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(12) Patent Application Publication (10) Pub. No.: US 2013/0251942 A1 Azimi Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2013/0251942 A1 Azimi Et Al US 2013025 1942A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2013/0251942 A1 Azimi et al. (43) Pub. Date: Sep. 26, 2013 (54) HYDROPHOBIC MATERIALS C04B 35/622 (2006.01) NCORPORATING RARE EARTHELEMENTS B22F 3/12 (2006.01) AND METHODS OF MANUFACTURE BOSD5/00 (2006.01) B32B I5/00 (2006.01) (76) Inventors: Gisele Azimi, Waltham, MA (US); B32B33/00 (2006.01) Kripa K. Varanasi, Lexington, MA (52) U.S. Cl. (US); Rajeev Dhiman, Malden, MA USPC ........... 428/141; 428/689: 428/698; 428/702: (US); Adam T. Paxson, Cambridge, MA 428/336; 41.9/39: 420/416: 501/152 (US); Kyukmin Kwon, Cambridge, MA (US) (57) ABSTRACT This invention relates generally to an article that includes a (21) Appl. No.: 13/428,652 base Substrate and a hydrophobic coating on the base Sub strate, wherein the hydrophobic coating includes a rare earth (22) Filed: Mar. 23, 2012 element material (e.g., a rare earth oxide, a rare earth carbide, a rare earth nitride, a rare earth fluoride, and/or a rare earth Publication Classification boride). An exposed Surface of the hydrophobic coating has a dynamic contactangle with water of at least about 90 degrees. (51) Int. Cl. A method of manufacturing the article includes providing the B32B 9/00 (2006.01) base Substrate and forming a coating on the base Substrate B32B 8/00 (2006.01) (e.g., through sintering or Sputtering). Patent Application Publication Sep. 26, 2013 Sheet 1 of 13 US 2013/0251942 A1 FIG. FIG. 2 Patent Application Publication Sep. 26, 2013 Sheet 2 of 13 US 2013/0251942 A1 300 302 304 FIG. 3 400 & 402 404 FIG. 4 500 502 504 FIG 5 Patent Application Publication Sep. 26, 2013 Sheet 3 of 13 US 2013/0251942 A1 5 s s S. : 3. 3 S Patent Application Publication Sep. 26, 2013 Sheet 4 of 13 US 2013/0251942 A1 702 700 704 802 808 804 Patent Application Publication Sep. 26, 2013 Sheet 5 of 13 US 2013/0251942 A1 000 900 FIG. O. 900 FG. FIG. 12 Patent Application Publication Sep. 26, 2013 Sheet 6 of 13 US 2013/0251942 A1 Patent Application Publication Sep. 26, 2013 Sheet 7 of 13 US 2013/0251942 A1 strik Nitrix at tie Rare arti (e. F.G. 14 Patent Application Publication Sep. 26, 2013 Sheet 8 of 13 US 2013/0251942 A1 keia surface free energy -- Piar surface free energy « existrface free erers 5 to 8. s: ... x* xx * - is : . FIG. 5 Patent Application Publication Sep. 26, 2013 Sheet 9 of 13 US 2013/0251942 A1 600 700 FG. 7 Patent Application Publication Sep. 26, 2013 Sheet 10 of 13 US 2013/0251942 A1 Patent Application Publication Sep. 26, 2013 Sheet 11 of 13 US 2013/0251942 A1 s CNer or en O s t s CN C- 8 en O bat P ea s c n S2 t gd C O N Patent Application Publication Sep. 26, 2013 Sheet 12 of 13 US 2013/0251942 A1 FG, 24 Patent Application Publication Sep. 26, 2013 Sheet 13 of 13 US 2013/0251942 A1 : : US 2013/025 1942 A1 Sep. 26, 2013 HYDROPHOBC MATERALS embodiments, novel hydrophobic ceramics comprising rare NCORPORATING RARE EARTHELEMENTS earth oxides are described that demonstrate superior water AND METHODS OF MANUFACTURE repellency and promote dropwise water condensation. These ceramics surpass the state-of-the-art in the field of water STATEMENT OF GOVERNMENT SUPPORT repellency in their capability to repel water droplets even from smooth surfaces and their ability to promote dropwise 0001. This invention was made with Government support condensation, with remarkably improved heat transfer coef under Grant No. CBET-0952564 awarded by the National ficients. Because these novel ceramic Surfaces are robust (i.e., Science Foundation. The Government has certain rights in capable of withstanding harsh environments), their deploy this invention. ment may enhance process efficiency, while reducing overall FIELD OF THE INVENTION costs and energy consumption in a wide variety of applica tions that are negatively affected by droplet impingement and 0002 This invention relates generally to nonwetting mate filmwise condensation. Examples include Steam turbine rials and, more particularly, to hydrophobic materials that blades, heat exchangers, condensers, and waterproof con include rare earth elements. Sumer products. 0007. The articles, devices, and methods described herein BACKGROUND OF THE INVENTION offer several advantages over previous approaches in the field 0003. Developing robust hydrophobic surfaces has been a of water repellency and superhydrophobic surfaces. For Subject of intense research over the past decades. Taking example, no previous coating materials have been reported inspiration from natural nonwetting structures, such as lotus that are both robust and hydrophobic. The materials and coat leaves, butterfly wings, duck feathers, and water striders, ings described herein are uniquely capable of repelling water many researchers over the past decades have aimed to deci droplets and offering mechanical resistance, chemical inac pher some of these peculiar designs to develop novel Surfaces tivity, thermal stability, ease of cleaning, and other advan that, similar to their natural counterparts, are water repellent. tages. Further, hydrophobic surfaces based on the materials Conventional approaches to designing hydrophobic/superhy described herein have the advantage of being more scalable drophobic Surfaces include creating a rough or textured Sur and practical for industrial applications, compared to previ face and then modifying the surface by materials with low ous low Surface energy organic materials that are physically Surface energies, such as polymers or fluoroalkylsilane. and thermally unstable and fail under harsh environments. These surfaces, although generally nonwetting, face major 0008. The articles and materials described herein may be material-related drawbacks and operational challenges that used in a wide variety of industrial applications where hydro limit their use in industrial applications. For example, mate phobicity, droplet repellency, and/or dropwise condensation rial incompatibility, physical instability, failure under harsh are desirable. These materials may also offer other industrial environments, and high cost of fabrication are drawbacks that implications in development of anti-fouling and anti-icing hinder widespread, large-scale utilization of conventional Surfaces. For example, these materials may be used in steam hydrophobic and superhydrophobic surfaces. Certain hydro turbines, condensers, heat exchangers, aircraft, wind tur phobic and superhydrophobic surfaces are described in bines, pipelines, evaporators, boilers, medical devices and Kesong Liu & Lei Jiang, Metallic Surfaces with Special Wet implants, and separators. tability, Nanoscale, 2011, 3,825–838. 0009. In one aspect, the invention relates to an article that 0004 Recent developments of water-repellent surfaces includes a base Substrate and a hydrophobic coating on the have pervasively stressed one aspect of hydrophobicity, i.e., base Substrate. The hydrophobic coating includes a rare earth designing more complex structures or textures, while over element material. An exposed surface of the hydrophobic looking the other aspect, i.e., choosing appropriate materials coating has a dynamic contact angle with water of at least or chemical compositions, which is equally, if not more, about 90 degrees. important. For example, the materials used for most hydro 0010. In another aspect, the invention relates to an article phobic surfaces have insufficient mechanical resistance, containing a rare earth element material. An exposed Surface chemical resistance, and thermal stability for many applica of the article has a dynamic contactangle with water of at least tions. On the other hand, metals and ceramics are materials of about 90 degrees. choice for harsh environments, but these materials are gener 0011. In certain embodiments, the rare earth element ally hydrophilic and may require conformal polymeric hydro material includes a rare earth oxide, a rare earth carbide, a rare phobic coatings or modifiers to render them hydrophobic or earth nitride, a rare earth fluoride, and/or a rare earth boride. superhydrophobic. These modifiers, however, break down or In some embodiments, the rare earth element material deteriorate in harsh environments. Robust superhydrophobic includes a combination of one or more species within one or surfaces have therefore been difficult to realize. more of the following categories of compounds: a rare earth 0005 What is needed, then, is a robust, hydrophobic mate oxide, a rare earth carbide, a rare earth nitride, a rare earth rial for use in harsh environments where conventional hydro fluoride, and a rare earth boride. For example, the rare earth phobic materials have failed. A particular need exists for element material may include a combination of at least two hydrophobic materials that are resistant to high temperatures, members selected from the group consisting of a first rare harsh chemicals, and mechanical wear and tear (e.g., abrasion earth oxide, a second rare earth oxide, a first rare earth car and impact). bide, a second rare earth carbide, a first rare earth nitride, a second rare earth nitride, a first rare earth fluoride, a second SUMMARY OF THE INVENTION rare earth fluoride, a first rare earthboride, and a second rare 0006. The articles, devices, and methods presented herein earth boride. For example, the rare earth element material provide robust hydrophobic surfaces with applications across may include a rare earth oxide. In one embodiment, the article a broad range of industries and technologies. In certain includes a metal and/or a ceramic. A thickness of the coating US 2013/025 1942 A1 Sep. 26, 2013 is preferably from about 100 nm to about 300 nm. In various 0016. In certain embodiments, the rare earth element embodiments, the coating includes a ceramic, a metal, and/or material includes a rare earth oxide, a rare earth carbide, a rare a polymer. The coating may be doped with the rare earth earth nitride, a rare earth fluoride, and/or a rare earth boride. element material.
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