pitch, the pillars can be made tall enough to cause the Cassie-Baxter state. As θ increases, the critical height decreases for the same original pitch, and the new contact angle increases.
Contact angle is a measure of static hydrophobicity, and contact angle hysteresis and slide angle are dynamic measures. Contact angle hysteresis is a phenomenon that characterizes surface heterogeneity. When a pipette injects a liquid onto a solid, the liquid will form some contact angle and three phase contact line. The three phase contact line is the line around the droplet where the three phases of solid, liquid, and vapor interact. As the pipette injects more liquid, the droplet will increase in volume, the contact angle will increase, but its three phase boundary will remain stationary until it suddenly advances outward. The contact angle the droplet had immediately before advancing outward is termed the advancing contact angle. The receding contact angle is now measured by pumping the liquid back out of the droplet. The droplet will decrease in volume, the contact angle will decrease, but its three phase boundary will remain stationary until it suddenly recedes inward. The contact angle the droplet had immediately before receding inward is termed the receding contact angle. The difference between advancing and receding contact angles is termed contact angle hysteresis which can be used to characterize surface heterogeneity, roughness, and mobility. Surfaces that are not chemically homogeneous will have domains which impede motion of the contact line. The slide angle is another dynamic measure of hydrophobicity and is measured by depositing a droplet on a surface and tilting the surface until the droplet begins to slide. Liquids in the Cassie-Baxter state generally exhibit lower slide angles and contact angle hysteresis than those in the Wenzel state.
In general, smaller structures resist higher pressure than larger structures. We analyzed the competing forces between surface tension and pressure as
where φ is area fraction of the tops of the microstructures, γ is surface tension of the liquid, θa is advancing contact angle, and λ is the ratio of the microstructure top area/perimeter. Pressure resistance is increased by high area fraction φ, low top area/perimeter ratio λ, and high advancing contact angle θa. Holding spacing and lattice type constant, top area/perimeter ratio λ decreases with decreasing structure size. Therefore, smaller structures maintain the Cassie-Baxter state under higher pressure than do larger structures.
The microfeatures can include various shapes including holes, pillars, steps, ridges, curved regions, raised regions, recessed regions, cones, columns, square columns, rectangular columns, pyramids, asymmetrical shapes and any combination of these. The microfeatures can also have cross sections that are circles, ellipses, triangles, squares, rectangles, polygons, stars, hexagons, letters, numbers, mathematical symbols, asymmetrical shapes, and any combination of these. The cross section of the first set of microfeatures can be different than that of the second set of microfeatures.
When the microstructure includes two or more sets of microfeatures, the distribution can be bimodal or multimodal. Each microfeature of a set of microfeatures can have approximately the same dimensions resulting in a uniform pattern of microfeatures. For example, the smaller the microfeatures shown in
In one embodiment, the first set of microfeatures can be adjacent to the second set of microfeatures. In one embodiment, a preselected pattern of microfeatures includes a region of microfeatures having multiple cross sectional shapes. In one embodiment, a preselected pattern of microfeatures refers to two or more arrays of microfeatures of two or more cross-sectional shapes. In a specific embodiment, the two or more arrays can be positioned side by side; that is, where the two arrays do not overlap. In another specific embodiment, the two or more arrays are positioned to overlap. Microfeatures having the two or more distinctive pattern areas result. In one embodiment, the microfeatures of the second set of microfeatures replace a portion of the microfeatures of the first set of microfeatures.
Microfeatures can be manufactured through the process of stamping, rolling, forging, casting, molding, etching, milling, drilling, plating, electroforming, power processing, electrical discharge machining, and any combination of these.
The smaller structures provide superhydrophobic performance while the larger structures carry the load that interacts with the surface, protecting the smaller structures. 10 μl droplets rested on three different silicone micropillar surfaces: homogeneous 5 μm diameter micropillars, homogeneous 50 μm diameter micropillars, and the heterogeneous combination of 5 and 50 μm diameter micropillars shown in
Referring to
The first and second set of microfeatures can be combined by a method selected from the group of interspersing the microfeatures of one set with those of another set; replacing some members of one set with members of another set, and stacking microstructures from one set on top of microstructures of another set.
In one embodiment, the first set of microfeatures are generally columns having a height over the range of 5 μm to 10 μm with a diameter over the range of 3 μm 7 μm with spacing over the range of 3 μm to 7 μm.
In one embodiment, the second set of microfeatures are generally a column having a height over the range of 10 nm to 200 μm, a width over the range of 10 nm to 200 μm, lengths over the range of 10 nm to 200 μm and spacing over the range of 10 nm to 200 μm.
In one embodiment, the height of the first set of microfeatures has a height of less than 10 nm and the height of said second set of microfeatures is greater than 200 μm. In one embodiment, at least one set of microfeatures includes dimensions over the range of 10 nm to 200 μm. In one embodiment, the microfeatures are comprised of varying dimensions selected from the group of: height, width, spacing, and any combination of these. Further, the orientation of one pattern to another, and the ordered array of the features can vary across the surface.
The first and second set of microfeatures can include holes, pillars, steps, ridges, curved regions, recessed regions, raised regions, and any combination of these employing any cross-sectional shape including circles, ellipses, triangles, squares, rectangles, polygons, stars, hexagons, letters, numbers, mathematical symbols, asymmetrical shapes, and any combination of these. The microfeatures of each of the sets can form a pattern.
In one embodiment, the first set of microfeatures provides advantageous properties selected form the group of: load carrying; protection of underlying surface features; hydrophobicity; hydrophilicity; self-cleaning properties; hydro and/or aerodynamic drag coefficients; optical effects such as prismatic effects, specific colors, reflection, directional dependent color changes, and gloss; tactile effects; grip; electrical characteristic control such as capacitance level; and surface frictional properties.
In one embodiment, the first set of microfeatures provides the function superhydrophobicity and the second set of microfeatures provides the function of load bearing. The first and second set of microfeatures can be carried by a curved surface.
In one embodiment, the set of first or second microfeatures includes one or more macro scale features where the macro scale features can be selected from the group comprising of: channels, grooves, bumps, ridges, recessed regions, raised regions, and any combination of these. The macro scale features can have dimensions selected over the range of 1 mm to 1 m.
In one embodiment, the first or second set of microfeatures comprises a lithographically patterned flexible polymer.
Referring to
In one embodiment, the microstructured prototype takes the form of a silicon wafer or a polymer and can be created by molding, casting and the like. The silicon wafer is patterned with a preselected set of microstructures. Using casting, the pattern is then transferred from the silicon wafer so that the microstructure pattern is formed into silicone rubber. The silicon rubber is then provided to mold the microstructures to an engineering polymer or metal roller surface material. This engineering polymer material transfers the microstructures to material entering the roller press, such as aluminum foil. Accordingly, this forms the microstructures on the object's surface, such as a thin metal foil, through cold-forge molding.
The predefined patterns of microstructures can be made using a method selected from the group consisting of: photolithography, laser ablation, laser cutting, printing, engraving, machining, replication molding, electron-beam lithography, nano-imprint lithography, and any combination of these.
In one embodiment, fabricating the microstructured prototype includes the steps of: providing a semiconductor wafer, patterning the semiconductor wafer with the preselected pattern of microfeatures, molding an uncured flexible polymer to the patterned semiconductor wafer, curing the polymer, thereby forming a microstructured flexible polymer having the preselected pattern of microfeatures, removing the microstructured flexible polymer from said patterned semiconductor wafer and deforming at least a portion of said microstructured flexible polymer so as to conform the microstructured flexible polymer to at least a portion of the surface of the one or more macro scale features of said microstructured prototype.
While a preferred embodiment of the invention has been described using specific terms, such description is for illustrative purposes only, and it is to be understood that changes and variations may be made without departing from the spirit or scope of the following claims.
Number | Date | Country | Kind |
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PCT/US2009/043307 | May 2009 | US | national |
PCT/US2009/049565 | Jul 2009 | US | national |
This application claims the benefit of and the priority from: provisional patent application Ser. No. 61/353,467 entitled Multi-Scale, Multi-Functional Microstructured Material and patent application Ser. No. 12/869,603 entitled Method of Manufacturing Products Having A Metal Surface, which in turn claims priority from patent applications 61/237,119 and Ser. No. 12/813,833, which in turn claims priority from patent applications PCT/US09/043,307 and PCT/US09/049,565, all of which are incorporated by reference.
Number | Date | Country | |
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61353467 | Jun 2010 | US |