Acs Langmuir 9b03908

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Invited Feature Article

Practical Applications of Superhydrophobic Materials and Coatings: Problems and Perspectives
H. Yildirim Erbil
Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.9b03908 • Publication Date (Web): 12 Feb 2020
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Page 1 of 55 Langmuir
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4 CANCEL
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WENZEL
8 POOR
9 & CASSIE
10 ANTI-ICING HIGH-COST
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12 EQNS.
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PERFORMANCE METHODS
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DRAWBACKS
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21 OF SURFACE
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23 SELF-HEALING CONTAMI-
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25 NATION
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REASONS TO PREVENT
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29 PRACTICAL APPLICATIONS
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32 INSUFFICIENT
OF SUPERHYDROPHOBIC
33 LACK
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WATER VAPOR MATERIALS
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OF
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CONDENSATION AND
ROBUSTNESS
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COATINGS
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45 TRANSPARENCY LACK
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47 & ANTI- OF
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49 REFLECTIVITY ABRASION
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51 PROBLEMS RESISTANCE
52 ONLY SHORT
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SMALL SCALE USEFUL
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57 PREPARATION SERVICE
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LIFE
ACS Paragon Plus Environment

Langmuir Page 2 of 55
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Practical Applications of Superhydrophobic Materials and
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6 Coatings: Problems and Perspectives
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H. Yildirim Erbil
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11 Gebze Technical University, Chemical Engineering Department,
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13 Gebze 41400, Kocaeli, Turkey.
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20 Abstract:
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23 Synthetic superhydrophobic (SH) surfaces were developed after 1990s and the number of
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25 publications in this field is around 13.500 at present. However, the industrial production of the
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27 SH coatings is very unsatisfying after the intensive research activity especially in the last two
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30 decades. The main reason is the loss of the water repellence properties when SH surfaces are
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32 exposed to outdoor conditions due to their weak mechanical properties and contamination from
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34 the medium which remove the initial SH properties. In this Feature Article, we focus on the
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scientific and technical reasons which prevent the application of the SH surfaces in our daily
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39 lives by highlighting some well-known, but mostly overlooked problems in this area (the
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41 synthesis methods of SH surfaces is not the subject of this article since they were reviewed
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previously in very good articles). The basic contact angle science and the issue of the
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46 cancellation of the Wenzel and Cassie & Baxter equations are reviewed in the first part. The
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48 issues of the expensive and small scale SH surface preparation problems, the difficulties to
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50 obtain a transparent SH surface, the troubles arising from the water vapor condensation on a
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53 SH surface, the lack of robustness and abrasion resistance of most of the SH surfaces, the
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55 drawbacks of the fabricated self-healing SH surfaces, the short useful service life of self-
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57 cleaning SH surfaces due to the surface contamination and the ineffective anti-icing SH
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coatings are reviewed in the following parts. Some important problems affecting the
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3 unsuccessful industrial applications of the SH surfaces are discussed critically in the
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conclusions and outlook section. Finally, some proposals are presented for the future directions
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8 on the synthesis and application of SH surfaces.
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59 Keywords: Superhydrophobic, water-repellent, industrial applications, coatings, transparent.
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3 INTRODUCTION
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8 Wettability depends on the magnitude of intermolecular interactions between contacting liquids
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10 and solids and it is an important property for many natural systems and industry.1-3 The
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measurement of the contact angle (θ) of a liquid droplet placed on a solid is used to quantify its
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15 wettability. θ is the observed angle between the tangent to the solid surface and the tangent to
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17 the liquid-fluid interface at the contact line between the three phases. A sessile droplet has a
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19 definitive volume, and wetted area on a solid substrate, which is confined by the three-phase
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22 contact line. Contact angle, contact radius and droplet height are parameters to define a droplet.
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24 The magnitude of θ indicates the balance of the intermolecular interactions between solid, fluid
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26 and liquid. If the solid/liquid adhesion forces are stronger than the cohesion forces within the
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liquid molecules, then the liquid spreads on the surface. Conversely, if the cohesive forces are
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31 stronger than the adhesive forces between the liquid and solid molecules, then the liquid forms
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33 a sessile droplet on the substrate.
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In general, an “apparent contact angle” is reported to describe the wettability of a surface
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38 in most of the publications.4,5 It is the θ measured on the macroscopic scale to represent the
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40 “average” θ for the entire three-phase contact line of a droplet. Other types of contact angles
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such as “advancing contact angle”, a and “receding contact angle”, r are also determined in
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45 order to estimate the roughness of the surface and its chemical heterogeneity. a, represents the
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47 angle when the volume of the droplet is increased and the three-phase contact line advances on
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50 a fresh solid surface. A maximum value of a is reached before the three-phase line is broken
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52 (the needle in the droplet which is joined to the syringe has to be placed in the middle of the
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54 droplet during the a measurement). As an alternative contact angle, r, is measured when the
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57 volume of a previously formed sessile droplet on the substrate is reduced by applying a suction
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59 of a portion of liquid from the droplet through a needle. r represents the minimum value of
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3
1
2
3 contact angle before the three-phase line is broken, and r mostly describes the strength of
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6 liquid/solid adhesion.4 The difference between a and r gives the “contact angle hysteresis”,
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8 CAH value. On ideal, atomically flat and chemically homogeneous surfaces, CAH is equal to
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0o and a=r. However, CAH can be quite large, around 5-30o in usual contact angle
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13 determinations on real surfaces. Some dynamic or static methods were used to measure a and
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r on surfaces other than the use of needle-syringe-video camera sets however, these methods
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18 have some drawbacks which were reported in the literature.1,4,6-11 Both a and r values depend
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20 on the surface roughness indicating the shapes, sizes and configurations of the patches or strips
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23 and also the chemical heterogeneity of a surface.1,4 The measurement and reporting ofa and r
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25 is mandatory for any surface, because a single apparent  is not adequate to characterize a solid
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surface.4 Good stated that “if an intentional effort is not made to measure a and r when contact
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30 angles are measured by the sessile drop method, the angle observed will be between a and r,
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and often nearer to a. Obviously, such an angle will be of a lower degree of scientific
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35 usefulness than will a true a and r”.6
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37 A “hydrophilic” surface has a water  smaller than 90°, and a “hydrophobic” surface
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40 has a water  larger than or equal to 90°. As an extension of these two basic definitions, solid
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42 surfaces having water ’s larger than 150° are called “superhydrophobic”, SH. Water droplets
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45 have to roll off easily from the SH surfaces at a roll-off angle of less than 10° at ambient
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47 conditions.12-14 The roll-off angle (tilt angle) is the inclination angle of the plane at which the
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49 drop starts rolling. A low value of the roll-off angle indicates a low CAH.
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Superhydrophobicity is a well-known phenomenon in nature. The lotus leaf repels dirt
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54 and mud and biologists Neinhuis and Barthlott performed investigations on lotus leaf, and
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56 reported that its water-repellent properties were due to specific two size range roughness of the
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leaf’s surface and proposed the term “lotus effect” for such surfaces.15,16 There are micrometer
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3 scale papillae (with diameters ranging from 5 to 9 µm) structure on the lotus leaf where nano-
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sized branches with average diameters of 124.3± 3.2 nm are present which could also be
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8 observed on the lower part of the leaf. The epicuticula wax covered these papillae provides the
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10 low surface free energy, and this two size ranged structure creates a large extent of air trapping
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when contacting with water, which is essential for superhydrophobicity.15,16 It was later found
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15 that, many other plants and animals such as rice leaves, butterfly wings, mosquito eyes, moth
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17 eyes, cicada wings, red rose petals, and gecko feet exhibit similar characteristics.17-20
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19 Synthetic SH surfaces were developed after 1990s. In principle, the methods to obtain
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22 SH surfaces can be divided into two main categories: introducing widespread nano- and/or
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24 micro scale roughness on a hydrophobic substance having low surface free energy; or
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26 modifying a former micro/nano-structured rough surface by coating with a hydrophobic layer
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having low surface free energy.12-14 The number of publication on SH surfaces approached to
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31 13.500 according to Web of Science database till to end of 2019 and some very good review
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33 articles were published on the synthesis, characterization and applications of SH’s.12, 14, 20-37
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There are many potential applications for the SH surfaces in industry. They can be used
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38 as self-cleaning exterior paints, transparent windows, windshield glass, car bodies, mirrors; as
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40 coatings for solar energy panels, surveillance cameras, sensors, lenses and telescopes in optical
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42 industry; as anti-icing coatings in aerospace and wind turbine industry, as stain and water
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45 resistant clothing in textile industry; as corrosion protection coating in metal industry, as anti-
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47 biofouling paints in marine industry.20-37 SH surfaces were also under investigation to be used
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49 in biomedical field ranging from blood vessel replacement to wound management.21 Under the
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influence of electric potential, some SH surfaces are able to switch between the hydrophobic
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54 and hydrophilic states or change its hydrophobic/philic properties and these studies are
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56 collected under the term “electrowetting”.38 It has been proposed that slip may be present in
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many microfluidic systems, due to the presence of an adsorbed layer of nanobubbles. A thin
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3 layer of air is formed on the SH surface thereby establishing a new air-water boundary.39 It is
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possible to improve the wetting control on surfaces by using functional and restructured
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8 surfaces.40, 41
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10 However, the industrial production of the SH coatings and materials is very unsatisfying
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after 20 years of intensive research activity. The main technical reason is that the SH surfaces
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15 lost their water repellent properties when they are exposed to harsh environmental conditions.
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17 Nakajima et al. was the first to point out that fabricating a SH surface requires a rough surface
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19 structure having tiny structures but such surfaces will show poor mechanical stability with the
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22 increasing roughness.35 When tiny structures are present on a substrate, then very small
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24 mechanical forces can demolish the surface texture and lead to the elimination of the SH
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26 properties, and water droplets cannot roll off on a previously SH surface, but stick to the
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damaged locations. The other important technical problem is the long-term instability of SH
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31 surfaces due to contamination in open conditions. The suspended matter in air such as dust,
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33 other particulate matter, volatile organic compounds (VOC) or surface-active materials can
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adsorb onto a water-repellent SH surface over time. This causes the corresponding increase in
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38 the surface free energy of the material and also the loss of air pockets which were previously
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40 present on the surface, terminating the initial SH surface properties.14
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42 In this Feature Article, we will focus on the scientific and technical reasons which
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45 prevent the application of the SH coatings in industry and in our daily lives by highlighting
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47 some well-known, but mostly overlooked problems in this area. The use of wrong Wenzel and
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49 Cassie & Baxter equations in SH field, the reduction of transparency due to the presence of
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surface roughness and the droplet condensation in the pores of SH surfaces with the presence
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54 of water vapor are the scientific reasons. The broad application of the very expensive fabrication
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56 methods which are suitable for only small scale, the lack of sufficient robustness and durability
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of SH surfaces, the lack of appropriate standard test methods for the abrasion resistance, the
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3 cancellation of SH properties due to contamination in open conditions are the most important
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negative technical reasons. Besides most of the SH surfaces performed insufficiently in anti-
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8 icing and anti-fouling fields due to for a number of arguments which will also be discussed.
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10 However, the review of SH surface synthesis methods is not the subject of this article since they
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have been described in some very good review articles.20-37
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17 WETTING AND CONTACT ANGLES
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19 Young’s Equation. Thomas Young was the first to report the thermodynamic
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22 equilibrium between the contact angle and the solid surface tension in words, in 1805.1-6, 42 As
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24 seen in Fig. 1, when the solid/vapor (SV), solid/liquid (SL) and liquid/vapor (LV) interfaces are
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26 in equilibrium, then the vectorial summation of these interfacial forces at the three-phase
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intersection point (“triple” or “three-phase contact point”) gives,
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33  SV   SL   LV cos  (1)
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38 where,  is the surface tension term. Young’s equation gives (   0o ) which corresponds to the
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41 complete spreading of the liquid on a solid. This condition exist if [  SV  (  SL   LV ) ] which
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44 shows that the solid has a high surface free energy.
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46 Young's equation is valid only on ideal solid surfaces where only a single and unique
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48 contact angle can form on such a surface. Ideal surfaces must be rigid, flat at an atomic scale,
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51 chemically homogeneous, and are not affected by vapor or liquid adsorption or any chemical
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53 interaction. However, most of the practical systems are far away from the ideal surface
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55 conditions and it is customary to measure a and r angles and calculate CAH on real surfaces.
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58 In general, there are four types of sources for the deviation from being an ideal surface and the
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60 existence of a CAH value. The presence of surface roughness and chemical heterogeneity of
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3 the substrates are the most important ones and the contamination of foreign materials on the
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surface and drop size effects are the remaining issues.1, 4, 6
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31 Figure 1. Schematic description of a liquid droplet on a flat solid surface. Contact angle (),
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contact radius (rB), height (h) and three interfacial tensions, between solid/liquid (SL),
34 solid/vapor (SV), and liquid/vapor (LV) phases.
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In addition, contact angles change by time due to the effects of reorientation of surface
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41 chemical functionalities especially for polymers41, or solvent imbibition into the surface and
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43 swelling of the substrate. Such CAH variations are termed as “kinetic CAH”.4, 43 “Surface
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45 reconstruction” or “surface reorientation” terms are also employed. Kinetic CAH is operative
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48 when the substrate has extensive polar or hydrogen bonding chemical groups in its structure.
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50 When a change occurs in the surrounding environment, the surface configuration of polymers
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52 also change. For example, the hydroxyl groups present in a polymer backbone chain are buried
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away from the hydrophobic air phase at the solid/air interface, when a polymer is under air.
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57 However, if we place a water sessile drop on the same polymer surface under air, then the
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59 hydroxyl groups revolve in order to form hydrogen-bonds with the water liquid. The extent of
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3 the reorientation of the chains on the polymer surface can be measured and reported as the time-
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dependent kinetic changes in contact angle.
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8 Dupre’s Equation. Young-Dupré equation was derived by Dupré after combining the
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10 “work of adhesion” concept with the Young’s equation.44 Work of adhesion is defined as the
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reversible work per unit area at constant pressure and temperature conditions, required to
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15 separate a column of two different liquids (or liquid/solid) at an interface creating two new pure
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17 material surfaces at equilibrium and splitting them to infinite distance [ W12a   G12
a
]. It is
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20 written as [ W12a   1   2   12 ] in surface tension terms. For the case of a solid/liquid
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22 interaction, it can be written as,
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25  GSL
a
 WSLa   SV   LV   SL (2)
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27 where GaSL is the interfacial Gibbs free energy. When Eqs. 1 and 2 are combined, Young-
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30 Dupré equation is obtained,
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32  GSL
a
 WSLa   LV (1  cos  ) (3)
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35 showing that  is a thermodynamical quantity on an ideal surface, and can be related to the
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37 work of adhesion and interfacial Gibbs free energy. The work of adhesion is high when  values
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40 are small, and a substantial energy has to be spent to separate the liquid from the solid. If  =
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42 180o, then, WSLa  0 , which indicates that no work is required to separate a completely spherical
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45 drop from a solid surface and such drops can roll down easily even with a 1o tilt angle. Young-
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47 Dupré equation is valid only on ideal surfaces where no CAH is present and a drop will slide
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49 easily without pinning to the substrate.
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52
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54 CANCELLATION OF WENZEL AND CASSIE-BAXTER EQUATIONS
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56 Wenzel’s Equation. When a surface roughness is present on a substrate, it indicates
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that the actual area of the surface is larger than its plan area. Wenzel suggested that for a given
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3 drop volume, the total magnitude of the liquid/solid interaction is larger on a rough surface than
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that of a flat surface in 1936.45 It was assumed that the drop liquid suffuses into the pits present
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8 on a rough surface completely and there is a relationship between determined ’s on flat and
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10 rough surfaces depending on their plan and actual areas.
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13 cos  er Ar
rW   (4)
14 cos  es As
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17 Ar is the actual liquid/solid contact area, As is the apparent, macroscopic liquid/solid plan area,
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19  er is the equilibrium  on the actual solid,  es is the equilibrium  on a flat, smooth surface of
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22 the same material and rW is the “Wenzel roughness ratio”. This expression indicates that a rough
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24 surface can be more rapidly wetted by the drop liquid since there is a larger net energy decrease
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26 to cause spreading.46
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Cassie and Baxter’s Equation. When chemical heterogeneity is present on a flat
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31 surface, CAH also exists. On such surfaces, the fields having different surface tensions form
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33 barriers against the motion of the droplet three-phase contact line. Thus, different contact angles
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are determined in each of these domains. For example, while a water droplet advances on a flat
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38 surface, a hydrophobic domain will pin the motion of the droplet contact line, thus will increase
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40 the value of a. Conversely, when a water drop recedes on flat surface, the hydrophilic domains
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will hold back the draining motion of the contact line thus decreasing the value of r. Cassie &
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45 Baxter derived an equation for the smooth solid surfaces having varying degrees of
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47 heterogeneity in 1944,47
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50 cos  er   f i cos  i (5)
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53
where fi is the surface area fraction with having a i. This expression can be written for a two-
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55 component surface as:47, 48
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cos  er  f1 cos 1  f 2 cos  2  f1 cos 1  1  f1  cos  2 (6)
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10
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3 Cassie & Baxter expression was also used for the  prediction of a water drop on a rough
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6 patterned substrate where air pockets are present. The contact angle of water in air is 180o, and
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8 this value corresponds to (cos 2 = -1), and by inserting into Eq.6 one obtains,
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cos er  f s cos  s  1  1 (7)
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13 where fs is the solid area fraction on a solid/air composite surface with having a s on the flat
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solid surface. Eqs. 6 and 7 were found to be useful in the contact angle estimates on surfaces
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18 having heterogeneity, however, these expressions cannot desribe the effect of the corrugation
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20 of the three-phase contact line on ’s. Wenzel and Cassie & Baxter states are shown
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schematically in Fig. 2.
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37 (a) (b)
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40 Figure 2. Profile of liquid sessile droplets on patterned surfaces. (a) Wenzel state, (b) Cassie &
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Baxter state.
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45 Objections against the use of Wenzel and Cassie & Baxter Equations on Rough
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47 and Patterned SH Surfaces. Pease was the first to attack against the use of Wenzel’s equation
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in 1945.49 He stated that the intersection of the air-liquid interface with the solid surface at the
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52 three-phase contact line is a 1-D system and the work of adhesion between the solid and the
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54 drop liquid cannot be calculated using contact angles since work of adhesion is dependent on a
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2-D system. Moreover, the line of intersection can hold many possible parallel positions on the
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59 plane of the solid, and these different positions result in different mean adhesion works
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1
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3 depending upon the presence and configurations of different chemical groups on the solid
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surface. The mean value of different tensions which are arranged linearly on a solid surface can
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8 give the resultant work of adhesion which can be calculated from the contact angles.49
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10 Subsequently, it was reported that the Wenzel’s equation could not be used estimate the contact
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angles of water, aqueous calcium chloride and glycerol drops on rough paraffin surfaces by
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15 Bartell and Shepard in 1953.50
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17 Oner and McCarthy found that the shape and arrangement of the three-phase contact
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line of a drop on a patterned surface has an important effect to determine the magnitude of ’s
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22 and also on the rate of drop mobility in 2000.51 Micro-patterned and hydrophobized Si-wafer
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24 surfaces containing posts of different sizes, shapes, and separation distances were prepared and
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26 used in the experiments. The authors determined the force required to move a water droplet on
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29 these patterned surfaces after placing them on an inclined plane. It was found that ’s were
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31 independent of the post heights (20-140 m) and also independent of the chemical groups on
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34 the surface. The receding ’s increased for the cases where the shapes of the posts were
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36 changed from square to staggered rhombus and star, due to the formation of more contorted
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38 contact lines. It was concluded that the continuity, shape, length, amount of surface contact of
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41 the three-phase contact line of a drop are the main factor to determine the a and r values.51
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43 Later, Gao and McCarthy reported that there were differences of the behavior of three-phase
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contact line during the measurement of a and r values. During the advancement of a droplet
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48 on a surface, the discontinuous contact line does not move, but, alternatively, the liquid-vapor
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50 interface sections move down onto the next posts to be wet. On the other hand, during the
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receding movement of a droplet, the discontinuous contact line cannot be withdrawn across the
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55 post tops and has to disjoin from entire post tops in concerted events in order to move.52 Later,
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57 Gao and McCarthy directly criticized the use of the Wenzel and Cassie equations since these
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59 expressions are dependent on solid/liquid interfacial areas and not lines.53 It was pointed out
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1
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3 that, most of the molecules at the liquid/solid interface do not move due to the no-slip boundary
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condition of fluid mechanics during the movement of a droplet horizontally from one to another
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8 contact area. Only the interfacial liquid molecules which can wet new surfaces and de-wet the
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10 previously wetted ones can move during this movement. Thus, the only interfacial liquid
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molecules that move are those which are present on the three-phase contact line, for the limiting
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15 case of a very small movement. As a result, no events happen over the area between the
16
17 liquid/solid interface which is away from the three-phase contact line. Only the molecules on
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19 the contact line can contribute to contact angle hysteresis since the shape and organization of
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22 the three-phase contact line is very important for the movement process. This clarification
23
24 invalidated the use of Wenzel and Cassie & Baxter equations.53
25
26 Gao and McCarty proved experimentally that contact areas under a drop are irrelevant but
27
28
29 only three-phase contact lines are correlated to determine the magnitude of a and r in an article
30
31 entitled “How Wenzel and Cassie were wrong” in 2007.54 Three different patterned surfaces
32
33 were fabricated and used for this purpose using silicon wafers and photolitography, as given in
34
35
36 Fig. 3. All the samples were hydrophobized by a vapor phase coating process. Afterwards,
37
38 hydrophilic spots were formed on these flat hydrophobic surfaces by using concentrated sodium
39
40 hydroxide droplets having a pre-determined spot diameter giving a hydrophilic circular spot
41
42
43
inside the sample as seen in Fig.3.a. For the second sample, a circular spot having considerable
44
45 roughness was formed in the flat sample as seen in Fig.3.b. For the third case, a flat circular
46
47 spot was formed in a large rough sample as seen in Fig.3.c. Then, water droplets with varying
48
49 contact diameters were located within the spot in some experiments, or out of the spot in the
50
51
52 other experiments and a and r values were measured for all of the cases.54
53
54
55
56
57
58
59
60
13
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7
8
9
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18
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20
21
22
23
24
25
26
Figure 3. Schematic description of a hydrophilic spot in a hydrophobic field (a), a roughened
27
28 spot in a flat field (b), and a flat spot in a roughened field (c). SEM image of roughened regions
29
30 in b and c with a scale bar of 10 µm (d). The value of D indicates the water droplet diameter
31
32 and d indicates the spot diameter in a, b and c. (Reproduced with permission from ref 54,
33 copyright 2007, American Chemical Society).
34
35
36
37 a and r results were investigated in two sets: For the first case where flat homogeneous/flat
38
39
40 heterogeneous surfaces were considered, the surface containing a hydrophilic spot inside the
41
42 hydrophobic flat sample was used as given in Fig. 3.a. At the beginning of the experiments,
43
44 Water a and r values on the smooth hydrophobic surface were measured as, a=119o, r=110o
45
46
47 and on the smooth hydrophilic surface, a=33-35o, r=9-11o. Later, water droplets having
48
49 varying volumes and contact diameters were positioned on the flat sample given in Fig.3.a and
50
51
52 a=33-35o, and r=9-11o values were measured in each instance when the spot was within.
53
54 However, always nearly same values of a=118-120o, and r=108-111o was observed when the
55
56
spot was away from the contact line, and there was no effect of f1, f2, d, and D, parameters on
57
58
59
60
14
1
2
3 these results. In conclusion, the a and r values predicted by Cassie & Baxter equation (Eq. 6)
4
5
6 which relied on the magnitudes of hydrophilic and hydrophobic portions were meaningless.54
7
8 On the other hand, for the case of flat homogeneous/rough homogeneous comparisons, the
9
10 rough spots and smooth fields were used as seen in Fig.3.b, and smooth spots and rough fields
11
12
13 were used as seen in Fig.3.c. When a large water droplet was placed on the large hydrophobic
14
15 smooth surface, the a and r values were nearly the same, a=118-120o and r=108-110o,
16
17 however when a small water droplet was located only inside the rough circular spot given in
18
19
20 Fig.3.b, then the a and r values increased up to a=165-168o and r=132-134o. This indicates
21
22 that the values of the water contact angles did not change and were nearly the same in the range
23
24
of a=118-120o and r=108-110o when the size of the liquid/solid contact area increased with
25
26
27 the increase in the diameter of the water droplet. This shows that there was no effect of the
28
29 magnitude of interfacial contact area of the rough substrates on the a and r values. These
30
31
32 results refute the use of Wenzel’s eqn. The contact angles on surfaces given in Figs. 3.b and 3.c
33
34 were found to be a=117-118o, r=81-82o for the case of smooth surfaces, irrespective of all the
35
36
values of f1, f2, d and D, although a rough spot was present within the contact line and a=165-
37
38
39 168o, r=132-134o were determined on apparently rough surfaces in all cases when a smooth
40
41 spot was present within the contact line. These result indicated that the  values calculated using
42
43
44 both Wenzel’s equation (Eq. 4) and Cassie & Baxter’s equation (Eq. 6) were meaningless. In
45
46 conclusion, no effect of the magnitude of the interfacial contact area was found on the measured
47
48 contact angle values and this experimental proof shows that both Wenzel and Cassie & Baxter
49
50
51 equations are wrong.54
52
53 The publications of Extrand, which refute the validity of Cassie & Baxter equation are
54
55 also important.55-58 A novel contact line density criterion was developed to predict the
56
57
58
possibility of the collapse or suspension of liquid drops on patterned rough surfaces in 2002. It
59
60 was concluded that the two important factors which are important to determine the  variations
15
1
2
3 instead of the absolute magnitude of surface roughness, are the linear fraction of the contact
4
5
6
line and slope of surface asperities.55 Extrand improved the contact line density approach by
7
8 incorporating the height of asperities and reported the critical values of the asperity heights and
9
10 contact line densities for the conditions of drop collapse by using liquid, solid properties in
11
12
2004.56
13
14
15 Later, Extrand evaluated the validity of Cassie & Baxter expression by designing some
16
17 original experiments. He formed circular polystyrene islands (lyophobic) on flat Si wafers
18
19 (lyophilic) and conversely, circular islands (lyophilic) by etching with sodium naphthalene on
20
21
22 perfluoroalkoxy fluoropolymer films (lyophobic).57 He placed water droplets on these samples
23
24 and forced their contact lines to advance beyond the island perimeter onto the surrounding area
25
26 by increasing the drop volumes. It was determined that a and r values were equal to the angles
27
28
29 displayed by the homogeneous periphery although the underlying contact area is consisted of a
30
31 mixture of lyophilic and lyophobic domains. Finally, Extrand made a deduction that the values
32
33 of ’s are the result of the interactions at the three-phase contact lines of drops, and are not
34
35
36 dependent to the liquid/solid interfacial contact area. In opposition to the expectations from the
37
38 Cassie & Baxter’s expression, no average value of on the heterogeneous surfaces can be found
39
40
41
which fits the experimental results.57 Afterwards, Extrand reported the drop retention forces in
42
43 terms of asperity height, shape, width and spacing to produce surfaces preserving liquid
44
45 repellency after exposure to large hydrostatic pressures created by impinging drops or liquid
46
47 columns.58 Meanwhile, Bormashenko and co-workers concluded that the dynamic transitions
48
49
50 between Cassie to Wenzel is mostly a one-dimensional than a 2D issue and force per unit length
51
52 of the three-phase triple line is the more significant parameter.59
53
54 Erbil and Cansoy tested the applicability of Wenzel and also Cassie & Baxter expressions.
55
56
57 A simple comparison method was developed in order to test the results of published 166
58
59 micro-patterned SH samples taken from 8 articles, consisting of both square and cylindrical
60
16
1
2
3 pillars.60 It was found that Wenzel expression did not fit the experimental results on SH surfaces
4
5
6
other than a few coincidental results. In addition, large deviations were found for the
7
8 experimental water results for the Cassie & Baxter expression case where 44% of the samples
9
10 containing square pillars and 65% of the samples containing cylindrical pillars could not be
11
12
13 estimated by using this expresion.60 In a subsequent publication, the utility of Cassie & Baxter
14
15 expression was also tested on micro-patterned SH samples. DRIE technique was applied on Si-
16
17 wafers with subsequent hydrophobization and 36 of samples were made of square and 24 from
18
19
20
cylindrical pillars. It was determined that the water results on these surfaces deviated
21
22 considerably from the Cassie & Baxter expression up to 88% for the square and up to 76% for
23
24 the cylindrical pillars.61
25
26
27 Yang et al. measured the apparent water ’s of droplets which was placed on micro-
28
29 structured surfaces consisting of cubic pillars after hydrophobization, in order to test the
30
31 possibility to apply the Wenzel and Cassie & Baxter expressions. The authors reported that the
32
33
34 state of outermost three-phase contact line was the most important parameter to determine the
35
36 apparent ’s and the contact area parameter under the outermost three-phase contact lines is
37
38 irrelevant.62 In another study, Liu et al. investigated the effect of the volume of a droplet on the
39
40
41 resultant ’s when the three-phase contact line is pinned. They developed a model showing that
42
43 the effective volume of a droplet on a micro-patterned surface is a monotonic function of the
44
45
macroscopic ’s. Finally, it was concluded that the experimental results were consistent with
46
47
48 the effect of the three-phase contact line rather than the contact area to determine the ’s.63
49
50 Bico et al. modeled the SH surface wetting behavior with spikes, holes, and stripes.64
51
52
53 Patankar also developed a model for SH surfaces using high square pillars.65 Dorrer and Ruhe
54
55 investigated the receding of a droplet on a SH surface. The authors indicated that the movement
56
57 of droplets was controlled by the ease of the retreat of the meniscus across the surface depending
58
59
60
on the size scale and topology of the surface.14 It was discussed that an analytical description is
17
1
2
3 possible for only extremely simplified topographies in order to estimate the CAH values, since
4
5
6
the problem is very complex.14 Shirtcliffe et al. investigated the relation of the spacing and
7
8 shapes of pillars at the three-phase contact line on the determination of the observed ’s. It was
9
10 reported that the possibility of the droplet to penetrate into the surface structure depends on the
11
12
13 spacing of features below the completeness of the droplet and a low CAH is more effective than
14
15 a high  for liquid shedding.22 In another article, it was reported that the one dimensional
16
17 (solid/liquid/vapor) three-phase contact line perspective is more useful, and consistent with the
18
19
20 experimental facts than the disproved however widely held-to-be-correct area based equations
21
22 of Wenzel and Cassie & Baxter.66 The author proposed that the origin of faulty intuition was
23
24 the confusion of the energy per unit area based surface free energy concepts with the force/per
25
26
27
unit length based surface tension concepts. This faulty conception is the reason of continuation
28
29 of the use of the wrong Wenzel and Cassie & Baxter models.66, 67
30
31 On the other hand, drop evaporation experiments were carried out to observe the
32
33
transition of so called “Cassie state” to “Wenzel state” on SH surfaces.68-70 The evaporation
34
35
36 process for water droplets located on top of the hydrophobized micro-pillars were monitored to
37
38 determine the process how could the droplets fall down into the space between the pillars.
39
40 McHale and co-workers reported that the water droplets which were previously located on the
41
42
43 tops of the circular pillars initially evaporated with the pinned contact line mode, before their
44
45 three-phase contact lines receded in a stepwise fashion by jumping from one pillar to another
46
47 pillar depending on the underlying pattern structure. After a while the droplets collapsed and
48
49
50
further evaporation happened with a completely pinned contact area.68
51
52 These results caused a debate between scientist defending or declining the use of the
53
54 Wenzel and Cassie & Baxter equations and was outlined in a review publication in 2014. 4 In
55
56
summary, the use of both of the Wenzel and Cassie & Baxter equations is not correct in the SH
57
58
59 field and must be avoided in the publications. On the other hand, “Wenzel State” or “Cassie
60
18
1
2
3 State” concepts may be used for visual description of droplets on patterned surfaces since these
4
5
6
states have been used for more than 70 years in the surface field. However, the discrimination
7
8 between the use of these “states” and incorrect “equations” should be kept in mind.
9
10
11
12
EXPENSIVE AND SMALL SCALE SH SURFACE PREPARATION ISSUE
13
14
15
16
17 Many good review articles were published describing the synthesis of various kinds of
18
19 SH surfaces12, 20-37 and the review of these preparation methods is not the subject of this paper.
20
21
22 A large number of different approaches have been used for the synthesis of SH surfaces,
23
24 including in-situ polymerization, polymer spraying, phase separation, sublimation, sol-gel
25
26 processing, wax solidification, hydrophobization by vapor deposition, fluorination, silane
27
28
29
deposition, using polymer/particle hybrid coatings including silica, inorganic or organic
30
31 particles, lithography, template methods, electrospinning, electrochemical methods on metal
32
33 substrates, hydrothermal synthesis, layer-by-layer deposition, one-pot reactions etc.20-37
34
35
Unfortunately, most of the reported SH preparation methods involve tedious multistep
36
37
38 approaches and severe conditions, or require the use of specialized instruments and chemicals.
39
40 Moreover, these methods are only applicable to produce very small SH areas or onto some
41
42 specific materials. For example, when a specific patterned surface roughness is formed on a
43
44
45 small low surface energy material by deep reactive ion etching (DRIE) technique, it is usually
46
47 very difficult to apply it for large areas.61 Another issue is the wide use of monomers or
48
49 hydrophobization compounds having fluorine atom in their structure to form SH (or
50
51
52
superoleophobic) surfaces. However, there is no requirement to use expensive and
53
54 environmentally harmful fluorine containing compounds to produce SH surfaces if we recall
55
56 that a water contact angle of 160° can be achieved on a lotus plant with a very small tilt angle
57
58
by the presence of paraffinic wax crystals comprising only the –CH2– and –CH3 groups. It is
59
60
19
1
2
3 clear that, the production of a hydrophobic surface having both micro- and nanometer length
4
5
6
scales is the key factor and there is no requirement to use fluorocarbons to achieve SH
7
8 properties.
9
10 Besides, most of reported methods in articles used to produce SH surfaces in the
11
12
laboratory cannot be used with large-scale low cost and rapid fabrication. Very few articles on
13
14
15 SH surfaces focus on the industrial applications and the durability and robustness issues of the
16
17 synthesized SH materials.20-37 In general, the use of low cost chemicals with a single-step
18
19 fabrication approach should be targeted to produce SH surfaces to be used in industry.
20
21
22
23
24 DIFFICULTIES TO OBTAIN A TRANSPARENT SH SURFACE
25
26
27
28
29
The cleaning of windows is usually a cumbersome process, especially if the windows
30
31 are located on a high building. The accumulation of dust particles is a common problem on all
32
33 glass surfaces, which are kept in outdoor environments but especially for solar panels, where
34
35
the dust films reduce the efficiency of the solar cells. Regular cleaning of the solar panels is a
36
37
38 tedious process and consumes considerable electricity and manpower. Self-cleaning SH
39
40 surfaces which were coated on glasses are particularly important for building windows, solar
41
42 panels, external windows of surveillance cameras, and mirrors that should be kept clean as long
43
44
45 as possible. However, for all of these applications the SH materials have to be highly
46
47 transparent. Unfortunately, transparency and SH properties are generally conflicting since light
48
49 transmittance in a medium decreases with the increase of the surface roughness because of Mie
50
51
52
scattering from a rough surface,71 especially if the roughness size exceeds the wavelength of
53
54 light.71-73
55
56 When light strikes to a surface, it can be reflected or absorbed before transmission. Thus,
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58
the transmissivity of light can be maximized by decreasing its absorptivity, and reflectivity. The
59
60
20
1
2
3 dimensions of the tiny structures imparting roughness on a SH surface should be lower than the
4
5
6
wavelength of the light (380 nm ∼ 760 nm for visible light) to obtain optically transparent
7
8 surfaces for human eyes, otherwise an extensive scattering of the propagated light takes place
9
10 because of the roughness presence. A SH coating becomes increasingly transparent when the
11
12
mean size of the rough particles on the surface is less than 100 nm since the intensity of
13
14
15 refraction at the air/coating interface is reduced due to refractive index difference between air
16
17 and the coating.72-75
18
19 On the other hand, the optical interference occurs when the light waves reflected by the
20
21
22 upper and lower boundaries of a thin film interfere with one another. This interference may
23
24 either enhance or reduce the reflected light. The multiple colors which can be seen in light
25
26 reflected from oil films on water are due to thin-film interference. The two reflected waves
27
28
29 strengthen each other when the film thickness is a multiple of a half of the light wavelength and
30
31 this situation increases the light reflection and reduce its transmission. On the contrary, when
32
33 the thickness of the film is an odd multiple of the quarter of the light wavelength on it, then the
34
35
36
reflected waves coming from both of the surfaces interfere to cancel each other giving complete
37
38 light transmission.
39
40 An anti-reflective coating is a type of coating applied to the surface of optical elements
41
42 such as lenses to reduce reflection and improve the effectiveness by resulting in less light loss.
43
44
45 Anti-reflectivity arises by step by step changing the refractive index as light passes through a
46
47 transparent medium. Alternating layers of contrasting refractive index are used for this purpose.
48
49 When a destructive interference is intentionally created by an anti-reflective coating in the
50
51
52 beams reflected from the interface on an optical substrate, then the reflected wave is
53
54 extinguished, and no reflection can emanate from such a surface. The thickness and properties
55
56 of the films are important. Preferentially, the incident light and the reflected light should be
57
58
exactly out of phase to accomplish this condition.
59
60
21
1
2
3 SH surfaces were used as antireflective coatings for optical material applications.76-82 It
4
5
6
is well-known that the simplest form of an interference anti-reflective coating can be made of
7
8 a single transparent thin layer having a refractive index which is equal to the square root of the
9
10 refractive index of the substrate. Thus, when air is the incidence medium and window glass
11
12
with a refractive index of 1.51 is the substrate, then an ideal single-layer antireflective coating
13
14
15 must have a refractive index value of 1.23.80 However, no solid materials are present having
16
17 such a low refractive index, and films of mesoporous silica nanoparticles are used as
18
19 antireflection coatings having refractive indices as low as 1.12. The incorporation of surface
20
21
22 roughness usually enhances light scattering for better anti-reflectivity but reduces
23
24 transparency.76-82 The optical properties of an transparent anti-reflective and self-cleaning
25
26 coating is given in Fig. 4.78
27
28
29
In summary, both reflection and absorption of light are negative issues for the
30
31 transparent surfaces. Thus, considerably transparent surfaces with light transmittance above
32
33 85% and having both self-cleaning property and anti-reflection ability indicate a great
34
35
application value. The degree of surface roughness should be carefully selected and controlled
36
37
38 to fabricate such transparent and good performing antireflective SH surfaces.32, 76-82
39
40 Roughness can be imparted onto a glass or a transparent polymer surface by a variety
41
42 of methods like plasma etching, chemical vapor deposition and spraying suitable hybrid
43
44
45 solutions. Many research groups produced transparent SH materials on windows using hybrid
46
47 materials based of silica and polymers. Self-assembly and self-organization based methods such
48
49 as chemical vapor deposition (CVD), layer-by-layer (LBL), and colloidal assemblies are
50
51
52
classified as bottom-up approaches. On the other hand, surface plasma treatment, lithographic
53
54 and template-based techniques are classified as top-down approaches. The hybrid methods to
55
56 combine both of the bottom-up and top-down approaches include solution casting using
57
58
polymer/inorganic mixtures, phase separation approaches and electrospinning.72-82
59
60
22
1
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3
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7
8
9
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26
27
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30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
Figure 4. Optical properties of transparent anti-reflective and self-cleaning coatings. (a)
46 Transmittance of double sided coated glass slides with 0 and 50 % nanocrystal (photocatalytic)
47
48 TiO2, (b) Reflectance of single side coated polyester having flexible properties. (Reproduced
49
50 with permission from ref 78, copyright 2013, American Chemical Society)
51
52
53
54 However, there are many drawbacks on the preparation methods of the transparent SH
55
56 surfaces, which were reported in the literature. Most of them involve special techniques that are
57
58 only suitable for laboratory scale studies with poor scale-up possibilities. Lithographic
59
60
23
1
2
3 processes or the use of templates with nano-scale roughness or surface coatings under vacuum
4
5
6
are too costly for large-scale applications. The sol-gel methods which require high-temperature
7
8 processes above 400 °C are not compatible with the manufacture of most of the optical devices.
9
10 A very suitable method without defects is still lacking to apply SH coatings on the large area
11
12
of glass or polymer surfaces. In addition, most of the articles have not reported any performance
13
14
15 results in relation with the recovering ability of surfaces against the applied abrasion induced
16
17 wear.32, 33
Thus, long-term durability of transparent SH surfaces and their poor abrasion
18
19 resistance are the major shortcomings. There is a need to improve the level of adhesion of
20
21
22 nanoparticle films onto substrates. For this purpose, the use of transparent adhesive coatings
23
24 containing previously loaded nanoparticles or embedding the nanoparticles into the transparent
25
26 polymeric substrates by the application of thermal methods are two promising approaches.
27
28
29
30
31 WATER VAPOR CONDENSATION ON A SH SURFACE ISSUE
32
33
34
35
Although seawater or brackish water desalination technology is effective, unfortunately
36
37
38 it is expensive and energy consuming which prevents its application in many regions of the
39
40 world. Thus, the application of bio-mimicking water-harvesting technology using drop
41
42 condensation from the water vapor present in the medium (fog collection) onto a SH surface
43
44
45 seems to be a potentially low cost alternative to obtain fresh water. The formation of sticky or
46
47 ball shaped water droplets on a SH surface by the condensation of water vapor from the medium
48
49 on this surface was proposed to be used in many applications other than water harvesting such
50
51
52
as anti-fogging, anti-icing, breathable, waterproof SH clothing.83-92
53
54 It was reported that liquid water penetrates into the structure of a lotus leaf by forming
55
56 sticky droplets when water vapor was condensed onto a cooled leaf surface. The SH property
57
58
of lotus leaf was lost after water condensation.83 Later, it was reported that condensation of
59
60
24
1
2
3 water vapor onto the synthetic micro-patterned SH surfaces generally leads to partial
4
5
6
penetration of the formed liquid water into the surface structure as shown in Fig. 5.84
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27 Figure 5. Water droplets after condensation on a surface of hydrophobized silicon posts of 40
28
29 µm tall, 2 µm wide, in 4 µm x 8 µm unit cell. The distortions of the three-phase contact line is
30 shown by black arrows. Water penetrates between the posts in darker areas, either underneath
31
32 and between the drops. (Reproduced with permission from ref 84, copyright 2006, American
33
34 Chemical Society)
35
36
37
38 In general, Wenzel state, Cassie state, and mixed Wenzel-Cassie state droplets can be
39
40 formed during the water vapor condensation onto patterned SH surfaces having micron sized
41
42 posts.84, 85 The droplets in the Wenzel state sometimes make a transition to the Cassie state
43
44
45 either entirely or partially during drop coalescencing.85 It was found that the presence of
46
47 nanometer sized features and certain roughness geometries (hairs and spikes) increase the
48
49 resistance of water vapor condensation on SH surfaces.14, 85-90 Superhydrophobic/hydrophilic
50
51
52 material composites or alternating hydrophobic/hydrophilic surface structures were
53
54 preferentially used for water harvesting where hydrophilic (or superhydrophilic) spots aim to
55
56 control the nucleation of water vapor and the surrounding SH area enhances droplet shedding.
57
58
59
When water condensation occurs, liquid water penetrates completely or partially into the
60
25
1
2
3 patterned surface structures.84-90 It is understood that the roughness size properties in relation
4
5
6
to the dimensions of the smallest stable droplets are important parameters. 91, 92
7
8 The external factors such as wind presence and speed, temperature, and moisture of the
9
10 medium are very important to affect the efficiency of water-harvesting apart from the properties
11
12
of SH surface and its structural factors. Unfortunately, most of the experiments about water-
13
14
15 harvesting were done under high humidity (over 60% RH) conditions to obtain more water
16
17 recovery, however future research should be focused on low humidity conditions which
18
19 represent the actual regions where most of the water shortage problems exist.90 Besides the
20
21
22 adverse effects of the usual external conditions, many of the water harvesting methods on the
23
24 SH surface have other drawbacks. The preparation of the test surfaces are time-consuming and
25
26 expensive, and there is no agreed standard to assess the water-harvesting efficiency. Lack of
27
28
29
robustness and short service life of the used SH materials is also a problem since some of the
30
31 surface structures can be easily ruined by the application of external force or lose its
32
33 functionality due to contamination when kept in the outdoor medium.
34
35
36
37
38 LACK OF ROBUSTNESS AND ABRASION RESISTANCE OF SH SURFACES
39
40
41
42 As given in the “Introduction” section, small mechanical forces can destroy the texture
43
44
45 on a SH surface having micrometer or nanometer sized structures in natural environments. This
46
47 mechanical weakness is the main reason for the loss of the SH properties in a short period of
48
49 time and then water droplets cannot roll off on the surface, but stick to the damaged locations
50
51
52
resulting in an irreversible decrease of contact angle and increase of contact angle hysteresis on
53
54 such locations. Patterns containing needle-like or pillar-like structures are ideal surfaces to
55
56 obtain a SH surface, but they have very poor abrasion resistance. Conversely, crater-like
57
58
structures or hemispherical protrusions are desirable to increase the mechanical resistance
59
60
26
1
2
3 however, the possibility of obtaining high water contact angles is very low on such surfaces.
4
5
6
When nanoscale structures are also involved on a surface as in two-size range SH materials,
7
8 even relatively small mechanical forces can easily destroy the complex surface texture and lead
9
10 to the local destruction of the SH properties.93, 94 Moreover, the removal of the dirt from
11
12
between the protrusions with mechanical rubbing becomes very difficult after the self-cleaning
13
14
15 effect fail. According to the explanation given above, it is expected that the most of authors
16
17 have to report the mechanical resistance properties of the newly synthesized SH surfaces in
18
19 their publications, but this is not the case in reality and was correctly criticized in several review
20
21
22 articles.32, 94
23
24 The most important parameters to assess the mechanical durability of a SH surface are
25
26 abilities of strong adhesion to the substrate, resisting tangential abrasive forces and preventing
27
28
29
the damage of dynamic impact (or scratching).32, 33 Adhesive ability of a SH surface to a
30
31 substrate can be simply tested by applying the “Tape peel test”. For this purpose, an adhesive
32
33 tape is pressed onto the test surface to eliminate air entrapment and to ensure uniform adhesive
34
35
contact. Then, the tape is stripped off from one end vertically and it is examined that whether
36
37
38 the coating is partially destructed or totally removed. After an individual peeling cycle, the
39
40 contact angle is measured again to test whether its value is still larger than 150o. Another peeling
41
42 test is the conventional “Cross-cut test” of surface coatings, which involves scoring marks on a
43
44
45 target region of the coating after forming a grid of small squares before applying the adhesive
46
47 tape which is then placed at a 45° angle across the grid and is removed afterwards. The adhesion
48
49 grading is based upon the amount of material removed after the tape peeling. ASTM D3359
50
51
52
standard reports the brand of tape, adhesion time and grading for cross-cut test.95 This test also
53
54 exhibits the brittleness of the coatings by examining the damaged patterns along the cut lines.
55
56 Another abrasion test is the application of linear shear abrasion with a solid abradant
57
58
moving across the sample surface. The test setup includes a horizontal arm holding a vertical
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60
27
1
2
3 cylinder that perform reciprocated motion in a linear direction. Different types of abradant
4
5
6
material such as different grades of sandpapers, cloth, rough rubber and poly(dimethyl siloxane)
7
8 films are attached to the bottom end of the cylinder which produce different degrees of
9
10 mechanical wear on a SH surface. The speed and the distance of the abrading cylinder can be
11
12
chosen for the specific needs. The pressure applied on the tested surface can be increased by
13
14
15 adding weights on to the vertical cylinder.96 Another abrasion test can be carried out via a rotary
16
17 system which involves mounting a flat square (or round) coated sample of around ~100 cm2 to
18
19 a turntable platform that is rotating on a vertical axis at a set speed. Two abradant wheels apply
20
21
22 a specific pressure onto the specimen surface rotating in the opposite directions, along a circular
23
24 track. The choice of abradant wheels and loading pressure is important to obtain repeatable
25
26 results. Grading can be done according to ASTM D4060 standard.97 Scratching tests such as
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28
29
“nano-scratching” using atomic force microscopy, or pencil of known hardness 98 and
30
31 blade/knife tests are also used for assessing the mechanical resistance of SH surfaces.99
32
33 However, scratching tests cannot replace peeling or abrasion tests, due to the fact it only causes
34
35
changes in a relatively small area around the scratch line.
36
37
38 On the other hand, a standardized mechanical test method is lacking to characterize the
39
40 abrasion resistance of the SH surfaces.32, 33, 94 In general, custom built in-house systems are used
41
42 to report linear abrasion resistance results in most of the articles. For example, rubbing the SH
43
44
45 samples with sandpaper,100, 101 some kind of cloth.100, 102 were tried. In any case, the applied
46
47 normal pressure, the abrasion distance and the number of abrasion strokes on the abraded SH
48
49 surface in the linear abrasion test must be controlled. The abrasion distance may not be uniform
50
51
52
over the abraded area if the abradant head is circular instead of square or rectangular and using
53
54 square abradant head is better.32, 94 For the selection of abradants, the use of silicon carbide
55
56 sandpapers with a definitive grit size (from coarse to ultrafine) seems to be reasonable for the
57
58
standardization of the test since these materials can be found easily worldwide. After the
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28
1
2
3 abrasion tests, the reporting only apparent contact angles is common but of little scientific value
4
5
6
and the advancing and especially receding contact angles should also be provided. After wear,
7
8 the receding contact angle is rapidly decreased showing large contact angle hysteresis and
9
10 resistance to droplet mobility. If possible, it is better to report the sliding or roll-off angle and
11
12
the droplet volume for a good comparison of abrasion results of SH surfaces.64, 94 Water jet tests
13
14
15 as given in Fig. 6103 or high speed scouring tests104 were also applied.
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26
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32
33
34
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36 Figure 6. The schematical description of waterfall/jet setup shown in front and side views
37
38 (Reproduced with permission from ref 103, copyright 2009, American Chemical Society).
39
40
41
42 Besides, there are problems with the correct use of “robust” or “mechanically durable”
43
44
terms in many articles. Many authors classified their samples as “durable” although they did
45
46
47 not properly test them against abrasion induced wear.33, 34, 105, 106 Some authors reported only
48
49 the good substrate adhesion results by the tape peel test without describing the applied force
50
51 and the number of cycles of the test. This is inadequate for the use of “durable” or “robust”
52
53
54 terms since a good substrate adhesion of the SH coating is a prerequisite.
55
56 Collision or impact tests with solids or liquids can also be applied as dynamic
57
58 mechanical resistance tests. SH samples are occasionally placed either horizontally or with a
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29
1
2
3 45° tilt and micron-sized sand or other suitable particles (or water droplets) are flowed down
4
5
6
onto the surface from a container placed mostly with at a constant speed from a predetermined
7
8 height from the surface. The height or mass parameters were increased to make more damage
9
10 on the SH surface when required.100 There is no need of any sophisticated equipment and a
11
12
standard procedure for the sand impact tests and thus many researchers adopted this method.32,
13
14 33, 106
15
16
17 In general, a successful method for maintaining mechanical durability is to use strong
18
19 materials that can resist the external effects by keeping the surface roughness as well as the
20
21
22 surface morphology of a SH surface under daily life conditions. In usual practice, some of the
23
24 materials used for making SH surface structures are hydrophilic and a thin layer of hydrophobic
25
26 surface coating is applied afterwards to transform such surfaces into SH. However, when such
27
28
29
a surface was scrubbed with a sandpaper, the top surface layers the microstructures were worn
30
31 off, exposing the hydrophilic parts.26, 100 Then the water contact angles decrease rapidly and
32
33 water-repellence is lost even though the Cassie state still holds. In order to avoid the above
34
35
problem, the use of already hydrophobic materials and imparting surface roughness with the
36
37
38 same or another hydrophobic material is a better choice to eliminate the need for an extra
39
40 hydrophobization. Another alternative is the incorporation of mechanically strong
41
42 microstructures into a nanostructure to carry most of the mechanical load during outdoor
43
44
45 applications.14 A composite containing some hard materials inside a polymer matrix improving
46
47 the resistance against mechanical wear and a covalently attached hydrophobic layer which can
48
49 withstand chemical and environmental durability tests can be a good candidate for the synthesis
50
51
52
of real robust SH surfaces. However, it should be kept in mind that such a material should be
53
54 easily applied to large areas.
55
56
57
58
DRAWBACKS OF SELF-HEALING SH SURFACES
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30
1
2
3
4
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6
Many plants in nature and some insect wings can repair or grow new structures if
7
8 mechanical damage and fouling happens on their surfaces to keep their water-repellence
9
10 property over their whole lifetime.107, 108 The mimicking of this self-healing mechanism in
11
12
artificial SH surfaces was suggested to prevent the exposure of hydrophilic bulk material.109, 110
13
14
15 Some suitable materials which can expose fresh layers onto top surface of a SH material upon
16
17 mechanical wear or chemical destruction was proposed to imitate the living systems which can
18
19 “heal” from these damages.32, 111-113 A self-healing surface can regenerate the surface structures
20
21
22 either as a result of the external wear or with the help of another stimulus to initiate a chemical
23
24 reaction in the surface layer. In some studies, roughness-shaping components having low
25
26 surface energy are embedded in polymer films, or heterogeneous interpenetrated networks, or
27
28
29
porous matrix and are then allowed to migrate to the surface by increasing the mobility of the
30
31 matrix through the influence of mechanical harm, external heat, moisture, etc., to restore the
32
33 initial SH properties. Another approach was based on the spontaneous self-organization of
34
35
hydrophobic colloidal particles at interfaces to impart roughness after wear.111-116
36
37
38 For example, a SH coating having self-healing ability can be obtained by the use of a
39
40 silane compound which was absorbed in the bulk coating and diffused onto the surface when
41
42 any mechanical damage happens in order to minimize its surface energy by transforming a
43
44
45 newly formed hydrophilic layer into hydrophobic and then restore the damaged layer.114
46
47 Similarly, a self-healing SH surface was produced using a fluorinated polyurethane elastomer
48
49 and extremely hydrophobic small heptadecafluorodecyl polyhedral oligomeric silsesquioxane
50
51
52
mixture by spraying onto surfaces. It was reported that this SH surface can recover its initial
53
54 water repellent properties after being eroded, plasma-cleaned, sonicated, burned or chemically
55
56 attacked as seen in Fig. 7.115 Inorganic particles are also used in self-healing of SH surfaces.
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58
All-in-one suspension that contains an aluminum phosphate binder, TiO2 nanoparticles, and
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31
1
2
3 alkylsilane was sprayed onto various substrates to fabricate SH surfaces which can repel water
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6
after the abrasion, and resistant to hot oil, water, and acetone for 24 h.116
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36 Figure 7. Superhydrophobic self-healing surfaces. (a) The change of roll-off angles for the four
37
binder/filler blend coating with the number of abrasion cycles. (b) The change of roll-off angles
38
39 of the FPU+15 wt % F-POSS coating after O2 plasma treatment, by recovery time at 80 °C. The
40
41 surface energy decreased with the blooming of fully fluorinated chains to the surface, with an
42
43 increase in water repellence. Water droplets (dyed blue) after the treatment of O2 plasma and
44 after thermal recovery are shown in the inset. (c) The change of roll-off angle of the FPU/F-
45
46 POSS coating with the change in temperature in 1 hour. TGA of the same coating is shown in
47
48 the inset at different temperatures. (d) The self-healing nature of the robust FPU/F-POSS
49
50
coating after ten successive O2 plasma/recovery cycles. (Reproduced with permission from ref
51 115, copyright 2017, American Chemical Society).
52
53
54
55 However, there are many inadequacies for the self-healing SH surfaces. The most
56
57 important difficulty arises from the fact that both the presence of surface hydrophobicity and
58
59 roughness should be regenerated simultaneously. The low molecular weight hydrophobic
60
32
1
2
3 components which was previously embedded in the matrix must quickly migrate towards the
4
5
6
damaged surface in order to regenerate the surface hydrophobicity. It was assumed that the
7
8 movement of the hydrophobic chemicals to the air interface can occur automatically due to the
9
10 surface free energy differences. However, the bulk system should be sufficiently soft and can
11
12
allow a high degree of mobility for this purpose. But if the matrix has this property, then it has
13
14
15 a poor ability to regenerate the surface roughness and thus, the accomplishment of the
16
17 simultaneous and spontaneous regeneration of topographic structures is very difficult. On the
18
19 other hand, most of the low surface tension chemicals are expensive, toxic or irritating and
20
21
22 especially perfluorinated chemicals slowly evaporate and lost during application.
23
24 In most publications on self-healing SH surfaces, some hard materials were incorporated
25
26 in the polymer matrix to act as a roughness supply and it was expected that when the SH surface
27
28
29
was mechanically damaged then these roughness-shaping particles would reach to the top of
30
31 the surface to generate new roughness profiles, or to replicate the initial surface roughness.
32
33 However, this step is the most difficult one and unfortunately the experimental results obtained
34
35
so far were not so successful. In other cases, it was planned that some external effects will be
36
37
38 applied to initiate the healing process such as temperature, moisture, light, or a pH switch.
39
40 However, in general, these stimuli do not match to many situations in daily life and it is possible
41
42 that no self-healing would occur at normal conditions. Another problem is the lack of standard
43
44
45 procedures to characterize self-healing materials and processes, making it difficult to evaluate
46
47 the most efficient self-healing strategies.
48
49
50
51
52
SURFACE CONTAMINATION AND SHORT USEFUL SERVICE LIFE OF SELF-
53
54 CLEANING SH SURFACES
55
56
57 The long-term stability of SH surfaces against contamination in outdoor conditions is
58
59
60 often overlooked, although it is a very important issue against self-cleaning process.14, 35 An
33
1
2
3 initially water-repellent SH surface can adsorb suspended particulate matter, volatile organic
4
5
6
compounds (VOCs), smudge and surface-active substances from air over time. This
7
8 contamination causes the loss of air pockets on the rough surface and the corresponding increase
9
10 in the surface free energy and decrease in water contact angles.14 Another problem is the transfer
11
12
of oily substances from fingers to SH surfaces due to their low surface tension. The “Wenzel
13
14
15 state” will become the favored wetting condition and contact angle hysteresis increase due to
16
17 newly formed hydrophilic defects. After a critical surface coverage with the contaminants is
18
19 reached then the surface lose all of its SH properties.
20
21
22 Generally, spray-coating of solutions containing fluorinated nanoparticles or polymers
23
24 is used to obtain thin self-cleaning coatings and there is no reliance of complex facility setup or
25
26 complicated operation process for this method.25-34, 117 Particulate matter contamination on SH
27
28
29
surfaces can be reduced by rinsing with water droplets that collect and remove the dirt from the
30
31 surface during rolling off in the self-cleaning mechanism.16 It was found that dirt removal can
32
33 be related to the tilt angle of the surface and on the speed and kinetic energy of water droplets.12,
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35 16, 20-27
In addition, it was reported that when nano- and hierarchical structures are present on a
36
37
38 SH surface, it shows more efficient self-cleaning than when microstructures are present.117
39
40 However, it is not possible to remove most of the contaminants by spraying water droplets since
41
42 the long exposure to outdoor conditions causes to gradual degradation of non-wetting SH
43
44
45 surfaces.73, 118, 119 A homemade contamination chamber and artificial water cleaning stage to
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47 test the surface contamination of SH surfaces in laboratory conditions is given in Fig. 8.118
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49 Unfortunately, only a few studies have reported the property loss of SH surfaces after they are
50
51
52
exposed to environmental conditions.14, 16, 26, 27, 73, 118-120 For example, Seeger and co-workers
53
54 kept their silicone nanofilament coatings under rainfall for one year. A slow increase in the tilt
55
56 angle was determined during the initial 6 months and organic contaminants covered the parts
57
58
of the coating which could not be cleaned by rain droplets at the end of one year.120
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34
1
2
3 It was proposed that the incorporation of a catalyst layer, usually TiO2 into a glass SH
4
5
6
coating would remove organic impurities deposited on the surface by photocatalysis. This
7
8 catalyst is activated by ultra-violet light, which causes the electrons to transfer to the conduction
9
10 bands and oxidize the impurities.73 However, such TiO2 containing coatings are not
11
12
superhydrophobic, they are superhydrophilic after UV irradiation because of the hydrophilic
13
14
15 nature of TiO2 which also cause the stain formation on the surface.121
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54 Figure 8. The schematical description of (a) chamber for contamination and (b) cleaning stage
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56 for artificial water (Reproduced with permission from ref 118, copyright 2009, American
57 Chemical Society).
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35
1
2
3 The prevention of the accumulation of impurities and the limitations of the self-cleaning
4
5
6
effect needs to be seriously examined before the applications of SH surfaces can be realized. 26
7
8 Unfortunately, the self-cleaning property tests of SH surfaces were not standardized. The actual
9
10 range of particles that can be removed by rinsing with water has not been systematically
11
12
determined. In many cases, only apparent contact angles were reported to evaluate the effect of
13
14
15 contamination on the SH surface but in reality only receding contact angles dramatically
16
17 decrease due to the presence of contamination and thus increasing the contact angle hysteresis
18
19 which prevents the rolling behavior of water droplets. The effect of the cleaning of the
20
21
22 particulate matter on the surface by wind action can also be studied by simulating air pressures
23
24 in the laboratory. Moreover, the selection of polluting particulate or oily materials is required
25
26 for the standardized tests.
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29
30
31 UNSUCCESSFUL ANTI-ICING SH COATINGS
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33
34
35
It was assumed that artificial SH surfaces can be successfully used in anti-icing
36
37
38 applications since it would repel the impinging water droplets and thus would eliminate their
39
40 presence on the surface before they can freeze.122-124 Moreover, ice adhesion strength was
41
42 expected to reduce after icing occurs, since only a small solid-ice interfacial contact area would
43
44
45 be formed because of the roughness present on the SH surfaces.122-127 Unfortunately, after much
46
47 experimentation, it was reported in many articles that the use of SH surfaces were not successful
48
49 in the anti-icing field.123, 128-138
50
51
52
The main reason is the loss of SH properties especially in sub-zero temperature
53
54 conditions having high humidity. In most cases, the condensed water droplets nucleate and
55
56 grow randomly within the hydrophobic microscale structures present on a SH surface, and this
57
58
fact can already be predicted from the classical nucleation theory.130, 139
The rate of
59
60
36
1
2
3 condensation on SH surfaces increases due to the existence of large surface area and
4
5
6
confinement within the microstructures. As a consequence, the growing water droplets are held
7
8 in the Wenzel state on the surface and prevented from being completely removed by the
9
10 application of external forces.130, 139 Another factor is the increase of the ice adhesion strength
11
12
when ice penetrates into the surface texture. After the ice formation on a SH, it usually destructs
13
14
15 the surface microstructures during the cycles of icing and deicing and also results in very high
16
17 ice adhesion strength, especially in a humid atmosphere.131, 132 In addition, SH surfaces having
18
19 dense nanoscale topography show longer droplet freezing times since they have condensation-
20
21
22 induced wetting resistance as can be seen in Fig. 9.129 Another reason may be the delayed ice
23
24 nucleation of sessile droplets on these hydrophobic nanostructures.127, 129, 140
25
26 On the other hand, the mechanism of the elimination of the presence of the water
27
28
29
droplets on a SH coating before they are totally frozen could not been materialized in
30
31 experiments. The reason is simple: The impacted droplets easily remove the air pockets present
32
33 on a SH surface if they can strike the surface with high velocity which corresponds to sufficient
34
35
kinetic energy and then they can imbibe into the rough structure. As a matter of course, the SH
36
37
38 property is lost and rapid heterogeneous ice nucleation occurs with the increased contact area
39
40 of the liquid droplet with the underlying solid which improves the heat transfer. The viscous
41
42 dissipation properties and initial droplet volumes and the size, structure of the surface patterns
43
44
45 all affect the vertical and horizontal motions of the droplets.124 When the temperature of the
46
47 medium is decreased then the viscosity of supercooled droplets increase with the corresponding
48
49 increase in contact time and decrease in the bouncing ability.141 In summary, the use of SH
50
51
52
surfaces for the passive anti-icing applications has not been fruitful, particularly in humid
53
54 weather conditions, which contradicts with the initial promising expectations.122-141
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29 Figure 9. The accumulation and freezing of a growing supercooled water drop on a SH surface.
30
The time is shown on each image from the onset of deposition. (a) The initial impacted
31
32 supercooled droplets have merged into one major unit and with small secondary satellite units.
33
34 (b) The main drop remains all liquid and has grown by the sequential impaction of ink-jetted
35
36 droplets from above. (c) The supercooled liquid was rapidly converted into a mushy liquid plus
37 ice phase shortly after the first freezing stage. (d, e) The crystallization front starts at the liquid-
38
39 solid contact area (horizontal dashed line) and gradually advances upward. (f) Completely
40
41 frozen drop. (Reproduced with permission from ref 129, copyright 2011, American Chemical
42
43
Society)
44
45
46
47
48 CONCLUSIONS AND OUTLOOK
49
50 The application areas of the SH surfaces have been enlarged very much especially in
51
52 the last decade by the contributions of many universities, national laboratories, and research
53
54
55 centers however, the volume of the industrial production of the SH coatings and materials is
56
57 not satisfactory when compared with the intensive research activity and number of published
58
59
60
38
1
2
3 articles in this field (more than 13.500) for the last 20 years. The reasons for this adverse
4
5
6
situation can be classified into several categories.
7
8
9
10 Scientific Reasons to Prevent Practical Applications of SH Materials and Coatings:
11
12
13
As given in “Cancellation of Wenzel and Cassie & Baxter equations” section, the use
14
15 of these equations is not correct and must be avoided in the SH studies. However, the “Wenzel
16
17 State” or “Cassie State” depictions may be used for the visual description of sessile droplets on
18
19
patterned surfaces since these names were under use for a long period of time.
20
21
22 As given in “Difficulties to obtain a transparent SH surface” section, light can be
23
24 transmitted, reflected, or absorbed through a coating and the transmissivity of light can be
25
26 maximized by decreasing its absorptivity, and reflectivity. A SH material becomes increasingly
27
28
29 transparent when the mean size of the rough particles on the surface is less than 100 nm. A very
30
31 suitable method without defects is still lacking to form large area transparent SH surfaces. Most
32
33 of the previously reported methods involve special expensive techniques that are only suitable
34
35
36
for laboratory scale studies with poor scale-up possibilities. Unfortunately, many articles have
37
38 not reported any performance results related to recovering ability of superhydrophobicity
39
40 against abrasion induced wear. Long-term durability of transparent SH surfaces and their poor
41
42
abrasion resistance are the major shortcomings. There is a need to improve the level of adhesion
43
44
45 of nanoparticle layers onto glass or transparent polymer substrates.
46
47 As given in “Water vapor condensation on a SH surface issue” section, when water
48
49 vapor is condensed onto a cooled SH surface, the liquid water penetrates into the
50
51
52 microstructures forming sticky droplets on the substrate depending on the size scale of the
53
54 roughness features and SH property is usually lost after the condensation of water.
55
56 As given in “Unsuccessful anti-icing SH coatings” section, there is a lack of the
57
58
59
discrimination of the liquid water repellent properties of a SH surface from the repellence of
60
39
1
2
3 ice and also water vapor from the same surface. It was experimentally proven several times that
4
5
6
the SH surfaces do not repel ice and water vapor and if a SH surface is kept in a condensation
7
8 condition (the solid temperature is below the dew point) then water vapor condensation will
9
10 occur in the surface microstructures giving significant surface wetting and strong icing behavior
11
12
on this SH surface. In addition, if a droplet strikes onto a SH surface with a sufficient kinetic
13
14
15 energy, then the air pockets present on the surface can be easily removed and water can imbibe
16
17 into the rough structure destructing the SH property. Thus, the use of SH surfaces for anti-icing
18
19 applications has been found ineffective especially in humid, below zero conditions.
20
21
22
23
24 Technical Reasons to Prevent Practical Applications of SH Materials and Coatings:
25
26 As given in “Expensive and small scale SH surface preparation issue” section, most of
27
28
29
the SH fabrication methods reported in the literature are applicable for only small area surfaces
30
31 by using high-cost materials. These methods were not suitable for large-scale production. In
32
33 addition, the use of many harmful chemicals to human health and environment such as organic
34
35
solvents and other materials were reported in many articles, which is impractical.
36
37
38 As given in “Lack of robustness and abrasion resistance of SH surfaces” section, most
39
40 of the SH surface fabrication methods did not consider the robustness and mechanical resistance
41
42 of the final coating and thus these methods could not be successfully implemented in industrial
43
44
45 applications. It is very easy to obtain a SH surface with plenty of fabrication methods, but
46
47 securing the mechanical durability of a SH surface even on small areas for an acceptable service
48
49 life-time in daily outdoor conditions is a great problem. If a SH surface is abraded, then its SH
50
51
52
property is usually lost, and that leads to critical disappointments in the industrial practice. The
53
54 use of a primer coating by spraying onto surfaces before the application of the final top-coats
55
56 are well known methods in the paint industry worldwide and only a very small part of the
57
58
publications on SH surfaces report the use of such methods.
59
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40
1
2
3 Moreover, there is the lack of the establishment of a standard mechanical abrasion (or
4
5
6
durability) test method for the SH surfaces. In the usual practice, researchers utilize homemade
7
8 tests such as applying linear abrasion with a sandpaper or flowing sand over a SH coating from
9
10 an arbitrary elevation. Unfortunately, the downward pressure and the type of abradant used
11
12
were not reported properly in many publications. However, it is not difficult to standardize the
13
14
15 abrasion tests since constant downward pressures on specific sandpapers and the constant flow
16
17 rates of specific sand grades from a specific elevation onto surfaces can be applied. On the other
18
19 hand, the results of pencil hardness test were reported without referencing the related ASTM
20
21
22 method and the applied load. In these conditions, the cross-comparisons of the results of the
23
24 different laboratories are not possible. In addition, other important tests such as substrate
25
26 adhesion, scratch resistance, erosion tests against powders, sand, chemicals and water droplet
27
28
29
spray should also be standardized.
30
31 The main requirements for the matrix polymers were not considered or even mentioned
32
33 in many articles reporting the inorganic/polymer hybrid SH coatings. The strong adhesion of
34
35
the SH layer to the target substrate, and the powerful bonding of inorganic particles in the
36
37
38 polymer matrix are two important requirements for practical applications. Besides, the control
39
40 of the particle burying level in the top polymer layer and the particle height over the flat surface
41
42 which would indicate the surface roughness degree should be controlled. Moreover, any SH
43
44
45 surface should not have any micro cracks on it after drying.
46
47 As given in the “Surface contamination and short useful service life of self-cleaning SH
48
49 surfaces” section, the long-term stability of SH surfaces against contamination in outdoor
50
51
52
conditions is often overlooked, although it is a very important issue against self-cleaning
53
54 process. When a SH surface is contaminated by suspended particulate matter, dust, VOCs,
55
56 smudge and surface-active substances in open conditions, the initial SH properties were lost,
57
58
preventing its use for long-term. Particulate matter contamination on SH surfaces can be
59
60
41
1
2
3 reduced by rinsing with water droplets that collect and remove the dirt from the surface during
4
5
6
rolling off in the self-cleaning. Dirt removal depends on the tilt angle of the surface and on the
7
8 kinetic energy of water droplets. However, on the adverse side, the pinned air layer associated
9
10 with a SH surface can be eliminated by a localized stream of water (or impingement of natural
11
12
rain). Unfortunately, only a few studies have reported the property loss of SH surfaces after
13
14
15 they were exposed to the outdoor conditions. There is no standardized method to evaluate the
16
17 self-cleaning effect. Only apparent contact angles were reported after the application of varying
18
19 cleaning process in most of the articles however it is well-known that receding contact angles
20
21
22 dramatically decrease due to the presence of any kind of contamination to prevent the rolling
23
24 of water droplets. Thus, receding water contact angles should be reported instead of useless
25
26 apparent contact angles.
27
28
29
As given in the “Drawbacks of self-healing SH surfaces” section, the roughness-shaping
30
31 components having low surface energy are embedded in polymer films which can expose fresh
32
33 layers onto top surface of a SH material upon mechanical wear, external heat, moisture,
34
35
chemical etching etc. was proposed to imitate the living systems having the ability to “heal”
36
37
38 from such damages. Another approach was the spontaneous self-organization of hydrophobic
39
40 colloidal particles at interfaces to impart initial roughness after wear. However, both the
41
42 presence of surface hydrophobicity and roughness should be regenerated simultaneously to
43
44
45 achieve the objective and this is a very difficult task. If the bulk system is sufficiently soft and
46
47 can allow a high degree of mobility for the transport of low surface tension materials to the
48
49 surface then it has poor ability to regenerate the surface roughness. On the other hand, most of
50
51
52
the low surface tension chemicals are expensive, toxic and sometimes can evaporate or drain
53
54 away during daily applications. In addition, standard procedures to characterize self-healing
55
56 materials and processes are lacking which makes it difficult to evaluate the most efficient self-
57
58
healing strategies.
59
60
42
1
2
3 For the future directions, it is anticipated that most of the research on the SH surfaces
4
5
6
should be directed toward large-scale production methods with the use of less expensive and
7
8 environmental friendly raw materials. There is no need to use fluorine containing expensive
9
10 materials in order to produce any SH surface, if we recall that lotus leaf has no fluorine groups
11
12
on its surface. Only the production of two different size scale roughness on a surface is
13
14
15 sufficient. The research on the use of cheap and suitable functional polymeric or inorganic
16
17 transparent primers or adhesive layers which can be applied between the target substrate and
18
19 the top-coat layer having SH properties may be a good choice. For transparent SH surfaces,
20
21
22 there is a need to improve the level of adhesion of the films containing nanoparticles onto
23
24 substrates. The use of transparent primer adhesive layers containing nanoparticles or embedding
25
26 the nanoparticles into a transparent polymeric substrate by applying moderate thermal methods
27
28
29
are two promising approaches for this purpose.
30
31 The research on the self-healing SH surfaces may be promising if the regeneration of
32
33 both of the hydrophobicity of the top coat and maintaining the initial roughness levels can be
34
35
successfully obtained. The development of the so-called “volumetric SH materials” which show
36
37
38 SH properties in every part of their bulk structure may be another solution if these coatings can
39
40 preserve the SH properties when their outer surface is abraded away. The newly exposed layers
41
42 should have a hierarchical texture with a hydrophobic chemistry after the regeneration. Finally,
43
44
45 it seems that we have to wait for a long period of time to achieve the widespread applications
46
47 of the SH surfaces in our daily life and in industry.
48
49
50
51
52
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26 Professor H. Yildirim Erbil graduated from Istanbul University as a chemical engineer in 1977.
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28 He obtained his MSc. from Aston University in Birmingham, England in 1978 and his PhD.
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30 from Istanbul Technical University in 1985. He was awarded the “British Council Research
31 Scholarship” in 1982-83 and “The Royal Society Exchange Scholarship” three times, between
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33 1998-2000. He worked in TUBITAK-Marmara Research Center (1979-1997), and as a part-
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35 time consultant in private sector companies (1992-1997), as a professor in Kocaeli University
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(1998-2004). He is now working in Gebze Technical University, Chemical Engineering
38 Department after 2004. He is the advisor of completed 34 MSc. and 10 PhD. thesis.
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42 Professor H. Yildirim Erbil’s main research subjects are surface modification of polymers,
43 contact angles and drop evaporation from surfaces. He authored two books, “Surface Chemistry
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45 of Solid and Liquid Interfaces”, Blackwell Publishing, Oxford in 2006 and “Vinyl Acetate
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47 Emulsion Polymerization and Copolymerization with Acrylic Monomers” CRC Press, Boca Raton
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49 in 2000, and two chapters in “CRC-Handbook of Surface and Colloid Chemistry” in 1997. He
50 obtained eight research grants from TUBITAK-Turkey, three from European Commission and
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52 one from NSF-USA. He published 80 papers in international journals (mainly in ACS and RSC
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54 journals) which was cited around 4090 times in Web of Science (6080 citations in Google
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Scholar) till November-2019.
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