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| {{Other uses|Hydrophobia (disambiguation)}}
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| [[File:150 deg water contact angle.png|thumb|150 deg water contact angle on a surface modified using plasma technology system surface chemistry]]
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| [[File:Dew 2.jpg|thumb|[[Dew]] drop on a hydrophobic [[plant cuticle|leaf surface]]]]
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| [[File:Cutting a water droplet using a superhydrophobic knife on superhydrophobic surfaces.ogv|thumb|Cutting a [[water droplet]] using a [[superhydrophobic]] knife on superhydrophobic surfaces]]
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| [[File:Drops I.jpg|thumb|Water drops on the hydrophobic surface of grass]]
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| In [[chemistry]], '''hydrophobicity''' (from the [[Attic Greek]] '''hydro''', meaning ''water'', and '''phobos''', meaning ''fear'') is the physical property of a [[molecule]] (known as a '''hydrophobe''') that is repelled from a mass of [[water]].<ref>Aryeh Ben-Na'im ''Hydrophobic Interaction'' Plenum Press, New York, ISBN 0-306-40222-X</ref>
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| Hydrophobic molecules tend to be [[non-polar]] and, thus, prefer other neutral molecules and non-polar [[solvent]]s. Hydrophobic molecules in water often cluster together, forming [[micelle]]s. Water on hydrophobic surfaces will exhibit a high [[contact angle]].
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| Examples of hydrophobic [[molecule]]s include the [[alkane]]s, [[oil]]s, [[fat]]s, and greasy substances in general. Hydrophobic materials are used for oil removal from water, the management of oil spills, and chemical separation processes to remove non-polar substances from polar compounds.<ref>{{cite journal|last=Akhavan|first=Behnam|coauthors=et al.|title=Hydrophobic Plasma Polymer Coated Silica Particles for Petroleum Hydrocarbon Removal|journal=ACS Appl. Mater. Interfaces|year=2013|date=November 2013|volume=5|issue=17|pages=8563–8571|doi=10.1021/am4020154|url=http://pubs.acs.org/doi/abs/10.1021/am4020154}}</ref>
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| Hydrophobic is often used interchangeably with [[lipophilic]], "fat-loving." However, the two terms are not synonymous. While hydrophobic substances are usually lipophilic, there are exceptions—such as the [[silicones]] and [[fluorocarbon]]s.
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| ==Chemical background==
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| {{main|Hydrophobic force }}
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| The hydrophobic interaction is mostly an [[entropy|entropic]] effect originating from the disruption of highly dynamic [[hydrogen bond]]s between molecules of liquid water by the nonpolar solute. By staying together, nonpolar molecules reduce the [[Accessible surface area|surface area exposed to water]] and minimize their disruptive effect.<ref>{{cite DOI|10.1021/ed075p116}}</ref> Thus, the two immiscible phases (hydrophilic vs. hydrophobic) will change so that their corresponding interfacial area will be minimal. This effect can be visualized in the phenomenon called [[phase (matter)|phase]] separation.
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| ==Superhydrophobicity==
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| {{main|Superhydrophobe}}
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| [[File:DropConnectionAngel.jpg|thumb|A water drop on a Lotus plant leaf.]]
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| '''Superhydrophobic''' surfaces, such as the leaves of the lotus plant, are those that are extremely difficult to wet. The [[contact angle]]s of a water droplet exceeds 150° and the roll-off angle is less than 10°.<ref>{{cite journal |first=Shutao |last=Wang |title=Definition of superhydrophobic states |journal=[[Advanced Materials]] |volume=19 |pages=3423–3424 |year=2007 |doi=10.1002/adma.200700934 |last2=Jiang |first2=L. |issue=21}}</ref> This is referred to as the [[Lotus effect]].
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| ===Theory===
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| In 1805, Thomas Young defined the contact angle ''θ'' by analyzing the forces acting on a fluid droplet resting on a solid surface surrounded by a gas.<ref>{{cite journal |first=T. |last=Young |title=An Essay on the Cohesion of Fluids |journal=[[Philosophical Transactions of the Royal Society|Phil. Trans. R. Soc. Lond.]] |volume=95 |pages=65–87 |year=1805 |doi=10.1098/rstl.1805.0005}}</ref> [[File:Contact angle.svg|thumb|right|400px|A liquid droplet rests on a solid surface and is surrounded by gas. The contact angle, ''θ''<sub>C</sub>, is the angle formed by a liquid at the three-phase boundary where the liquid, gas, and solid intersect.]] [[File:Microstruct superhydrophobic.png|thumb|right|400px|A droplet resting on a solid surface and surrounded by a gas forms a characteristic contact angle ''θ''. If the solid surface is rough, and the liquid is in intimate contact with the solid asperities, the droplet is in the Wenzel state. If the liquid rests on the tops of the asperities, it is in the Cassie–Baxter state.]]
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| : <math>\gamma_\text{SG}\ =\gamma_\text{SL}+\gamma_\text{LG}\cos{\theta} \,</math>
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| where
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| : <math>\gamma_\text{SG}\ </math> = Interfacial tension between the solid and gas
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| : <math>\gamma_\text{SL}\ </math> = Interfacial tension between the solid and liquid
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| : <math>\gamma_\text{LG}\ </math> = Interfacial tension between the liquid and gas
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| ''θ'' can be measured using a [[Goniometer|contact angle goniometer]].
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| Wenzel determined that when the liquid is in intimate contact with a microstructured surface, ''θ'' will change to ''θ''<sub>W*</sub>
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| ::<math>\cos{\theta}_W* = r \cos{\theta} \, </math>
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| where ''r'' is the ratio of the actual area to the projected area.<ref>{{cite journal |first=RN |last=Wenzel |title=Resistance of Solid Surfaces to Wetting by Water |journal=[[Ind. Eng. Chem.]] |volume=28 |pages=988–994 |year=1936 |doi=10.1021/ie50320a024 |issue=8}}</ref> Wenzel's equation shows that microstructuring a surface amplifies the natural tendency of the surface. A hydrophobic surface (one that has an original contact angle greater than 90°) becomes more hydrophobic when microstructured – its new contact angle becomes greater than the original. However, a hydrophilic surface (one that has an original contact angle less than 90°) becomes more hydrophilic when microstructured – its new contact angle becomes less than the original.<ref>{{cite book |first=Pierre-Gilles |last=de Gennes |title=Capillarity and Wetting Phenomena |year=2004 |isbn=0-387-00592-7}}</ref>
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| Cassie and Baxter found that if the liquid is suspended on the tops of microstructures, ''θ'' will change to ''θ''<sub>CB*</sub>:
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| : <math>\cos{\theta}_\text{CB}* = \varphi(\cos\theta + 1) - 1 \,</math>
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| where φ is the area fraction of the solid that touches the liquid.<ref>{{cite journal |first=ABD |last2=Baxter |last=Cassie |first2=S. |title=Wettability of Porous Surfaces |journal=[[Trans. Faraday Soc.]] |volume=40 |pages=546–551 |year=1944 |doi=10.1039/tf9444000546}}</ref> Liquid in the Cassie–Baxter state is more mobile than in the Wenzel state.
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| We can predict whether the Wenzel or Cassie–Baxter state should exist by calculating the new contact angle with both equations. By a minimization of free energy argument, the relation that predicted the smaller new contact angle is the state most likely to exist. Stated in mathematical terms, for the Cassie–Baxter state to exist, the following inequality must be true.<ref>{{cite journal |first=D |last=Quere |title=Non-sticking Drops |journal=[[Reports on Progress in Physics]] |volume=68 |pages=2495–2532 |year=2005 |doi=10.1088/0034-4885/68/11/R01 |issue=11 |bibcode=2005RPPh...68.2495Q}}</ref>
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| : <math>\cos\theta>\frac{\varphi-1}{r-\varphi}</math>
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| A recent alternative criterion for the Cassie–Baxter state asserts that the Cassie–Baxter state exists when the following 2 criteria are met: 1) Contact line forces overcome body forces of unsupported droplet weight and 2) The microstructures are tall enough to prevent the liquid that bridges microstructures from touching the base of the microstructures.<ref>{{cite journal |first=C |last=Extrand |title=Modeling of ultralyophobicity: Suspension of liquid drops by a single asperity|volume=21 |pages=10370–10374 |year=2005 |journal=[[Langmuir (journal)|Langmuir]] |doi=10.1021/la0513050 |issue=23}}</ref>
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| A new criterion for the switch between Wenzel and Cassie-Baxter states has been developed recently based on surface roughness and surface energy.<ref>{{cite journal |first=YL |last=Zhang |title=Superhydrophobic engineering surfaces with tunable air-trapping ability |journal=[[Journal of Micromechanics and Microengineering (journal)|Journal of Micromechanics and Microengineering]] |volume=18 |pages=035024 |year=2008 |doi=10.1088/0960-1317/18/3/035024 |last2=Sundararajan |first2=Sriram |issue=3|bibcode = 2008JMiMi..18c5024Z }}</ref> The criterion focuses on the air-trapping capability under liquid droplets on rough surfaces, which could tell whether Wenzel's model or Cassie-Baxter's model should be used for certain combination of surface roughness and energy.
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| Contact angle is a measure of static hydrophobicity, and contact angle hysteresis and slide angle are dynamic measures. Contact angle hysteresis is a phenomenon that characterizes surface heterogeneity.<ref>{{cite journal |first=RE |last2=Dettre |last=Johnson |first2=Robert H. |title=Contact Angle Hysteresis |volume=68 |pages=1744–1750 |year=1964 |journal=[[J. Phys. Chem.]] |doi=10.1021/j100789a012 |issue=7}}</ref> When a pipette injects a liquid onto a solid, the liquid will form some contact angle. As the pipette injects more liquid, the droplet will increase in volume, the contact angle will increase, but its three-phase boundary will remain stationary until it suddenly advances outward. The contact angle the droplet had immediately before advancing outward is termed the advancing contact angle. The receding contact angle is now measured by pumping the liquid back out of the droplet. The droplet will decrease in volume, the contact angle will decrease, but its three-phase boundary will remain stationary until it suddenly recedes inward. The contact angle the droplet had immediately before receding inward is termed the receding contact angle. The difference between advancing and receding contact angles is termed contact angle hysteresis and can be used to characterize surface heterogeneity, roughness, and mobility. Surfaces that are not homogeneous will have domains that impede motion of the contact line. The slide angle is another dynamic measure of hydrophobicity and is measured by depositing a droplet on a surface and tilting the surface until the droplet begins to slide. In general, liquids in the Cassie–Baxter state exhibit lower slide angles and contact angle hysteresis than those in the Wenzel state.
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| ==Research and development==
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| [[File:A-simple-and-fast-fabrication-of-a-both-self-cleanable-and-deep-UV-antireflective-quartz-1556-276X-7-430-S1.ogv|thumb|Water droplets roll down an inclined hydrophobic surface.]]
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| The self-cleaning property of superhydrophobic micro-[[nanotechnology|nanostructured]] surfaces was reported in 1977,<ref name=Barthlott1977>{{cite journal|first = Wilhelm|last = Barthlott|coauthors = Ehler, N.|year = 1977|title = Raster-Elektronenmikroskopie der Epidermis-Oberflächen von Spermatophyten|journal = Tropische und subtropische Pflanzenwelt|volume = 19|publisher = Akad. Wiss. Lit. Mainz|pages = 110}}</ref> and perfluoroalkyl and perfluoropolyether [[superhydrophobic]] materials were developed in 1986 for handling chemical and biological fluids. Other biotechnical applications have emerged since the 1990s.<ref name=Barthlott1997>{{cite journal |last = Barthlott|first = Wilhelm|coauthors = C. Neinhuis|year = 1997|title = The purity of sacred lotus or escape from contamination in biological surfaces|journal = [[Planta (journal)|Planta]]| volume = 202|pages = 1–8 |doi = 10.1007/s004250050096}}</ref><ref name=Cheng2005>{{cite journal|title=Is the lotus leaf superhydrophobic?|journal = [[Appl. Phys. Lett.]]| year = 2005|volume = 86|issue = 14|pages = 144101|author = Cheng, Y. T., Rodak, D. E.|doi=10.1063/1.1895487|bibcode=2005ApPhL..86n4101C}}</ref><ref name=Narhe2006>{{cite journal|title = Water condensation on a super-hydrophobic spike surface|journal = [[Europhys. Lett.]]|year = 2006|volume = 75|issue = 1|pages = 98–104|author = Narhe, R. D., Beysens, D. A.|doi = 10.1209/epl/i2006-10069-9|bibcode=2006EL.....75...98N}}</ref><ref>{{Cite web|title = Mimicking nature: Physical basis and artificial synthesis of the Lotus effect|author = Lai, S.C.S.|url = http://members.ziggo.nl/scslai/lotus.pdf}}</ref><ref name=Koch2008>{{Cite journal|author = Koch, K.|coauthors = Bhushan, B. & Barthlott, W.|year = 2008|title = Diversity of structure, Morphology and Wetting of Plant Surfaces. Soft matter|doi = 10.1039/b804854a|journal = Soft Matter|volume = 4|pages = 1943|issue = 10|bibcode = 2008SMat....4.1943K }}</ref>
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| In recent research, superhydrophobicity has been reported by allowing alkylketene [[Dimer (chemistry)|dimer]] (AKD) to solidify into a nanostructured fractal surface.<ref>{{cite journal |first=T. |last=Onda |last2=Shibuichi |first2=S. |last3=Satoh |first3=N. |last4=Tsujii |first4=K. |title=Super-Water-Repellent Fractal Surfaces |journal=[[Langmuir (journal)|Langmuir]] |volume=12 |pages=2125–2127 |year=1996 |doi=10.1021/la950418o |issue=9}}</ref> Many papers have since presented fabrication methods for producing superhydrophobic surfaces including particle deposition,<ref>{{cite journal |first=M |last2=Nakajima |last=Miwa |first2=Akira |last3=Fujishima |first3=Akira |last4=Hashimoto |first4=Kazuhito |last5=Watanabe |first5=Toshiya |title=Effects of the Surface Roughness on Sliding Angles of Water Droplets on Superhydrophobic Surfaces |journal=[[Langmuir (journal)|Langmuir]] |volume=16 |pages=5754–60 |year=2000 |doi=10.1021/la991660o |issue=13}}</ref> sol-gel techniques,<ref>{{cite journal |first=NJ |last=Shirtcliffe |last2=McHale |first2=G. |last3=Newton |first3=M. I. |last4=Perry |first4=C. C. |title=Intrinsically superhydrophobic organosilica sol-gel foams |journal=[[Langmuir (journal)|Langmuir]] |volume=19 |pages=5626–5631 |year=2003 |doi=10.1021/la034204f |issue=14}}</ref> plasma treatments,<ref>{{cite journal |first=DOH |last=Teare |last2=Spanos |first2=C. G. |last3=Ridley |first3=P. |last4=Kinmond |first4=E. J. |last5=Roucoules |first5=V. |last6=Badyal |first6=J. P. S. |last7=Brewer |first7=S. A. |last8=Coulson |first8=S. |last9=Willis |first9=C. |title=Pulsed plasma deposition of super-hydrophobic nanospheres |journal=[[Chemistry of Materials]] |volume=14 |pages=4566–4571 |year=2002 |doi=10.1021/cm011600f |issue=11}}</ref> vapor deposition,<ref>{{cite journal |first=M |last2=Nakajima |last=Miwa |first2=Akira |last3=Fujishima |first3=Akira |last4=Hashimoto |first4=Kazuhito |last5=Watanabe |first5=Toshiya |title=Effects of the surface roughness on sliding angles of water droplets on superhydrophobic surfaces |journal=[[Langmuir (journal)|Langmuir]] |volume=16 |pages=5754–5760 |year=2000 |doi=10.1021/la991660o |issue=13}}</ref> and casting techniques.<ref>{{cite journal |first=J |last2=Marzolin |last=Bico |first2=C |last3=Quéré |first3=D |title=Pearl drops |journal=[[Europhysics Letters]] |volume=47 |pages=743–744 |year=1999 |doi=10.1209/epl/i1999-00453-y |issue=6 |bibcode=1999EL.....47..743B}}</ref> Current opportunity for research impact lies mainly in fundamental research and practical manufacturing.<ref>{{cite journal |first=C |last=Extrand |title=Self-Cleaning Surfaces: An Industrial Perspective |journal=[[MRS Bulletin]] |pages=733 |year=2008}}</ref> Debates have recently emerged concerning the applicability of the Wenzel and Cassie–Baxter models. In an experiment designed to challenge the surface energy perspective of the Wenzel and Cassie–Baxter model and promote a contact line perspective, water drops were placed on a smooth hydrophobic spot in a rough hydrophobic field, a rough hydrophobic spot in a smooth hydrophobic field, and a hydrophilic spot in a hydrophobic field.<ref>{{cite journal |first=LC |last=Gao |title=How Wenzel and Cassie Were Wrong |journal=[[Langmuir (journal)|Langmuir]] |volume=23 |pages=3762–3765 |year=2007 |doi=10.1021/la062634a |pmid=17315893 |last2=McCarthy |first2=TJ |issue=7}}</ref> Experiments showed that the surface chemistry and geometry at the contact line affected the contact angle and contact angle hysteresis, but the surface area inside the contact line had no effect. An argument that increased jaggedness in the contact line enhances droplet mobility has also been proposed.<ref>{{cite journal |first=W |last2=Fadeev |last=Chen |first2=Alexander Y. |last3=Hsieh |first3=Meng Che |last4=Öner |first4=Didem |last5=Youngblood |first5=Jeffrey |last6=McCarthy |first6=Thomas J. |title=Ultrahydrophobic and ultralyophobic surfaces: Some comments and examples |journal=[[Langmuir (journal)|Langmuir]] |volume=15 |pages=3395–3399 |year=1999 |doi=10.1021/la990074s |issue=10}}</ref>
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| Many very hydrophobic materials found in nature rely on [[Cassie's law]] and are [[Phase (matter)|biphasic]] on the submicrometer level with one component air. The [[Lotus effect]] is based on this principle. Inspired by it, a lot of functional superhydrophobic surfaces were prepared.<ref>{{cite journal |doi=10.1142/9789812772374_0013 |first=S.T. |last2=Liu |last=Wang |first2=Huan |last3=Jiang |first3=Lei |title=Recent process on bio-inspired surface with special wettability |journal=[[Annual Review of Nano Research]] |volume=1 |pages=573–628 |year=2006}}</ref>
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| An example of a [[bionics|biomimetic]] superhydrophobic material in [[nanotechnology]] is [[nanopin film]]. In one study, a [[vanadium pentoxide]] surface that can switch reversibly between superhydrophobicity and [[superhydrophilicity]] under the influence of UV radiation is presented.<ref>''UV-Driven Reversible Switching of a Roselike Vanadium Oxide Film between Superhydrophobicity and Superhydrophilicity''Ho Sun Lim, Donghoon Kwak, Dong Yun Lee, Seung Goo Lee, and Kilwon Cho [[J. Am. Chem. Soc.]]; '''2007'''; 129(14) pp. 4128–4129; (Communication) {{DOI|10.1021/ja0692579}}
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| </ref> According to the study, any surface can be modified to this effect by application of a [[suspension (chemistry)|suspension]] of rose-like V<sub>2</sub>O<sub>5</sub> particles, for instance with an [[inkjet printer]]. Once again hydrophobicity is induced by interlaminar air pockets (separated by 2.1 [[nanometer|nm]] distances). The UV effect is also explained. UV light creates [[electron-hole pair]]s, with the holes reacting with lattice oxygen, creating surface oxygen vacancies, while the electrons reduce V<sup>5+</sup> to V<sup>3+</sup>. The oxygen vacancies are met by water, and it is this water absorbency by the vanadium surface that makes it hydrophilic. By extended storage in the dark, water is replaced by oxygen and [[hydrophilicity]] is once again lost.
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| ===Potential applications===
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| Active recent research on superhydrophobic materials might eventually lead to industrial applications. For example, a simple routine of coating cotton fabric with [[silica]]<ref>C-H Xue et al. "Preparation of superhydrophobic surfaces on cotton textiles" Sci. Technol. Adv. Mater. 9 (2008) 035008 [http://dx.doi.org/10.1088/1468-6996/9/3/035008 free download]</ref> or [[titanium dioxide|titania]]<ref>C-H Xue et al. "Superhydrophobic cotton fabrics prepared by sol–gel coating of TiO2 and surface hydrophobization" Sci. Technol. Adv. Mater. 9 (2008) 035001 [http://dx.doi.org/10.1088/1468-6996/9/3/035001 free download]</ref> particles by [[sol-gel]] technique has been reported, which protects the fabric from UV light and makes it superhydrophobic. Also, an efficient routine has been reported for making [[polyethylene]] superhydrophobic and thus self-cleaning<ref>Z. Yuan et al. "Preparation and characterization of
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| self-cleaning stable superhydrophobic linear low-density polyethylene" Sci. Technol. Adv. Mater. 9 (2008) 045007 [http://dx.doi.org/10.1088/1468-6996/9/4/045007 free download]</ref>—99% of dirt absorbed on such surface is easily washed away. Patterned superhydrophobic surfaces also have the promises for the lab-on-a-chip, microfluidic devices and can drastically improve the surface based bioanalysis.<ref name=Ressine2007>{{cite journal|author = Ressine, A.|coauthors = Marko-Varga, G., Laurell, T.|year = 2007|title = Porous silicon protein microarray technology and ultra-/superhydrophobic states for improved bioanalytical readout|journal = Biotechnology Annual Review|volume = 13|pages = 149–200|doi = 10.1016/S1387-2656(07)13007-6|pmid = 17875477}}</ref>
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| ==See also==
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| {{portal|Underwater diving}}
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| * [[Amphiphile]]
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| * [[Froth flotation]]
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| * [[Hydrophile]]
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| * [[Hydrophobic effect]]
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| * [[Hydrophobicity scales]]
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| * [[Superhydrophobe]]
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| * [[Superhydrophobic coating]]
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| ==References==
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| {{Reflist|2}}
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| ==External links==
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| * [http://www.micronaut.ch/sidemenu/show/2011-Superhydrophobic-Structures/references Highly magnified image of a superhydrophobic surface of a mosquito egg]
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| {{Chemical solutions}}
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| {{Diving medicine, physiology and physics}}
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| [[Category:Chemical properties]]
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| [[Category:Intermolecular forces]]
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| [[Category:Underwater diving physics]]
| |
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