Search Images Maps Play Gmail Drive Calendar Translate More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3354022 A
Publication typeGrant
Publication date21 Nov 1967
Filing date31 Mar 1964
Priority date31 Mar 1964
Publication numberUS 3354022 A, US 3354022A, US-A-3354022, US3354022 A, US3354022A
InventorsDettre Robert Harold, Jackson Harold Leonard, Jr Rulon Edward Johnson
Original AssigneeDu Pont
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Water-repellant surface
US 3354022 A
Abstract  available in
Images(3)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

Nov. 21, 1967 R. H. DETTREI ET AL 3,354,022

'y wATER-REPELLANT SURFACE Filed March 31, 1964 v 5 Sheetsfsheet s MEMS/NG ROLLER COL@ /7//P United States Patent 3,354,022 WATER-REPELLANT SURFACE Robert Harold Dettre, Wilmington, Harold Leonard Jackson, Hociressin, and Rulon Edward Johnson, Jr., Wilmington, Del., assignors to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware Filed Mar. 31, 1964, Ser. No. 356,155 8 Claims. (Cl. 161--123) ABSTRACT OF THE DISCLOSURE This invention relates to water repellent, solid surfaces and to a process for their preparation. More particularly, this invention relates to solid surfaces having configurations which endow the surfaces with improved water repellent properties and a method for imparting these configurations to solid surfaces.

Prior to this invention, major efforts in combatting the problem of producing water repellent materials centered around the application of coatings to substrates. A variety of water impervious coatings have been used, but they have the inherent disadvantages characteristic 4of coatings in general, namely, gradual absorption of water by the coating and contact angle hysteresis both of which reduce repellency. These and other problems have prevented the art from producing a durable, highly water repellent surface.

Literature concerning the theoretical requirements for good water repellency has created certain misleading postulates. For example, it is generally believed that water repellency is greatest when the contact angle 0 is as large as possible. Contact angle 6 is defined as the angle (measured through the liquid) which a liquid makes with a solid'. While it is true that increases in the advancing contact angle (the largest experimentally measured contact angle, 0a) and receding contact angle (the smallest experimentally measured contact angle, 0r) can improve repellency, in certain instances increases in both these angles result in decreased depellency. Water repellency, which is defined in terms of the angle a (relative to the horizontal) to which a surface must be tilted in order for a water drop to roll off, depends on the differences in the cosines of the advancing and receding contact angles. This relationship is given by:

` (1) Sin a=KW (cos r-cos 0,) where K'=a constant for a given volume of water W=width of drop Therefore, as mentioned above, repellency can be reduced if the increases in 0r and 0a are such that the difference in their cosines increases.

. The existing literature also gives the impression that formation of a composite surface, i.e., a surface composed of high portions and low portions which when contacted with water will create air-liquid and solid-liquid interfaces between the water drop and the repellent surface, will give improved repellency regardless of the air content of the composite surface. The air content of a composite surface is determined by taking an imaginary plane parallel to the surface passing through the tops of the high portions of the surface and measuring at this plane the percentage of the total surface area which is air.

This hypothesis found in the prior art is partially based on the premise that an increase in contact angle alone is sufficient to improve repellency. However, composite surfaces can be obtained which are less repellent than their smooth counterparts. FIGURE l illustrates graphically the effect of the air content of a surface on the advancing contact angle 9a and the receding contact angle 0!- for a representative solid surface of this invention having a constant chemical composition and an intrinsic advancing water contact angle (0a) of 110 and an intrinsic receding water contact angle (0r) of 92. The intrinsic contact angle (for 0 and 0,) is defined as the contact angle exhibited by a given solid surface when smooth. By a smooth surface is meant a surface having high portions not greater thanabout 0.5 micron in height. Whether a composite surface will be more or less repellent than the corresponding smooth surface depends on the air content of the composite surface. Actually, there is a reduction in repellency for composite surfaces having low percentages of air in the surface when compared to their smooth solid counterparts. This is due to the fact that the advancing contact angle 0 increases more rapidly than does the receding angle 0r when the air content of the surface is increased within certain limits, i.e., from about 0 to about 60% as shown in FIGURE 1. This increase in air content results in an increase in the difference between the contact angles. Referring to Equation 1, this increase in difference causes a concomitant increase in the tilt angle u.

FIGURE 2 further illustrates graphically the relationship between tilt angle a and air content of the fsurface. As shown in the graph, initial increases in air content decrease water repellency until at a certain air content the l tilt angle equals the tilt angle for the smooth surface.

Beyond this critical air content tilt angles decrease drastically. The critical air content is about 60% or morerfor most solid surfaces. Surfaces having low tilt angles when contacted with water droplets exhibit characteristics similar to mercury droplets on glass.

The manufactures, process and theory of this invention will be better appreciated by .reference to the drawing wherein several embodiments of the invention are illusi trated.

FIGURE 1, discussed above, is a graph summarizing the effect of increasing aircontent on 0a and 0r for a given solid surface. Y y

FIGURE 2, discussed above, is a graph summarizing the variations in tilt angle a with increasing air content for a given solid surface.

FIGURE 3 is a plan view in partial section of one embodiment of the present invention wherein b is the distance between the centers of adjacent high portions,

' c is the distance between the outer extremities of adjacent high portions and d is the diameter of a high portion.

FIGURE 4 is a cross-sectional view of the embodiment represented in FIGURE 3 taken along line 2 2 wherein h is the height of a given high portion.

FIGURE 5 is a plan view in partial section of another specific embodiment of the present invention wherein b, c and d have the same meaning as in FIGURE 3.

FIGURE 6 is a cross-sectional view of the embodiment represented in FIGURE taken along line 4--4 wherein h has the same meaning as in FIGURE 4.

FIGURE 7 is a photomicrographic plan view of a representative non-uniform composite surface of this invention wherein the dark areas indicate low portions and the light areas indicate high portions. The angle of illumination of the original photograph was to the plane of the' surface.

FIGURE 8 is a diagrammatic side elevation view of apparatus for preparing surfaces having the configurations dis-closed in this application.

It is an object of this invention to provide a permanent,

solid, water repellent surface. Another object is to provide a method for the production of solid water repellent surfaces. A further object is to provide intermediate means utilizable in processes for the production of these surfaces. These and other objects will become readily apparent from the following description and claims.

These objects are accomplished in accordance with lthe present invention whereby a surface is produced having configurations which impart a greater degree of water repellency to the surface than the corresponding unmodified solid surface.

The tendency for a solid surface to repel water is dependent upon contact angle hysteresis, Le., the difference between advancing (0a) and receding (0,.) contact angles of a water droplet on the solid surface. Where the difference in the above angles is great, there is a tendency for the water droplet to remain on the solid surface, i.e., the surface does not repel water. However, when hysteresis is reduced by lessening the difference between 0a and c1I water droplets are repelled from the solid surface and roll off the surface. When solid surfaces consisting of compositionsv having a high intrinsic contact angle are suiciently modified to produce a composite surface having an air content greater than the critical air content, low contact angle hysteresis is observed and high repellency is obtained.

This can be theoretically explained by considering the thermodynamic properties of a water drop on a composite surface. Qualitatively, these considerations show that when a drop moves over a composite surface the advancing portion of its periphery rnoves rapidly over the solid areas and comes to rest at solid-air boundaries or edges. At these points the contact angle 0 increases to very high values, approaching 180 This behavior reinforces the tendency of the drop, due to its surface tension, to minimize its surface area. The receding portion of the drop periphery tends to remain on solid regions and the contact angle 0r at thesey points approaches the receding contact angle for water on the smooth solid. The extent to which this takes place depends on how much high solid area is present in the composite surface. Opposing the tendency to remain on solid regions is the previously mentioned tendency to minimize surface area. Therefore, as the air content of the composite surface increases and less solid is present to restrain the periphery, the surface tension of the water predominates and the receding contact angle' increases to high values, approach ing those of the advancing portions of the drop.

Specifically, the present invention is directed to a solid surface having an intrinsic advancing water contact angle 0a of greater than 90 and a receding water contact angle 0r of at least 75, Said SOlid surface comprising high portions and low portions, said low portions being at least 60% of the total surface area of the solid surface (i.e., an air content of at least 60% air).and said high portions having an average distance between adjacent high portions of not greater than 1000 microns, the average height of the high portions above the low portions. being at least .5 times the averagedistance between adjacent high portions, said high portions having con gurations which produce a lower tilt angle on said solid surface than exhibited on the corresponding smooth surface.

One embodiment of the present invention involves a solid surface comprising an @ordered arrangement of projections (high portions) consisting of non-contiguous vertically oriented columns of solid rising from the low surface, the maximum distance between the columns being given by where Cm is distance in centimeters, 0a is the intrinsic advancing water contact angle and f is air content expressed as a fraction (i.e., the fraction of the total surface area that consists of low portions), the height of the columns being at least .5 times the distance between adjacent columns, said surface having an air content of at least air (low portions) and the advancing intrinsic water contact angle being greater than 90 and the receding intrinsic water contact angle being at least Another embodiment of the present invention involves a solid surface comprising high portions having therein an ordered arrangement of depressions (low portions), said high portions consisting of interconnected vertical walls of solid which enclose chambers of air, the maximum distance between the walls being given by Cm=0.587 cos 0a where C,m is the distance in centimeters, Qa is the intrinsic advancing water contact angle and the depth of the depressions being at least .5 times the distance between the walls, said surface having an air content of at least 60% air (depressions), the solid surface having an intrinsic advancing water contact angle of greater than and an intrinsic receding water contact angle of at least 75.

A third embodiment involves solids having rough surfaces comprising non-uniform arrangements of high and low portions which on an average fall within the necessary height, distance and air content requirements generic to this invention.

Preferred embodiments of the present invention involve solid surfaces having intrinsic advancing water contact angles of greater than and intrinsic receding Water Contact angles of greater than 85 with air contents of 75% air or above and heights of high portions above low portions about equal to the average distances between adjacent high portions.

In systems comprising ordered arrangements of high portions (projections) the preferred distance between adjacent high portions is about 250 microns or below. On surfaces having an ordered arrangement of depressions surrounded by interconnected vertical walls the preferred distance between adjacent walls is 600 microns or below.

The water repellent surfaces of this invention may be made from any solid surface having an intrinsic advancing water contact angle 0a of greater than 90 and `a receding Water contact angle (if of at least 75. It is necessary that the surfaces have high intrinsic advancing contact angles to prevent liquid penetration in the composite surface due to the hydrostatic pressure of the liquid drops. Receding contact angles of at least 75 are necessary to avoid having to increase the air content of the surface to impractically high values to overcome the attractive forces between the drops and the high solid portions.

Solids found to have the necessary intrinsic contact angles are for example: alkyl polysiloxanes; polyfluoroalkyl polysiloxanes; waxes having a softening temperature greater than 40 C. which are essentially halogen free and water insoluble; and polymers comprising polymerizable or copolymerizable ethylenic compounds which will form polymers having the following surface constitutions:

as described by Shafrin and Zisman, l. Phys. Chem. 64, 519, 521 (1960).

Speciiic examples of operable ethylenic compounds which fall within the definition of the invention are as follows:

where n is from 3 to 13.

Examples of polymers which arev not satisfactory are the homo-polymers of: CF2=CC12, CHZZCHOI,

CHFCClz, CHFCHCN The waxes which are operable in this invention are:v Natural waxes such as beeswax, candelilla wax, carnauba Wax, esparto wax; petroleum waxes such as paratiin waxes, micro-crystalline waxes; fossil or earth waxes such as montan wax, ozocerite, peat wax and synthetic waxes such as Fischer-Tropsch waxes and hydrogenated waxes.

While most solid surfaces exhibiting the required intrinsic contact angle show improved repellency over thesmooth unmodified surface when the air content is above about 60% and the other conditions mentioned above are met certain surfaces (e.g., polyethylene) do not show improved repellency until the air content of the surface is about 75% to 80% air.

The expressions listed above for the distance between adjacent high portionsare derived from a consideration of the water penetration pressure on the surfaces as follows: When a cylindrical capillary is made of a material which when smooth has an advancing water contact angle, 0a, greater than 90, a pressure, P, is required in order 6. to force the water into the capillary. The magnitude of the pressure is given by 2 P=47 cos 6a where Fy is the surface tension of water and c is the diameter of the capillary. Using the value for the surface tension of water at 25 C. and expressing P in centimeters of water, Equation 2 becomes cos 6a cos 0, c

where 0r is the receding contact angle. if Hr is less than the water will show no tendency to come out of the capillary. For most solids with non-zero Contact angles, @a and 0, are not equal (0r being less than 0a). In this situation the angles 0a and 0r are not to be confused with the angles actually observed forl water drops on the embossed surface. The present angles 9a and 0r refer to the water angles on the solid regions of the embossed surface. In some instances surfaces can be prepared where 6:0r but this requires special procedures to obtain smooth surfaces and elaborate purication methods to obtain homogeneous surfaces; It is probably impossible to obtain homogeneous polymer surfaces; even adsorbed monolayers are, to some extent, heterogeneous. Many materials possess surfaces when smooth which have 0g greater than 90 and 0r less than 90. It is therefore necessary to emboss the surfaces of these materials in order to have high repellency. For a given surface (with a 9a 90) the penetration pressure is determined by the distance, c,- in Equation 3. The maximum distance that could be tolerated would be one which prevents water drops from penetrating under their own hydrostatic pressure. The maximum 'height that a water drop can attain in the presence of gravity is about 0.5 cm. The maximum distance, Cm (in cm.), is then given by i (5) Cm=0.587 cos 0,L

edv cos 0a where d is the diameter of the cylinders and b is the center-to-center distance between cylinders. Expressed in terms of f (the fraction 'of the total surface area that is air) and the distance, c, between the outer walls of the cylinders (c=b-d) and using the value for the surface tension of water at 25 C., Equation 6 becomes P= [\/2.721 1-f) -rraau-fo'g) @OS 0 Where P is expressed in centimeters of water. ImposingV the condition that a water drop should not penetrate into the surface under its own hydrostatic pressure gives for the maximum distance between cylinder walls,

In a system of random dispersed high portions (rough surfaces) it is difficult to give exact mathematical definitions of distance ranges. However, prepared surfaces having average distances between adjacent high portions falling within the generic requirements of this invention provide improved water repellency. Preferred non-uniform surfaces having distances of from about 20 microns to about 400 microns have been found to impart superior water repellency to surfaces provided the largest average spacing between adjacent high portions is below about 300 microns.

The high portions of the composite surfaces of this invention must have certain configurations in order to provide the proper air content while at the same time avoiding penetration of the liquid into the low portions of the surface. Optimum results are achieved when the sides of the walls or projections are perpendicular to the plane of the surface, however, it is not necessary that the sides of the projections or walls be absolutely vertical or perpendicular to the surface. It is sufficient if somewhere on all sides of a given high portion there is a point at which a line drawn tangent to the side will make an angle between the tangent and the horizontal, measured through the high portion, of about 80 or more.

Methods of preparing water repellent surfaces The present invention is also directed to a process for the preparation of water repellent solid surfaces which comprises contacting a solid surface having an intrinsic advancing water conta-ct angle of greater than 90 and an instrinsic receding contact angle of at least 75 with means for softening said solid surface, contacting the solid surface with a die capable of producing a positive configuration comprising high portions and low portions on the solid surface wherein the height of the high portions and the distance between adjacent high portions will conform to the requirements previously stated and removing said die from contact with the solid surface.

Alternatively, the softening step may be dispensed with provided the die form or mold is of sufficient mechanical strength to withstand pressures necessary to impart the desired configurations to the surface materials of this invention without damage to the die or loss of detail in the resulting surface configuration.

Die forms or molds utilizable in the practice of this invention include commercially available screens or mesh plates, photosen-sitive polymers which after exposure to actinic light are treated to produce the negative of the desired surface configuration, metallic dies produced by contacting the metal with photosensitive polymers having the positive configuration desired to be reproduced on the solid surface and masses of hollow fibers rigidly held together by suitable means. These holiow fiber die forms or molds are aligned together in parallel manner in bundles and cut or sliced approximately perpendicular to their length to create a die surface of their cross-section. The outer diameter of these hollow fibers must be on an average in the range of from about l to about 450 microns and the inner diameter must be on an average less than about .6 times the outer diameter. The length of hollow fibers used in the die must be at least .5 times the difference between the inner and outer diameters of the hollow fibers.

I. Surfaces consisting of projections A novel and convenient method for preparing a surface consisting of vertical projections has now been provided by utilizing a mass of hollow fibers as a die form or mold. The hollow fibers may be obtained as described in U.S. Patent 2,999,296 and French Patent 990,726. The outer diameter of the fibers used measure within the range of 10 to 450 microns and are 1.2 to 3.0 times the inner diameter. The fibers are compacted together and cut or sliced approximately perpendicular to their length exposing the cross-section. The truncated ends are then used as a mold or die. The surface to be treated is softened slightly, by heating or other suitable means (e.g., solvents) to facilitate impression of the surface by the mold. The surface hardens as it cools, whereby high portions (projections) resembling vertical columns corresponding to the hollow cores of the fibers are permanently developed on the surface. The hollow fibers may be assembled into bundles of various shapes and sizes or may be attached to a roller having the truncated ends of the fibers as the roller surface. A large quantity of the object having the surface to be treated may be conveyed in such a manner under the roller so that the pattern is stamped on the surface.

II. Surfaces consisting of depressions One method of producing a pattern of depressions on a surface is now provided by first preparing a -grid conforming to the required surface dimensions by drawing the pattern on a sheet of paper which transmits actinic light. The pattern so drawn is a model of the pattern desired on a large scale. By reducing photographically, the pattern is obtained in the small scale desired. A halftone screen, such as is used in photography, may also be used in place of the paper pattern. A relief image of the pattern is made on photosensitive plastic by placing the paper pattern on halftone screen over the plastic and exposing to actinic light, as described in U.S. Patent 2,760,- 863. There is formed on the plastic a relief image of the pattern. This plastic grid is now used as a die and impressed onto another surface capable in itself of being used as an embossing die, eig., Woods metal. This die, bearing a reverse pattern of the grid, is impressed on the surface to be made water repellent in the same manner as described above for the hollow fiber surface. The lines of the original paper pattern thus become the walls of the depressions. The embossing dies may also be made of any metal or non-metal which can be chemically or mechanically modified to give the desired surface pattern with the desired spacings and dimensions, providing the material is of sufficient strength to permit its use as a die. Alternatively, a photosensitive glass available commercially, such as described in Glass Engineering Handbook, E. B. Shund, McGraw-Hill, New York, 2nd ed., 1958, p. 363, may be used in the preparation of such a surface. By following the lmethod described in the above reference for preparing patterned glass, a surface having an array of depressions may be produced directly.

However, glass in itself does not possess the requisite advancing and receding water contact angles. It must therefore be treated with a material having the necessary intrinsic advancing and receding water contact angles to achieve the desired water repellency by a physical coating process. Or, for example, monoor multilayers of a substance having the required Contact angles may be chemisorbed on the glass to form a strongly adherent coating. The coating acquires the configuration of the glass substrate thereby forming a highly water repellent surface.

The following examples are given to illustrate various specific embodiments of this invention and do not limit the invention in any way.

Contact angles were measured directly on profiles of sessile drops using the general method described in Surface Chemistry by I. J. Bikerman, Academic Press, Inc., New York (1958), 2nd ed., p. 343. In these examples contact angles were measured on profiles of sessile drops using a microscope fitted with a goniometer eyepiece; magnification was about 20X. Error in angle measurements by this method is estimated to be about if. Drop addition and size changes were made using a hypodermic syringe. Advancing angles were measured after the drop size was increased and the periphery advanced over the surface; receding angles Were measured after the drop size was reduced and the periphery receded. Unless otherwise stated, readings were taken with 30 seconds of drop formation and/or size change, and drop volumes were between 0.03 and 0.10 ml. Receding angles were measured on drops that had been in contact with the surface for some time (several minutes) before being receded and on fresh drops which were placed on the surface and immediately (several seconds) reduced in size. There was little difference between these two methods as long as the drop size was kept below 0.1 ml. Each contact angle value is the average of at least 8 measurements. All measurements were made at 25 il C. and 50% relative humidity.

In these examples the air content of the surface was determined by photomicrographs (plan view) of the surface. The photomicrographs are taken with the plane formed by the tops of the high portions of the surface in focus. The fraction of the total area of the photomicrographs that is air is taken as the air content of the surface. The magnification is chosen such that each photomicrograph includes enough of the area of the surface to give a reliable and reproducible value for surface porosity (air content).

The method used to determine tilt angles (a) in these examples is essentially that described in I. Colloid. Sci., vol. 17, p. 309 (1962), by C. G. L. Furmidge. The surface to be studied was placed on a hinged brass plate. A drop of water of the required volume was placed on the experimental surface using a hypodermic syringe. The hinged plate was immediately `rotated until' the 'drop started to roll off the surface. The angle to which the plate was rotated was then measured .to the nearest degree lwith a protractor. With only slight differences the tilt anglennecessary to cause the drop to commence rolling is equal to the angle necessary to keep the drop rollmg.

EXAMPLE 1 An embossing die is made in the following manner: A bundle of hollow fibers of a copolymer of tetraiiuoroethylene and hexauoropropylene is compressed, using a hose clamp, to give a close-packed arrangement of the fibers. The hollow fibers have an inside diameter of 250 microns and an outside diameter of 430 microns. The clamped Ibundle is then cut with a microtome knife so that the surface thereby formed is iiush with one end of the hose clamp. This surface (1.5 cm. in diameter), which consists of the truncated ends of the hollow fibers, is used as an embossing die.

The die described above is pressed (by hand) against the warm surface of a piece (2 cm. x 2 cm. x 1 cm.) of paraffin wax. The surface of the Wax is previously heated to 35 to 40 C. (to a depth of about 1 mm.) in order to soften it and thereby facilitate fiow into the holes of the die. There is negligible adhesion of the paralin wax to the hollow fiber die. The embossed surface consists of an array of cylindrical projections oriented at right angles to the original wax surface. There is negligible penetration of wax into the spaces between the fibers of the die because these spaces are sufficiently small, the applied pressure during embossing is low enough and the flow properties of the wax at 35 to 40 C. are poor enough to prevent penetration.

The cylindrical projections are about 250 microns in diameter and 150 to 200 microns high. The distance between centers of adjacent projections is about 430 microns and the area of the surface, measured at the plane formed by the tops of the projections, is approximately 70% air. The advancing contact angle for a water drop has increased from 113 on the original surface to 144 on the embossed surface and the receding angle has increased from 100 to 129. The tilt angle necessary for a 0.05 ml. water drop to roll olf the surface has decreased-from to 9.

A lower tilt angle for one surface than for another means that if both surfaces are vertical the surface with the lower tilt angle will permit roll-off of smaller water drops. This is equivalent to saying that liquid 'retention will be lower on the surface with the lower tilt angle.

In actual practice the hollow fiber dies can be many times larger in area then the one described above and the embossing process can be carried out using conventional presses. For example, the fibers can be mounted in closepacked array on any rigid backing such as a metal or hard plastic plate, the dimensions of the plate being determined by the size of the surface to be embossed or by the size of the embossing press. A plate of several square feet in area is possible. The close packing can be achieved and maintained by exerting lateral pressure at the periphery of the plate or by sealing the fiber ends to the plate using a suitable adhesive. l

Alternatively, for applications where continuous embossing of large areas is desirable, the fibers can be mounted on a roller of several feet in length and of sufficient diameter so that close packing of the fibers is possible at the outer surface of the die.

The parafiin wax in this example need not be a solid piece of the wax alone. It can just as well be a thin coating of wax (as thin as 0.1 mm.) on another surface, such as a sheet of glass or metal. I'

EXAMPLE 2 An embossing die is made in the manner described in Example 1 using hollow fibers of polyethylene. These fibers have an inside diameter of 80 to 95 microns and an outside diameter of 220 microns. This die (1.5 cm. in diameter) is used to emboss the parafiin wax surface of Example 1 using the method described in Example 1.

The resulting -cylindrical projections of the embossed surface are 80 to 95 microns in diameter and 200 to 300V microns high. The distance between centers of adjacent projections is 240 to 300 microns and the area of the surface, measured at the plane formed by the tops of the projections, is approximately 87% air. The advancing contact angle for a drop of Water has increased from 113 to 156 and the receding angle has increased from 100 to 148. The tilt angle necessary for a 0.05 ml. water drop to roll off the surface has decreased from 15 to 4.

As with the hollow fiber dies of Example 1, it is also possible to fabricate dies which are much larger than the one used in this example.

EXAMPLE 3 The hollow ber die of Example 1 is pressed (by hand) against the surface of a piece of polypropylene film (2 cm. x 2 cm. x 0.05 cm.) having a melting point of about 165 C. and a melt index of about 0.5. The film is previously heated to 150 to 155 C. to soften it and thereby facilitate flow into the holes of the die. The die is also heated (to to 120 C.). The embos-sed surface consists of an array of cylindrical projections 250 microns in diameter and 500 to 6.00 microns high. There is negligible penetration of polypropylene between the fibers of the die. The average distance between centers of adjacent projections is about 450 microns and the area of the surface, measured at the plane formed by the tops of the projections, is approximately 75% air. The ad` vancing contact angle for a water drop has increased from on the original fiat surface to 139 on the embossed surface and the receding Contact angle has increased from 85 to 115. The tilt angle necessary for a 0.10 ml. water drop to roll off the surface has decreased from 21 to 16.

The larger dies described in Example 1, particularly the roller type, can be used to emboss large sheets of polypropylene to produce the surface described in this ex. ample.

1 1 EXAMPLE 4 The hollow fiber die of Example 1 is pressed (by hand) against the surface of a piece of polyethylene film (2 cm. x 2 cm. x 0.1 cm.) having a melting point of about 110 C. and a melt index of 1.8. The film is previously heated to 102 to 105 C. to soften it and thereby facilitate ow into the holes of the die. The die is also heated (to 95 to 100 C.). The embossed surface consists of an array of cylindrical projections 250 microns in diameter and 450 to 500 microns high. There is negligible penetration of polyethylene between the fibers of the die. The average distance between centers of adjacent projections is about 450 microns and the area of the surface, measured at the plane formed by the tops of the projections, is about 75% air. The advancing contact angle for a water drop has increased from 98 on the original at surface to 140 on the embossed surface and the receding contact angle has increased from 76 to 105 The tilt angle necessary for an 0.05 ml. water drop to roll off the surface has decreased from 30 to 22.

EXAMPLE 5 A relief image of the configuration desired is prepared according to the method described in U.S. Patent 2,760,863, whereby the surface of a photosensitive polymer (1 mm. thick coating of the polymer on a 2.5 mm. thick sheet of aluminum) is irradiated with actinic light which has first passed through a photographic transparency on which there is an ordered array of opaque squares separated by ne spacings that transmit the actinic light. The exposed regions of the photosensitive polymer undergo a chemical reaction which makes them more resistant than the unexposed regions to attack by caustic solution. After a thorough washing with caustic solution the resulting polymer surface consists of a network of interconnecting walls (intersecting at right angles) enclosing square-shaped depressions. The walls are 27 microns thick and 130 microns high. The distance between walls (centerto-center) is 195 microns. The network is approximately 1 cm. square in area.

An impression of this network is obtained by covering the surface with molten (80 to 100 C.) Woods metal (a 0.5 cm. thick layer of the liquid metal covers the surface), applying a vacuum (0.1 mm. of mercury) to remove air from between the Woods metal and the polymer surface, and then restoring atmospheric pressure in order to force the liquid metal into the depressions of the polymer surface. rIhe solidified metal impression is used to emboss the paraiin wax surface of Example 1. The same embossing procedure is used as in Example 1.

Alternatively the negative form of the desired surface configuration can be produced on the photosensitive polymer. However, a caustic Washing procedure is necessary to -completely flush out the narrow (27 microns) channels which result if the negative form is made. Therefore, the procedure utilizing the Woods metal impression is preferred in order to obtain the negative form for use in embossing other surfaces.

The embossed wax surface is a replica of the original photopolymer surface. However, some loss in surface detail has resulted from the above procedure of making an impression of an impression. The center-to-center dis tance between walls is 190` microns; the walls are 37 microns thick and 130 microns high. The area of the surface, measured at the plane formed by the tops of the walls, is 65% air. The advancing contact angle for a water drop has increased from 113 on the original flat surface to 137 on the embossed surface and the receding angle has increased from 100 to 116. No decrease in tilt angle was obtained here since this example represents the lower limit to the air content of a parafin wax surface.

EXAMPLE 6 An embossing die is produced in the manner described in Example 5 and a at parafn wax surface is embossed in the manner described in Example 1. The embossed wax surface consists of interconnecting walls 15 microns thick and 130 microns high. The distance between walls (centerto-center) is 195 microns and the area of the surface, measured at the plane formed by the tops of the walls, is about air. The advancing contact angle for water has increased from 113 on the original flat surface to 155 on the embossed surface and the receding contact angle has increased from 100 to 145. rl`he tilt angle necessary for a 0.015 ml. water drop to roll off the surface has decreased from 15 to 4.

In actual practice the embossing dies described in this example and in Example 5 can be many times larger and can be used in plate or roller form. The Woods metal die described here would be applicable only to surfaces of materials which have the desirable flow characteristics at temperatures below 65 C. For other materials, dies of higher melting metals or alloys must be used.

If suficient care is taken in washing technique, the negative photopolymer surfaces can be fabricated and used directly as embossing dies.

EXAMPLE 7 A fluorocarbon wax dispersion in 1,1,2-trichloro-1,2,2 triiiuoroethane, obtained by reacting methanol and tetraiiuoroethylene in the manner described in U.S. Patent 3,067,262 (the Wax having a crystalline melting point of 278 C., an approximate molecular weight of 2000) and containing about 20% solids, is diluted with a solution of 50 parts of trichloroiiuoromethane and 50 parts of dichlorodifluoromethane to give a solids concentration of about 1%. This mixture is sprayed onto a 1" x 3 glass microscope slide to give a coating which is 0.1 to 0.2 mm. thick. All components of the above mixture except the wax are volatile. The wax particles at the top of the coating are 5 to 80 microns in diameter, the spacing between them is 20 to 160 microns and the area of the surface in the plane formed by the top of the coating, is approximately 88 to 90% air. The advancing contact angle for a water drop on this surface is 159 and the receding angle is 156; the corresponding angles for a smooth, flat surface of the wax are 111 and 95 re spectively. The tilt angle necessary for a 0.05 ml. water `drop to roll off the surface is 18 for the smooth wax and about 1 for the sprayed wax.

EXAMPLE 8 A mixture containing 90 parts of a 12.5% solution of paraiiin wax in n-hexane and 10 parts of glass beads of a diameter in the range 3 to 12 microns, is heated to 40 to 50 C. and sprayed onto a 1" x 3 glass microscope slide to give a coating which is 0.1 to 0.2 mm. thick. The n-hexane rapidly evaporates from the surface leaving agglomerates of wax-coated glass beads. The agglomerates at the top of the coating are 15 to 250 microns in diameter, the spacing between them is 50 to 350 microns and the area of the surface in the plane formed by the top of the coating, is approximately 88% air. The advancing contact angle for a water drop on this surface is 158 and the receding angle is 156; the corresponding angles on a smooth, flat paran wax surface are 113 and 101 respectively. The tilt angle necessary for a 0.05 ml. water drop to roll off the surface is 15 for the smooth wax and about 1 for the sprayed wax-glass bead mixture.

In Examples 7 and 8 above, all parts are by weight.

EXAMPLE 9 A 400 line per inch nickel mesh plate, commercially available from the Buckbee Mears Co., St. Paul, Minn. (6" x 6) with a square array of holes (28 to 29 microns square with a center-to-center distance of 60 microns and a depth of 25 microns) is used as a die to emboss a lm (3 cm. x 6 om. x 15 cm.) of a copolymer of tetrafluoroethylene and hexaiiuoropropylene. The plate iS 13 pressed against the film in a Carver laboratory press at 12,000 to 14,000 p.s.i. and 100 C. for 15 minutes. The plate` is then peeled from the film; there is negligible adhesion between plate and film. The embossed surface consists. of a regular 'l arrayof square-shaped projections oriented at right angles to the original film surface..'l`hese projections are 28 to 29 microns on a side and 22 to 25 microns high. The centertocenter distance of adjacent projections is 60 microns and the area of the surface, measured at the plane formed by thetops of the' projections is 75 to 78% air. The advancing vangle for a water drop has increased from 114V on the original surface to 157H on the embossed surface and the receding angle has 4increased from 97 to 134. Thetilt angle necessary for a 0.05 ml. drop to roll off the surface has decreased from'23 on the smooth surface to 12 on the embossed surface. v EXAMPLE 10 The nickel mesh plate of Example 9 above is pressed against the surface of -a film of polypropylene (3 cm. x 6 cm. x 0.05 cm.) at 16,000 p.s.i.,and 140 C. for 20 minutes. The plate is peeled from"the film; there is negligible adhesion between plate and film. The embossed surface is asdescribed in Example 9 above. The advancing angle for a-water drop has increased from 107 on the original surface to 158 on the embossed surface and the receding angle has increased from, 83 to 110. The tilt angle necessary-forv a 0.05 mlfdrop to roll off the surface has decreased from 34 to 22.

EXAMPLE 1l A fiuorocarbon wax having a melting range of 95 to 135 C. and the general formula where n varies from 3 to 9 but is predominately 7 and 8, is dissolved in 1,1,2-trichloro-1,2,2-triuoroethane to the extent of about 5%. About 100 parts of the above solution and parts of glass beads having diameters in the range of 3 to 12 microns are mixed together, heated to about 40 C. and sprayed onto a 1 by 3 glass microscope slide to give a coating which is 0.1 to 0.2 mm. thick. The 1,1,2-trichloro-1,2,2-trifluoroethane rapidly evaporates from the surface leaving agglomerates of waxcoated glass beads. The agglomerates at the top of the coating are to 300 microns in diameter, the spacing between them is 80 to 300 microns and the area of the surface in the plane formed by the top of the coating, is approximately 82% air. The advancing contact angle for a water drop on this surface is 157 and the receding angle is 154; the corresponding angles on a smooth, flat surface of the wax are 128 and 114 respectively. The tilt angle necessary for a 0.05 ml. water drop to roll off the surface is 13 for the smooth wax and about 1 for the sprayed wax-glass `bead mixture. In the above example, all parts are by weight.

EXAMPLE 12 A continuous film of polyethylene (3 ft. wide, 150 microns thick) having a melting point of 110 C. and a melt index of 1.8 is passed beneath a suitable heater which heats the top half of the film to 102 to 104 C. The lm is then passed between two rollers. The surface of one roller is covered with the close-packed ends of hollow fibers of a copolymer of tetrauoroethylene and hexafluoropropylene. The hollow fibers have an inside diameter of 50 microns and an outside diameter of 123 microns. The surface of the embossing roller is heated to 95 to 100 C. just before it comes into Contact with the film as shown in FIGURE 8. This facilitates 4fiow of the polyethylene into the holes of the die. Before the film is separated from the embossing roller, a stream of cold air is directed -at the film in order to cool it to about C. Adhesion of the polyethylene to the copolymer is negligible and the film readily separates from the surface of the embossing roller.

The embossed surface consists of an array of cylindrical projections 50 microns in diameter and 200 microns high. The average distance between centers of adjacent projections is 123 microns and the area of the surface, measured at the plane-formed by the tops of the projections, is air. The film thickness, excluding the projections,v isnow microns. The advancing Contact angle for a water drop has increased from 98 on the original fiat surface to on the embossed surface and the receding -anglehas increased from 76 to 120. The tilt angle necessary for a 0.05 ml. water drop to roll olf the surface has decreased from 30 to 18".

Several of these 3-feet sheets, sealed together, can be used in shower curtains to make them more resistant to accumulation of undesirable film since much of this accumulation on ordinary curtains results from wetting of the surface and subsequent evaporation of the water thereon. l y

The embossed surfaces prepared as described in the preceding examples exhibit a lower tilt angle and thereby a vastly improved water repellency. The configuration of projections or depressions causes the advancing and receding contact angles to increase so that the drop width a'nd the difference in the cosines of the receding and advancing contact angles are decreased. The high water repellency is thus due to the intrinsic structure of the surface.

The novel water repellent surfaces of the invention are useful in the production of numerous articles which shed water easily, such as ranwear, shower curtains, tenting material and plastic and ceramic tiles. These surfaces may also constitute condenser surfaces of solar stills land serve as surfaces where ice formation is to be minimized.

While the composite surfaces of this invention have ben shown to have utility in repelling water, they also sh'ow improved repcllency to other liquids both water and oil based which exhibit intrinsic advancing contact angles of greater than 90 and intrinsic receding contact angles of at least 75. For example, liquids with surface tensions considerably lower than that lof water ('yf=72.8 dynes/cm. at 20 C.) will show increased repellency on the spray-coated surface of Example 11. That composite surface has shown improved repellency over the corre sponfding smooth, flat surface to motor oils with surface tensions las low as 32 dynes/cm. Examples of other liquids to which the surface of Example 11 will show improved repellency include:

'y (dynes/cm. at 20 C.)

Composite surfaces of this invention have shown improved repellency to liquids with viscosities in the range of from 5,000 to 10,000 centipoises and surface tensions greater than 40 Idynes/cm. and viscous, aqueous sugar solutions with viscosities of 3000 centipoises and surface tensions close to that of water. Aqueous solutions of inorganic salts will also be repelled more readily since their surface tensions range from 72 to 85 dynes/cm.

As many apparently wi'dely different embodiments of this invention may be made Without departing from the spirit and scope thereof, yit is to be understood that this invention is not limited to the specific embodiments thereof.

What is claimed is:

1. A solid composition having projections extending from the surface thereof, said projections having an average rdistance of not greater than 1000 microns between adjacent projections and having an average height of -at least .5 times the avenage distance, said projections spaced such that the air content of the surface of the composition is at least 60% air, said projections shaped such thiat a line drawn tangent to the sides thereof makes an angle between the tangent land the plane of said surface of =at least 80 when measured through the projection, said surface 'of said projection having an intrinsic advancing Water contact angle of greater than 90 and an intrinsic receding water contact :angle of aft least 75, said surface having a lower tilt angle for water than the corresponding smooth surface.

2. The composition vof claim 1 wherein the average distance between adjacent projections is not greater than 600 microns and the avenage height of the projections is equal to the average distance between adjacent projections, wherein said |air content is at least 75% air, and wherein the intrinsic advancing Water Contact angle is greater than 100 and the intrinsic receding water Contact angle is at least 85.

3. The composition of claim 1 wherein said composition is polyethylene @and wherein the ail content is at least 75 air.

4. The composition Iof claim 1 wherein said projection-s are 11o-contiguous, vertically oriented celums, and wherein the miaximum distance between columns is given by the equation {1339} COS wherein Cm is the distance in centimeters, 6EL is the intrinsic advancing water contact angle and A is the ai-r content expressed las 'a fraction.

5. The composition of claim l-wh'ere'in said projections are ordered interconnected vertical walls and wherein the maximum distance between |adjacent Walls is given by the equation 'Cm=0.587 cos 6a where Cm is the distance in centimeters and 0a is `the intrinsic advancing Water content langle.

6. The composition of claim 1 wherein `said projections are nonuniformlly arranged, and wherein the average distance between adjacent projections is not greater than 300 microns. .f

7. The composition of claim 1 in the form of a film having said projections Ion one side thereof. v

8. The composition of claim 1 in the form of a sheet having said projections on one `side therof.

References Cited Bird Y 161- 116 MORRIS sUssMAN, Primary Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1409768 *11 Jul 191714 Mar 1922Barrett CoFloor covering
US2582294 *31 Oct 194715 Jan 1952Dow Chemical CoContinuous method for cooling and shaping thermoplastics
US2667436 *21 Sep 195026 Jan 1954Carborundum CoPressure sensitive adhesive coated sheet material
US2865046 *18 Jul 195623 Dec 1958Collins & Aikman CorpApparatus and method for producing patterned foam rubber coated fabrics
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3502765 *24 Aug 196724 Mar 1970Eastman Kodak CoMethod of controlling edge flatness of mechanically embossed oriented polymer sheeting
US3969565 *26 Mar 197513 Jul 1976Norman ForrestCard clothing method for treating thermoplastic sheet material
US4219376 *5 Mar 197926 Aug 1980L. E. Carpenter & Company, Inc.Flexible acoustical wall covering, method of making same, and wall panel employing same
US4324749 *18 Jun 198013 Apr 1982Akzona IncorporatedThree-dimensional exchange element for liquid guidance in liquid-gas contact systems
US5599489 *25 May 19954 Feb 1997Onoda Cement Co., Ltd.Preparing molded articles of fluorine-containing polymer with increased water-repellency
US666036325 Jul 19959 Dec 2003Wilhelm BarthlottSelf-cleaning surfaces of objects and process for producing same
US668312625 Apr 200127 Jan 2004Basf AktiengesellschaftCompositions for producing difficult-to-wet surface
US671293212 Feb 200230 Mar 2004Papierfabrik Schoeller & Hoesch Gmbh & Co. KgMethod of producing self-cleaning and non-adhesive paper or paper-like material
US6764745 *25 Feb 199920 Jul 2004Seiko Epson CorporationStructural member superior in water repellency and method for manufacturing the same
US6773786 *16 Aug 200010 Aug 2004Asten Privatgesellschaft Mit Beschraenkter HaftungPaper machine cover
US680035412 Dec 20015 Oct 2004Ferro GmbhSubstrates with a self-cleaning surface, a process for their production and their use
US681185612 Apr 20022 Nov 2004Creavis Gesellschaft Fuer Technologie Und Innovation MbhProperties of structure-formers for self-cleaning surfaces, and the production of the same
US683080021 Jun 200114 Dec 2004The Procter & Gamble CompanyElastic laminate web
US684119714 Nov 200111 Jan 2005Degussa Agn-Propylethoxysiloxanes, their preparation and use
US68582849 Apr 200222 Feb 2005Creavis Gesellschaft Fuer Technologie Und Innovation MbhSurfaces rendered self-cleaning by hydrophobic structures, and process for their production
US686396021 Jun 20018 Mar 2005The Procter & Gamble CompanyUser-activatible substance delivery system
US6872441 *13 Mar 200129 Mar 2005Ferro GmbhGlass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof
US687843321 Jun 200112 Apr 2005The Procter & Gamble CompanyApplications for laminate web
US688449421 Dec 199926 Apr 2005The Procter & Gamble CompanyLaminate web
US692228723 Oct 200126 Jul 2005Unaxis Balzers AktiengesellschaftLight coupling element
US6946170 *21 Feb 200320 Sep 2005Gottlieb Binder Gmbh & CompanySelf-cleaning display device
US69770945 Dec 200220 Dec 2005Degussa AgProcess for producing articles with anti-allergic surfaces
US69970182 Jun 200314 Feb 2006Ferro CorporationMethod of micro and nano texturing glass
US703756920 Dec 20002 May 2006The Procter & Gamble CompanyLaminate web comprising an apertured layer and method for manufacturing thereof
US708382818 Dec 20031 Aug 2006Goldschmidt GmbhProcess for producing detachable dirt- and water-repellent surface coatings
US719604322 Oct 200327 Mar 2007S. C. Johnson & Son, Inc.Process and composition for producing self-cleaning surfaces from aqueous systems
US72113133 May 20021 May 2007Degussa AgSurfaces rendered self-cleaning by hydrophobic structures and a process for their production
US722033230 Jan 200422 May 2007The Procter & Gamble CompanyElectrical cable
US742300314 Aug 20019 Sep 2008The Procter & Gamble CompanyFold-resistant cleaning sheet
US752453127 Apr 200528 Apr 2009Ferro CorporationStructured self-cleaning surfaces and method of forming same
US753159813 Jun 200612 May 2009Goldschmidt GmbhProcess for producing detachable dirt- and water-repellent surface coatings
US760414725 Nov 200320 Oct 2009Anheuser-Busch Inbev S.A.Keg with an inner bag
US7650848 *5 Dec 200626 Jan 2010University Of Florida Research Foundation, Inc.Surface topographies for non-toxic bioadhesion control
US7722951 *15 Oct 200425 May 2010Georgia Tech Research CorporationInsulator coating and method for forming same
US772758317 May 20051 Jun 2010Basf AktiengesellschaftMethod for the production of structured surfaces
US779023829 Jan 20047 Sep 2010Basf AktiengesellschaftMethod for hydrophobing textile materials
US779937827 Nov 200321 Sep 2010Japan Science And Technology AgencyProcess for producing micropillar structure
US782888931 Oct 20059 Nov 2010The Clorox CompanyTreatments and kits for creating transparent renewable surface protective coatings
US7846529 *21 Dec 20057 Dec 2010Evonik Degussa GmbhSelf-cleaning surfaces comprising elevations formed by hydrophobic particles and having improved mechanical strength
US78510454 Jul 200114 Dec 2010Saint-Gobain Glass FranceTransparent textured substrate and methods for obtaining same
US78510569 Jun 200514 Dec 2010University Of Florida Research Foundation, Inc.Ultralyophobe interfaces
US7901731 *30 Jun 20108 Mar 2011The Clorox CompanyTreatment and kits for creating transparent renewable surface protective coatings
US790617211 Sep 200615 Mar 2011Basf AktiengesellschaftMethod for coating surfaces and suitable particles therefor
US792740523 Apr 200719 Apr 2011Gore Enterprise Holdings, IncPorous composite article
US795551829 Jun 20107 Jun 2011Basf AktiengesellschaftMethod for hydrophobing textile materials
US795981521 Dec 200714 Jun 2011Saint-Gobain Glass FranceTransparent textured substrate and methods for obtaining same
US797269616 Mar 20075 Jul 2011Wacker Chemie AgParticles with structured surface
US8007638 *4 Jul 200630 Aug 2011Astenjohnson, Inc.Sheet-like products exhibiting oleophobic and hydrophobic properties
US803417331 Oct 200511 Oct 2011Evonik Degussa GmbhProcessing compositions and method of forming the same
US804365427 Sep 201025 Oct 2011The Clorox CompanyTreatments and kits for creating transparent renewable surface protective coatings
US807566922 Apr 200813 Dec 2011Gore Enterprise Holdings, Inc.Composite material
US81100378 Nov 20107 Feb 2012The Clorox CompanyTreatments and kits for creating transparent renewable surface protective coatings
US812418916 Jan 200828 Feb 2012Honeywell International Inc.Hydrophobic coating systems, suspensions for forming hydrophobic coatings, and methods for fabricating hydrophobic coatings
US814760726 Oct 20093 Apr 2012Ashland Licensing And Intellectual Property LlcHydrophobic self-cleaning coating compositions
US825820613 Apr 20074 Sep 2012Ashland Licensing And Intellectual Property, LlcHydrophobic coating compositions for drag reduction
US828656118 Sep 200916 Oct 2012Ssw Holding Company, Inc.Spill containing refrigerator shelf assembly
US829552212 Feb 200923 Oct 2012Widex A/SFilter for a hearing aid and a hearing aid
US83092332 Jun 200913 Nov 2012Integran Technologies, Inc.Electrodeposited metallic-materials comprising cobalt on ferrous-alloy substrates
US833835129 Mar 201125 Dec 2012Ashland Licensing And Intellectual Property, LlcCoating compositions for producing transparent super-hydrophobic surfaces
US835416023 Jun 200615 Jan 20133M Innovative Properties CompanyArticles having durable hydrophobic surfaces
US836721727 Aug 20095 Feb 2013Integran Technologies, Inc.Electrodeposited metallic-materials comprising cobalt on iron-alloy substrates with enhanced fatigue performance
US840971011 May 20112 Apr 2013Wacker Chemie AgParticles with structured surface
US84201633 Nov 201016 Apr 2013Evonik Degussa GmbhProcess for forming a surface comprising elevations of hydrophobic particles
US848631924 May 201016 Jul 2013Integran Technologies Inc.Articles with super-hydrophobic and/or self-cleaning surfaces and method of making same
US854599424 May 20101 Oct 2013Integran Technologies Inc.Electrodeposited metallic materials comprising cobalt
US85573359 Dec 200815 Oct 2013Beneq OyMethod for manufacturing an extremely hydrophobic surface
US8574713 *9 Mar 20065 Nov 2013Massachusetts Institute Of TechnologySuperhydrophobic fibers and methods of preparation and use thereof
US859620515 Oct 20123 Dec 2013Ssw Holding Company, Inc.Spill containing refrigerator shelf assembly
US8596264 *2 Feb 20013 Dec 2013Pari GmbH Spezialisten für effektive InhalationInhalation nebulizer
US8629070 *26 Feb 200214 Jan 2014Evonik Degussa GmbhFlat textile structures with self-cleaning and water-repellent surface
US863285620 Dec 200621 Jan 20143M Innovative Properties CompanyHighly water repellent fluoropolymer coating
US86638199 Nov 20124 Mar 2014Integran Technologies, Inc.Electrodeposited metallic coatings comprising cobalt with enhanced fatigue properties
US869139731 Oct 20128 Apr 2014Integran Technologies, Inc.Biocidal metallic layers comprising cobalt
US87632381 Jul 20091 Jul 2014Widex A/SMethod of manufacturing a component for a hearing aid
US878471331 May 201322 Jul 2014Integran Technologies Inc.Method of making articles with super-hydrophobic and/or self-cleaning surfaces
US880884810 Sep 201019 Aug 2014W. L. Gore & Associates, Inc.Porous article
US885868123 Apr 200714 Oct 2014W. L. Gore & Associates, Inc.Patterned porous venting materials
US89745904 Jan 201210 Mar 2015The Armor All/Stp Products CompanyTreatments and kits for creating renewable surface protective coatings
US8997672 *24 Nov 20097 Apr 2015University Of Florida Research Foundation, Inc.Surface topographies for non-toxic bioadhesion control
US9016221 *31 Aug 200928 Apr 2015University Of Florida Research Foundation, Inc.Surface topographies for non-toxic bioadhesion control
US905633224 Mar 200316 Jun 2015P2I LimitedMethod and apparatus for the formation of hydrophobic surfaces
US90678217 Apr 201130 Jun 2015Ross Technology CorporationHighly durable superhydrophobic, oleophobic and anti-icing coatings and methods and compositions for their preparation
US90747781 Nov 20107 Jul 2015Ssw Holding Company, Inc.Cooking appliance surfaces having spill containment pattern
US90967867 Apr 20114 Aug 2015Ross Technology CorporationSpill resistant surfaces having hydrophobic and oleophobic borders
US913974416 Jun 201422 Sep 2015Ross Technology CorporationComposition and coating for hydrophobic performance
US917977310 May 201310 Nov 2015Ssw Holding Company, Inc.Spill containing refrigerator shelf assembly
US920701219 Aug 20148 Dec 2015Ssw Holding Company, Inc.Spill containing refrigerator shelf assembly
US92170868 Apr 201322 Dec 2015Wayne State UniversityMethod of fabricating transparent anti-reflective article
US924317530 Jun 201426 Jan 2016Ross Technology CorporationSpill resistant surfaces having hydrophobic and oleophobic borders
US92495214 Nov 20112 Feb 2016Integran Technologies Inc.Flow-through consumable anodes
US927907330 Jun 20148 Mar 2016Ross Technology CorporationMethods of making highly durable superhydrophobic, oleophobic and anti-icing coatings
US928558430 Sep 201115 Mar 20163M Innovative Properties CompanyAnti-reflective articles with nanosilica-based coatings and barrier layer
US930332224 May 20105 Apr 2016Integran Technologies Inc.Metallic articles with hydrophobic surfaces
US9314973 *11 Jun 201219 Apr 2016Dean LavalleeShipping structure and methods of making and using same
US933999630 Jun 201117 May 20163M Innovative Properties CompanyDurable hydrophobic structured surface
US934697328 Mar 201424 May 2016Ross Technology CorporationElastomeric coatings having hydrophobic and/or oleophobic properties
US938832528 Mar 201412 Jul 2016Ross Technology CorporationElastomeric coatings having hydrophobic and/or oleophobic properties
US9427908 *10 Oct 200730 Aug 2016Agency For Science, Technology And ResearchModification of surface wetting properties of a substrate
US952802227 Aug 201527 Dec 2016Ross Technology CorporationComposition and coating for hydrophobic performance
US953264912 Feb 20163 Jan 2017Ssw Holding Company, Inc.Spill containing refrigerator shelf assembly
US954629921 Aug 201317 Jan 2017Ross Technology CorporationSuperhydrophobic and oleophobic coatings with low VOC binder systems
US9636941 *27 Oct 20112 May 2017Hewlett-Packard Indigo B.V.Embossing die creation
US970157610 Oct 201211 Jul 2017Schott AgCoated glass or glass ceramic substrate with haptic properties
US20020022426 *21 Jun 200121 Feb 2002The Procter & Gamble CompanyApplications for elastic laminate web
US20020084553 *13 Dec 20014 Jul 2002Creavis Gesellschaft Fuer Techn. Und Innov. MbhProcess for molding hydrophobic polymers to produce surfaces with stable water- and oil-repellent properties
US20020148601 *28 Dec 200117 Oct 2002Martin RoosApparatus for accelerating condensation with the aid of structured surfaces
US20020150723 *9 Apr 200217 Oct 2002Creavis Gesellschaft F. Techn. U. Innovation MbhSurfaces which are self-cleaning by hydrophobic structures, and a process for their production
US20030013795 *3 May 200216 Jan 2003Creavis Gesellschaft F. Techn. U. Innovation MbhSurfaces rendered self-cleaning by hydrophobic structures and a process for their production
US20030028165 *20 Dec 20006 Feb 2003Curro John JLaminate web comprising an apertured layer and method for manufacture thereof
US20030089366 *2 Feb 200115 May 2003Erik SommerInhalation nebulizer
US20030096083 *17 Mar 200122 May 2003Robert MorganSurface, method for the production therof and an object provided with said surface
US20030108716 *4 Dec 200212 Jun 2003Creavis Gesellschaft Fuer Tech. Und Innovation MbhLight-scattering materials which have self-cleaning surfaces
US20030124301 *5 Dec 20023 Jul 2003Markus OlesProcess for producing articles with anti-allergic surfaces
US20030134086 *14 Nov 200217 Jul 2003Creavis Gesellschaft Fur Tech. Und Innovation MbhDiffuse-reflection surfaces and process for their production
US20030147932 *8 Aug 20027 Aug 2003Creavis Gesellschaft Fuer Tech. Und Innovation MbhSelf-cleaning lotus effect surfaces having antimicrobial properties
US20030152780 *13 Mar 200114 Aug 2003Martin BaumannGlass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof
US20030167667 *21 Feb 200311 Sep 2003Gottlieb Binder Gmbh & Co.Self-cleaning display device
US20030187170 *19 Nov 20022 Oct 2003Axel BurmeisterProduction of nano- and microstructured polymer films
US20040014865 *12 Oct 200122 Jan 2004Harald KellerComposition for producing surfaces which are difficult to wet
US20040037961 *21 Aug 200326 Feb 2004Cedric DielemanProduction of surfaces to which liquids do not adhere
US20040067339 *4 Jul 20018 Apr 2004Christophe GandonTransparent textured substrate and methods for obtaining same
US20040127393 *22 Oct 20031 Jul 2004Valpey Richard S.Process and composition for producing self-cleaning surfaces from aqueous systems
US20040154106 *26 Feb 200212 Aug 2004Markus OlesFlat textile structures with self-cleaning and water-repellent surfaces
US20040185736 *30 Jan 200423 Sep 2004The Procter & Gamble CompanyElectrical cable
US20040191480 *31 Mar 200430 Sep 2004Yasushi KarasawaStructural member superior in water repellency and method for manufacturing the same
US20040213904 *18 Dec 200328 Oct 2004Goldschmidt AgProcess for producing detachable dirt-and water-repellent surface coatings
US20040237590 *2 Jun 20032 Dec 2004Ferro CorporationMethod of micro and nano texturing glass
US20050036918 *18 Dec 200117 Feb 2005Lange Frederick F.Microchannels for efficient fluid transport
US20050136217 *2 Feb 200523 Jun 2005Wilhelm BarthlottMethod for the preparation of self-cleaning removable surfaces
US20050145285 *29 Oct 20047 Jul 2005Entegris, IncFluid handling component with ultraphobic surfaces
US20050170098 *16 Feb 20054 Aug 2005Ferro GmbhGlass, ceramic and metal substrates with a self-cleaning surface, method of making them and their use
US20050276962 *9 Jun 200515 Dec 2005University Of Florida Research Foundation, Inc.Ultralyophobe interfaces
US20060035062 *14 Oct 200516 Feb 2006Degussa AgProcess for producing articles with anti-allergic surfaces
US20060051561 *24 Mar 20039 Mar 2006University Of DurhamMethod and apparatus for the formation of hydrophobic surfaces
US20060081394 *15 Oct 200420 Apr 2006Georgia Tech Research CorporationInsulator coating and method for forming same
US20060097361 *27 Nov 200311 May 2006Masaru TanakaMicroprotrusion structure, and process for producing the same
US20060110541 *31 Oct 200525 May 2006Russell Jodi LTreatments and kits for creating transparent renewable surface protective coatings
US20060110542 *31 Oct 200525 May 2006Thomas DietzProcessing compositions and method of forming the same
US20060127643 *3 Feb 200615 Jun 2006Creavis Gesellschaft Fuer Tech. Und Innovation MbhLight-scattering materials which have self-cleaning sufraces
US20060127644 *3 Feb 200615 Jun 2006Creavis Gesellschaft Fur Tech. Und Innovation MbhDiffuse-reflection surfaces and process for their production
US20060144870 *25 Nov 20036 Jul 2006Ian AndersonKeg with an inner bag
US20060147675 *21 Dec 20056 Jul 2006Degussa AgSelf-cleaning surfaces comprising elevations formed by hydrophobic particles and having improved mechanical strength
US20060174418 *29 Jan 200410 Aug 2006Harald KellerMethod for hydrophobing textile materials
US20060222815 *21 Apr 20045 Oct 2006Degussa AgUse of particles hydrophobized by fluorosilanes for the production of self-cleaning surfaces having lipophobic, oleophobic, lactophobic and hydrophobic properties
US20060235143 *13 Jun 200619 Oct 2006Felix MullerProcess for producing detachable dirt- and water-repellent surface coatings
US20060246277 *27 Apr 20052 Nov 2006Ferro CorporationStructured self-cleaning surfaces and method of forming same
US20060292369 *9 Mar 200628 Dec 2006Rutledge Gregory CSuperhydrophobic fibers and methods of preparation and use thereof
US20070028588 *1 Aug 20068 Feb 2007General Electric CompanyHeat transfer apparatus and systems including the apparatus
US20070031639 *2 Aug 20068 Feb 2007General Electric CompanyArticles having low wettability and methods for making
US20070059490 *14 Sep 200615 Mar 2007Fuji Photo Film Co., Ltd.Protective film
US20070197111 *17 May 200523 Aug 2007Basf AktiengesellschaftMethod for finishing absorbent materials
US20070227428 *5 Dec 20064 Oct 2007Brennan Anthony BSurface topographies for non-toxic bioadhesion control
US20080014432 *17 May 200517 Jan 2008Basf AktiengesellschaftMethod for the Production of Structured Surfaces
US20080190574 *4 Jul 200614 Aug 2008Astenjohnson, Inc.Sheet-Like Products Exhibiting Oleophobic and Hydrophobic Properties
US20080199659 *18 Mar 200821 Aug 2008Wayne State UniversityTransparent hydrophobic article having self-cleaning and liquid repellant features and method of fabricating same
US20080221009 *28 Jan 200811 Sep 2008Subbareddy KanagasabapathyHydrophobic self-cleaning coating compositions
US20080221263 *31 Aug 200711 Sep 2008Subbareddy KanagasabapathyCoating compositions for producing transparent super-hydrophobic surfaces
US20080245012 *5 Apr 20079 Oct 2008LafargeSuperhydrophobic gypsum boards and process for making same
US20080250978 *17 Jan 200816 Oct 2008Baumgart Richard JHydrophobic self-cleaning coating composition
US20080254212 *11 Sep 200616 Oct 2008Basf SeMethod for Coating Surfaces and Suitable Particles Therefor
US20080257153 *23 Apr 200723 Oct 2008Harp Gary PPatterned Porous Venting Materials
US20080257155 *23 Apr 200723 Oct 2008Bacino John EPorous Composite Article
US20090011222 *13 Dec 20068 Jan 2009Georgia Tech Research CorporationSuperhydrophobic surface and method for forming same
US20090014416 *21 Dec 200715 Jan 2009Saint-Gobain Glass FranceTransparent textured substrate and methods for obtaining same
US20090018249 *30 Jan 200715 Jan 2009Subbareddy KanagasabapathyHydrophobic self-cleaning coating compositions
US20090029043 *20 Aug 200829 Jan 2009Haitao RongMultifunctional star-shaped prepolymers, their preparation and use
US20090029177 *20 Dec 200629 Jan 20093M Innovative Properties CompanyHighly water repellent fluoropolymer coating
US20090064894 *4 Sep 200812 Mar 2009Ashland Licensing And Intellectual Property LlcWater based hydrophobic self-cleaning coating compositions
US20090154747 *12 Feb 200918 Jun 2009Widex A/SFilter for a hearing aid and a hearing aid
US20090176920 *16 Mar 20079 Jul 2009Wacker Chemie AgParticles with structured surface
US20090181237 *16 Jan 200816 Jul 2009Honeywell International, Inc.Hydrophobic coating systems, suspensions for forming hydrophobic coatings, and methods for fabricating hydrophobic coatings
US20090231714 *16 Mar 200917 Sep 2009Yang ZhaoTransparent anti-reflective article and method of fabricating same
US20090262966 *1 Jul 200922 Oct 2009Widex A/SComponent for a hearing aid and a method of making a component for a hearing aid
US20090304983 *1 Mar 200710 Dec 2009Wilhelm BarthlottNon-Wettable Surfaces
US20100009188 *11 Jul 200814 Jan 2010John Haozhong XinNano-structured surface and an in situ method for forming the same
US20100033818 *7 Aug 200911 Feb 2010Uni-Pixel Displays,Inc.Microstructures to reduce the appearance of fingerprints on surfaces
US20100040790 *15 Nov 200718 Feb 2010Basf SeAqueous formulations and use thereof
US20100119755 *12 Nov 200913 May 2010University Of Florida Research Foundation, Inc.Method of patterning a surface and articles comprising the same
US20100120970 *12 Dec 200713 May 2010University Of LeedsReversible micelles and applications for their use
US20100126404 *24 Nov 200927 May 2010University Of Florida Research Foundation, Inc.Surface Topographies for Non-Toxic Bioadhesion Control
US20100129608 *10 Oct 200727 May 2010Agency For Science, Technology And ResearchModification of Surface Wetting Properties of a Substrate
US20100144225 *20 May 200810 Jun 2010Basf SeMethod for treating surfaces
US20100226943 *31 Aug 20099 Sep 2010University Of FloridaSurface topographies for non-toxic bioadhesion control
US20100266761 *9 Dec 200821 Oct 2010Beneq OyMethod for manufacturing an extremely hydrophobic surface
US20100304172 *2 Jun 20092 Dec 2010Integran Technologies, Inc.Electrodeposited metallic-materials comprising cobalt
US20100304179 *24 May 20102 Dec 2010Integran Technologies, Inc.Electrodeposited metallic materials comprising cobalt
US20100304182 *27 Aug 20092 Dec 2010Integran Technologies, Inc.Electrodeposited metallic-materials comprising cobalt
US20100305256 *29 Jun 20102 Dec 2010Basf AktiengesellschaftMethod for hydrophobing textile materials
US20100330347 *14 Jul 201030 Dec 2010Surface Innovations LimitedMethod and apparatus for the formation of hydrophobic surfaces
US20110027475 *9 Dec 20083 Feb 2011Beneq OyMethod and device for structuring a surface
US20110045247 *3 Nov 201024 Feb 2011Evonik Degussa GmbhSelf-cleaning surfaces comprising elevations formed by hydrophobic particles and having improved mechanical strength
US20110054096 *8 Nov 20103 Mar 2011Jodi Lynn RussellTreatments and Kits For Creating Transparent Renewable Surface Protective Coatings
US20110094417 *26 Oct 200928 Apr 2011Ashland Licensing And Intellectual Property LlcHydrophobic self-cleaning coating compositions
US20110177252 *29 Mar 201121 Jul 2011Ashland Licensing And Intellectual Property LlcCoating compositions for producing transparent super-hydrophobic surfaces
US20120315415 *11 Jun 201213 Dec 2012Dean LavalleeShipping structure and methods of making and using same
US20140283699 *27 Oct 201125 Sep 2014Hewlett-Packard Indigo B.V.Embossing Die Creation
US20150108032 *5 Jul 201323 Apr 2015Toyo Seikan Group Holdings, LtdPacking container having excellent slipping property for the content
US20170043911 *13 Jan 201516 Feb 2017Toyo Seikan Co., Ltd.Plastic formed body for pouring out liquid
CN102424354A *23 Aug 201125 Apr 2012东南大学Rough surface for fractal structure
CN102424354B23 Aug 20116 Aug 2014东南大学Rough surface for fractal structure
DE10028772A1 *7 Jun 200024 Jan 2002Univ Dresden TechUltrahydrophobe Oberflächen, Verfahren zu deren Herstellung sowie Verwendung
DE10028772B4 *7 Jun 200017 Mar 2005Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.Aluminiumwerkstoff mit ultrahydrophober Oberfläche, Verfahren zu dessen Herstellung sowie Verwendung
DE10202513A1 *23 Jan 20027 Aug 2003Infineon Technologies AgAn image producing sensor with a structured adhesion decreasing surface useful in the surface examination of automobile parts making use of the lotus effect
DE10202513B4 *23 Jan 200230 Mar 2006Infineon Technologies AgSelbstreinigende Oberflächen für bildgebende Sensoren
DE19860137A1 *24 Dec 199829 Jun 2000Bayer AgVerfahren zur Herstellung einer ultraphoben Oberfläche auf Basis von strukturiertem Aluminium
DE19860137C2 *24 Dec 199818 Jul 2002Sunyx Surface NanotechnologiesVerfahren zur Herstellung einer ultraphoben Oberfläche auf Basis von strukturiertem Aluminium und deren Verwendung
DE19913601C1 *25 Mar 199910 Aug 2000Wilhelm BarthlottApparatus for transporting or discharging hydrophilic liquids has hydrophobic peaks or recesses on the side facing the liquid
DE19923175A1 *20 May 199923 Nov 2000Borsi Kg FCovering plastic support panel, e.g. to display commercial information and confer self-cleaning properties, adds textured surface of hydrophobic material and parting layer, in design also offering scratch resistance and anti-reflection
DE102008041920A19 Sep 200811 Mar 2010Evonik Degussa GmbhNeue Katalysatoren für die Vernetzung von funktionellen Silanen oder funktionellen Siloxanen, insbesondere mit Substraten
EP1247636A2 *8 Nov 20019 Oct 2002Creavis Gesellschaft für Technologie und Innovation mbHProcess for shapping hydrophobic polymers for the production of surfaces with durable water and oil repellent properties
EP1247636A3 *8 Nov 200111 Dec 2002Creavis Gesellschaft für Technologie und Innovation mbHProcess for shapping hydrophobic polymers for the production of surfaces with durable water and oil repellent properties
EP1318228A1 *25 Nov 200211 Jun 2003Creavis Gesellschaft für Technologie und Innovation mbHMethod for manufacturing items with antiallergic surfaces
EP1582329A1 *27 Nov 20035 Oct 2005Japan Science and Technology AgencyMicroprotrusion structure and process for producing the same
EP1582329A4 *27 Nov 200320 Dec 2006Japan Science & Tech AgencyMicroprotrusion structure and process for producing the same
EP1613541A2 *15 Apr 200411 Jan 2006Entegris, Inc.Carrier with ultraphobic surfaces
EP1613541A4 *15 Apr 200414 Jun 2006Entegris IncCarrier with ultraphobic surfaces
EP1613866A2 *15 Apr 200411 Jan 2006Entegris, Inc.Fluid handling component with ultraphobic surfaces
EP1613866A4 *15 Apr 200414 Jun 2006Entegris IncFluid handling component with ultraphobic surfaces
EP1622819A2 *14 Apr 20048 Feb 2006Entegris, Inc.Tray carrier with ultraphobic surfaces
EP1622819A4 *14 Apr 200414 Jun 2006Entegris IncTray carrier with ultraphobic surfaces
EP1750018A3 *31 Jul 200614 Dec 2011General Electric CompanySurfaces and articles resistant to impacting liquids
EP2404739A19 Jul 201011 Jan 20123M Innovative Properties Co.Durable hyrophobic structured surface
EP2522377A131 May 201014 Nov 2012Integran Technologies Inc.Antibacterial electrodeposited metallic materials comprising cobalt
EP2592056A1 *9 Oct 201215 May 2013Schott AGCoated glass or glass ceramic substrate with haptic characteristics
EP2859053A4 *10 Jun 20132 Mar 2016Univ HoustonSelf-cleaning coatings and methods for making same
WO1996004123A1 *25 Jul 199515 Feb 1996Wilhelm BarthlottSelf-cleaning surfaces of objects and process for producing same
WO2000058415A1 *18 Mar 20005 Oct 2000Wilhelm BarthlottMethod and device for the loss-free transport of liquids
WO2001056639A1 *2 Feb 20019 Aug 2001Pari GmbH Spezialisten für effektive InhalationInhalation nebulizer
WO2001074672A19 Mar 200111 Oct 2001Creavis Gesellschaft Für Technologie Und Innovation MbhContainer with structured fluid repellent and fluid wettable partial regions of the inner surfaces
WO2001074739A113 Mar 200111 Oct 2001Dmc?2¿ Degussa Metals Catalyts Cerdec AgGlass ceramic and metal substrates with a self-cleaning surface, method for the production and use thereof
WO2001079142A112 Apr 200125 Oct 2001Nanogate Technologies GmbhCeramic material surface with hydrophobic or ultraphobic properties and method for the production thereof
WO2002049762A2 *18 Dec 200127 Jun 2002The Regents Of The University Of CaliforniaMicrochannels for efficient fluid transport
WO2002049762A3 *18 Dec 200126 Jun 2003Frederick F LangeMicrochannels for efficient fluid transport
WO2002101761A2 *14 Dec 200119 Dec 2002Ccs Technology, Inc.Cable and method for producing a cable
WO2002101761A3 *14 Dec 20012 Oct 2003Ccs Technology IncCable and method for producing a cable
WO2003013731A1 *19 Jun 200220 Feb 2003Creavis Gesellschaft Für Technologie Und Innovation MbhPipette tips with partly structured surfaces having improved pipetting properties
WO2003013827A1 *19 Jun 200220 Feb 2003Creavis Gesellschaft Für Technologie Und Innovation MbhStructured surfaces that show a lotus effect
WO2003032042A2 *20 Sep 200217 Apr 2003Unaxis Balzers AktiengesellschaftLight coupling element
WO2003032042A3 *20 Sep 200224 Jul 2003Unaxis Balzers AgLight coupling element
WO2003073045A1 *27 Jan 20034 Sep 2003Infineon Technologies AgIndirect measurement of surface contact angle of liquids
WO2003090943A1 *10 Apr 20036 Nov 2003Chemco International LimitedNon-scratch flooring top coat
WO2005123581A1 *9 Jun 200529 Dec 2005University Of Florida ResearchUltralyophobe interfaces
WO2007053242A2 *15 Sep 200610 May 2007Wayne State UniversityTransparent hydrophobic article having self-cleaning and liquid repellant features and method of fabricating same
WO2007053242A3 *15 Sep 200615 Nov 2007Univ Wayne StateTransparent hydrophobic article having self-cleaning and liquid repellant features and method of fabricating same
WO2007075287A1 *7 Dec 20065 Jul 2007Kimberly-Clark Worldwide, Inc.Rough channel microfluidic devices
WO2008025355A1 *31 Aug 20066 Mar 2008Widex A/SFilter for a hearing aid and a hearing aid
WO2008036074A2 *3 Aug 200627 Mar 2008General Electric CompanyArticles having low wettability and methods for making
WO2008036074A3 *3 Aug 20067 Aug 2008Gen ElectricArticles having low wettability and methods for making
WO2008080397A1 *3 Jan 200710 Jul 2008Widex A/SComponent for a hearing aid and a method of making a component for a hearing aid
WO2009074715A19 Dec 200818 Jun 2009Beneq OyMethod for manufacturing an extremely hydrophobic surface
WO2010017503A1 *7 Aug 200911 Feb 2010Uni-Pixel Displays, Inc.Microstructures to reduce the apperance of fingerprints on surfaces
WO2010028877A19 Jul 200918 Mar 2010Evonik Degussa GmbhNew catalysts for the cross-linking of functional silanes or functional siloxanes, particularly with substrates
WO2010139054A1 *31 May 20109 Dec 2010Integran Technologies, Inc.Electrodeposited metallic materials comprising cobalt
WO2011147756A121 May 20111 Dec 2011Integran TechnologiesMetallic articles with hydrophobic surfaces
WO2011147757A121 May 20111 Dec 2011Integran TechnologiesArticles with super-hydrophobic and/or self-cleaning surfaces and method of making same
WO2012006207A130 Jun 201112 Jan 20123M Innovative Properties CompanyDurable hyrophobic structured surface
WO2013004704A13 Jul 201210 Jan 2013Syngenta LimitedFormulation
WO2014041501A1 *12 Sep 201320 Mar 2014Ariel - University Research And Development Company, Ltd.Featured surface and method of making featured surface
WO2014097309A118 Feb 201326 Jun 2014Asian Paints Ltd.Stimuli responsive self cleaning coating
WO2014108892A1 *1 Jan 201417 Jul 2014Elad MorSuper-hydrophobic surfaces in liquid-comprising systems
WO2015082178A1 *12 Nov 201411 Jun 2015BSH Hausgeräte GmbHHousehold appliance
WO2016203411A1 *16 Jun 201622 Dec 2016Stora Enso OyjContainer with oleophilic/oleophobic pattern on a sealing surface
Classifications
U.S. Classification428/167, 428/171, 264/284
International ClassificationB08B17/06, C09K3/18, B08B17/02, B29C59/02
Cooperative ClassificationC03C2217/475, B08B17/06, B29K2827/12, C03C2217/48, B08B17/02, B29K2995/0093, C03C2217/76, C09K3/18, C03C2217/445, B29K2023/06, B29C59/022, B08B17/065, C03C12/00, C03C17/007
European ClassificationB08B17/06B, B08B17/06, B08B17/02, B29C59/02C, C09K3/18