Fabrication techniques for bioinspired, mechanically-durable, superliquipho-
bic surfaces for water, oil, and surfactant repellency

Samuel Martin, Philip S. Brown, Bharat Bhushan

PII: S0001-8686(16)30303-7
DOI: doi:10.1016/j.cis.2017.01.004
Reference: CIS 1713

To appear in: Advances in Colloid and Interface Science

Please cite this article as: Martin Samuel, Brown Philip S., Bhushan Bharat, Fabri-
cation techniques for bioinspired, mechanically-durable, superliquiphobic surfaces for
water, oil, and surfactant repellency, Advances in Colloid and Interface Science (2017),
doi:10.1016/j.cis.2017.01.004

This is a PDF file of an unedited manuscript that has been accepted for publication.
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12/7/2016

Fabrication techniques for bioinspired, mechanically-durable, superliquiphobic

surfaces for water, oil, and surfactant repellency

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Samuel Martin, Philip S. Brown, and Bharat Bhushan1

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Nanoprobe Laboratory for Bio & Nanotechnology and Biomimetics (NLBB)

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The Ohio State University

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201 W. 19th Avenue, Columbus, Ohio 43210-1142, USA
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Abstract
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Nature provides inspiration for liquid-repellant and low-adhesive surfaces, such as

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the lotus leaf and pitcher plant. While water-repellency is frequently found in nature, oil-

repellency and surfactant-repellency are uncommon to nonexistent. To obtain oil- and

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surfactant-repellency, hierarchical, re-entrant, bioinspired surface structures along with

low surface energy materials are needed. This overview presents wetting literature,

common liquids and their composition, and fabrication techniques for superliquiphobic

surfaces with repellency toward water, oil, and surfactant-containing liquids. Four

techniques for creating such surfaces are explained in detail: nanoparticle/binder, layer-

by-layer, nanoparticle-encapsulation, and liquid-impregnation. Static contact and tilt

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Corresponding author: bhushan.2@osu.edu
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angles with water and hexadecane liquids, morphology, wear, transparency, self-cleaning,

anti-smudge, and oil–water separation data are examined to compare the techniques. Data

for these techniques are presented showing evidence of re-entrant geometry and the

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ability for these surfaces to repel surfactant-containing liquids such as shampoo and

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laundry detergent. The data will provide guidance in implementing superliquiphobic

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surfaces for self-cleaning, anti-smudge, antifouling, and low-adhesion properties for

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various applications including plastic packaging and biomedical devices.
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Keywords: Superoleophobic, superhydrophobic, superliquiphobic, nanoparticles,

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fluorination, water-repellency, oil-repellency, surfactant-repellency

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1. Introduction

Liquid-repellant surfaces are of interest and may include self-cleaning, anti-

smudge, antifouling, and low-adhesion characteristics. These properties have applications

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in a large number of industries which include automotive, aerospace, electronics, plastic

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packaging, and biomedical devices [1]. When the liquid-repellant surfaces are also

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transparent, additional applications include smart screens for electronic display, camera

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lenses, window glass, and solar panels. A range of materials are used in these

applications which require superliquiphobic2 surfaces. As an example, materials of

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interest for smart screens in electronic displays include soda-lime silica, polyethylene

terephthalate (PET), and polycarbonate (PC). For plastic bottles and caps, materials
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include high-density polyethylene (HDPE), PET and polypropylene (PP). For automotive

applications, materials include glass, PC, polydimethylsiloxane (PDMS), PET, nylon,

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HDPE, polyurethane, polymethyl methacrylate (PMMA), PP, steel, aluminum, and

leather.
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Inspiration can be taken from nature in order to create liquid-repellent and low-

adhesive surfaces. The lotus leaf (Nelumbo nucifera) [2] and the pitcher plant

(Nepenthes) [3] exemplify these characteristics and their water-repellent and slippery

surfaces are shown in Fig. 1. In the lotus leaf example, a water droplet on a leaf is shown

with a contact angle of ~164°. This superhydrophobicity originates from the hierarchical

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The nomenclature superliquiphobic surfaces implying repellency to range of liquids was coined by Bhushan
(2016).
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structure formed by the combination of papillose epidermal cells as the microstructure

and 3-D epicuticular wax tubules covering these cells as the nanostructure [2,4].

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In contrast to the roughness-induced superhydrophobicity of the lotus leaf, the

carnivorous pitcher plant derives its properties from a slippery rim, known as a

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peristome. The peristome has a microstructure formed with regular ridges of smooth,

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overlapping epidermal cells. The microstructure can be wet by nectar and rainwater to

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form a continuous liquid film, resulting in an extremely slippery surface. Insects are

unable to adhere to the slick surface, and therefore, they aquaplane across the surface, fall
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inside the pitcher trap, and become ingested by the plant [3].
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By understanding the resourceful designs in nature, mimicking them, and

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improving upon them, many applications can be found that aid humanity and be of
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commercial interest. Nature has a limited material toolbox, but by incorporating synthetic
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materials and better manufacturing processes, the surface properties can be enhanced.
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Understanding structures found in nature and using them as design inspirations is the

field of biomimetics [1,4].

1.1. Wettability

The applications of a surface depend on the wetting characteristics of a droplet on

the surface. A droplet can be any liquid and is commonly denoted as hydro- for water or

oleo- for oil. A suffix of -philic or -phobic is used when the droplet is attracted or

repelled, respectively. Therefore, four states can be obtained: hydrophilic or oleophilic

for wetting with a water or oil droplet and hydrophobic and oleophobic for repelling with
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a water or oil droplet, respectively. When the contact angle (CA) is less than 10° in a -

philic state or greater than 150° in a -phobic state, the prefix super- is added. These

wetting states and their possible applications are shown in Fig. 2 [1].

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The wetting of a droplet on a solid surface is dependent upon surface chemistry

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and surface roughness. On a flat surface with a low surface energy, the maximum

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achievable CA with a water droplet is ~120° [5]. In order to increase the CA, roughness-

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induced superhydrophobicity can be utilized [1,6]. For self-cleaning, anti-smudge,

antifouling, and low-adhesion, another property of interest is contact angle hysteresis

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(CAH), which is the difference between advancing and receding contact angles. CAH can

be shown to be related to the energy dissipation of a droplet flowing along a surface. Low
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CAH results in a droplet rolling along a surface at a very low tilt angle (TA), which

facilitates particle removal for self-cleaning [1].

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On a rough surface, two wetting states have been observed: the Wenzel regime
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and the Cassie-Baxter regime. In the Wenzel state, liquid fully penetrates the roughness

features, which creates complete wetting of the solid interface [7]. In the Cassie-Baxter

state, the liquid droplet sits on top of the roughness asperities with air pockets trapped in

between, which creates a composite solid-air-liquid interface [8]. The Cassie-Baxter state

leads to higher CA with a given surface roughness and is preferred for liquid-repellent

surfaces. The high liquid-air fractional contact area also leads to low CAH, which is

important for droplets to easily roll off a surface at a low TA to facilitate self-cleaning.

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While superhydrophobicity is common in nature, superoleophobicity is

uncommon and more difficult to accomplish, as the surface tensions of oils are much

lower than that of water as shown in Table 1 [9,10]. Certain species of leaf hopper

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display high CA for diiodomethane and ethylene glycol [11] and springtails show

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repellency to olive oil [12]. However, surfaces from nature with repellency to liquids <30

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mN/m have not yet been found.

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Fluorinated components help repel low surface tension liquids such as oils by

reducing adhesion forces. Oil is non-polar and therefore only interacts with another
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molecule through a London dispersion force, which is a temporary attractive force due to

a pair of induced dipoles. Polarizability depends on the mobility of electrons and

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therefore quantifies the ability of a molecule to form instantaneous dipoles. Fluorine is

commonly chosen to create low surface energy materials due to its low polarizability. In
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addition, fluorine is highly electronegative, which measures the tendency of an atom to

attract bonding electrons to itself. Fluorine only requires one more electron in its 2p
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electron shell to create a stable electron configuration. The low polarizability and high

electronegativity of fluorine leads to weak London dispersion, cohesive, and adhesive

forces. Consequently, fluorinated materials are good choices for creating materials with a

low surface energy [10].

Fluorinated materials are combined with re-entrant geometries for improved

repellency. Re-entrant geometries are shapes that have overhang structures where the

surface features become narrower at the base. Re-entrant curvatures can be inverse

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trapezoidal, spherical, etc. and lead to higher CA than non-re-entrant geometries [6,10].

These geometries are necessary for repelling low surface tension liquids, and particularly

surfactant-containing liquids such as shampoos and laundry detergents due to their low

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surface tension components and active groups [13,14]. Common ingredients in shampoos

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and laundry detergents are shown in Fig. 3 and Fig. 4, respectively. Both liquids contain

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surfactants that act as detergents, wetting agents, and foaming agents. Surfactants are

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molecules that can lower the interfacial tension between phases. They typically comprise

a hydrophilic head group and a long hydrophobic tail. Common anionic surfactants
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feature a sulfate head group with a sodium counter-ion. Both examples of shampoo and

laundry detergent contain a mix of anionic, amphoteric, and non-ionic surfactants. This
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mixing of ionic and amphoteric surfactants is common in formulations for these types of

products [15]. The anionic surfactants are typically the main surfactant for cleaning
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purposes, while the amphoteric surfactant serves as a foaming agent. All surfactants have

the potential to lower the surface tension of the liquid, as well as adsorb at the interface of
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any solid with which the liquid comes into contact. These components typically have

surface tension values of 25–60 mN/m, depending on concentration with higher surface

tensions in the product if the surfactant is heavily diluted [16,17]. The surface tensions of

surfactants are on the same order as oils. However, a surfactant has polar head groups

that are highly active and adhere to surfaces stronger than oils. These liquids readily coat

the inside of plastic bottles, leading to wasted product and issues with recyclability.

Plastic bottles are typically made of high density polyethylene (~70%), polyethylene

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terephthalate (~25%), and polypropylene (~5%). Bottle caps are typically made of

polypropylene. Creating surfaces repellent to surfactant-containing liquids is important

for the consumer packaging industry.

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1.2. Re-entrant geometry

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A schematic explaining re-entrant geometries is shown in Fig. 5. In the Cassie-

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Baxter state, previously explained, air pockets are formed due to surface roughness (Fig.

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5a) and results in a higher CA than the complete wetting in the Wenzel state. For the

geometry shown in Fig. 5a, the ability to achieve the Cassie-Baxter state relies on the fact
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that the CA of the liquid on the corresponding flat surface (θflat) is ≥90°. The θflat CA is

the angle formed by the surface and the tangent of the solid-liquid interface. The surface
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tension force is directed along the surface and acts in the direction opposite to the tangent

of the solid-liquid interface. As shown in Fig. 5b, a non-re-entrant surface has a flat CA
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<90° with a surface tension force directed straight down. This geometry is not sustainable

and results in full wetting of the surface by the liquid.

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However, a high CA can be achieved, even if the CA of a liquid on the flat surface

is small, by creating re-entrant structures. Re-entrant geometries are shapes that have

overhang structures where the surface features become narrower at the base. For

example, Fig. 5c shows a re-entrant surface with inverse trapezoidal features where the

combination of the re-entrant angle (α) and θflat is ≥90°. This geometry supports a

favorable shape for the liquid–vapor interface with the surface tension force pointing

upward along the trapezoidal features. In this scenario, the liquid does not fully wet the

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surface, but has vapor pockets and a composite interface with a low liquid-solid contact

fraction) [10]. If the combination of angles (α + θflat) is still <90°, then the liquid will wet

the re-entrant geometry as seen in Fig. 5d with a surface tension force pointed downward.

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Structures with re-entrant curvature (spherical, cylindrical, oval, etc.) as shown in

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Fig. 5e are able to support high droplet CA for various liquids with flat CA <90° since it

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is possible to draw multiple tangents of a corresponding flat surface, as demonstrated in

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Fig. 5f. Therefore, liquids with various flat CA can wet the re-entrant curvature to

different extents to achieve a favorable liquid–vapor interface shape with the surface
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tension force directed upwards [10].
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1.3. Objective
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This paper covers strategies and fabrication techniques for liquid repellant surfaces
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in a comprehensive manner. The work is split into five sections. In Section 1, background
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literature has been presented on biomimetics, wetting, re-entrant geometry, and common
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liquids and their composition. In Section 2, fabrication techniques for repellency of

water, oil, and surfactant-containing liquids will be reviewed and compared. In Section 3,

experimental procedures for four fabrication techniques that have been shown to repel

oils and surfactant-containing liquids will be explained in detail. The characterization

methods for these samples will also be discussed. Section 4 will discuss data for these

four techniques using static contact and tilt angles, morphology, and wear. Additional

data will be presented showing evidence of re-entrant geometry and the ability for these

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surfaces to repel surfactant-containing liquids and other related properties. Section 5 will

present a summary of the techniques and future outlook.

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2. Literature review

A number of fabrication techniques have been advanced in the literature to obtain

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superhydrophobicity and superoleophobicity [1,10,18–20]. In this section, selected

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techniques that have been used to create superoleophobic surfaces will be discussed.

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Different studies claim superoleophobicity using a variety of oils. Various oils are shown

in Table 1 where edible oils generally have surface tensions greater than 30 mN/m and
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alkanes-based oils generally have surface tensions of 20–30 mN/m. Studies that solely

investigate repellency using diiodomethane (50.80 mN/m) and/or ethylene glycol (47.70
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mN/m) are less likely to be repellent to other lower surface tension oils. A more

appropriate choice for oil-repellency testing is hexadecane (27 mN/m).

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In order to achieve superoleophobicity, combinations of roughness and

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fluorination methods are commonly used as shown in Fig. 6. Roughness methods include

etching, micropatterning, combining nanoparticles and polymer, and encapsulating

nanoparticles in a substrate. Fluorination methods include using fluoropolymer,

fluorosilane or fluorothiol, fluoroplasma, or fluorosurfactant.

The etching roughness method has been demonstrated on metals such as

aluminum, copper, steel, titanium, and zinc using acid-etching and/or electrochemical-

etching [21–23]. Etching on various polymers including polystyrene and PMMA has

been completed using plasma treatment [24]. Etching is advantageous in that it typically
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treats an entire surface, regardless of geometries, and is an aggressive process. However,

it can be difficult to control and only suitable for small-scale experiments, making it

unsuitable for scale-up. Micropatterning allows for accurate replication of features with

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complex and possible re-entrant geometries. It has been successfully used to create

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flower-shaped structures [25], inverse-trapezoidal pillars [26], and mushroom-like pillars

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[27]. The nanoparticle + polymer and nanoparticle-encapsulation roughness methods are

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explained in Sections 2.1 and 2.3, respectively.

The fluoropolymer fluorination method has been applied to many different forms
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of roughness. This technique is straightforward, but if the fluoropolymer coating is too

thick, the surface roughness features are compromised and durability is poor. In contrast,
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a thin, self-assembled fluorinated layer can be formed from a deposition of fluorosilane

or fluorothiol. The fluorosilane method typically requires -OH surface groups to form a
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covalently bonded layer. Because silanes are sensitive to moisture and may require a

chemically activated surface, this method can be limited in application. Fluoronated

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thiols have limitations due to their instability toward oxidation and require particular

surfaces such as silver, gold, platinum, palladium, or copper. Fluoroplasma can etch and

deposit fluorination or simply fluorinate the surface. In both cases, it can easily treat an

entire surface, but it can be difficult to control and may be unsuitable for scale-up.

Similar to the fluorosilane and fluorothiol methods, a fluorosurfactant layer may require -

OH surface groups typically created by chemically activating the surface.

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Fluorosurfactants repel oil, but attract water, which is attractive for oil–water separation

applications [10,28].

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An overview of the studies on superoleophobicity will now be discussed. These

studies are broadly split into four categories: nanoparticle + polymer, layer-by-layer,

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nanoparticle-encapsulation, and liquid-impregnation.

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2.1. Nanoparticle + polymer technique

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The nanoparticle + polymer technique involves using a mixture of nanoparticles
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and polymer in order to create a coating. The nanoparticles create a nanoscale, rough

structure for superoleophobicity, and the polymer is used as a binder to hold the
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nanoparticles and adhere to the substrate. In addition, roughening of the substrate via
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etching or micropatterning can also be carried out in order to add microscale roughness.
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Lastly, a low-surface energy coating is generally applied in order to repel the low surface
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tension of oils. The idea of hierarchical roughness is similar to the hierarchical roughness
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found in the lotus leaf. However, by using synthetic materials and better manufacturing

processes, not only can superhydrophobicity be obtained, but superoleophobicity as well.

Using a binder of fluorinated acrylic copolymer and nanoparticles of various

composition and size, superoleophobicity has been obtained. TiO2 nanoparticles (20–50

nm) spray coated on a Si wafer resulted in ethylene glycol CA of 144° [29]. ZnO

nanoparticles (50 nm) spray coated on glass resulted in hexadecane CA of 154° [30].

SiO2 nanoparticles have been spin coated on glass for ethylene glycol CA of 165° using

30–50 nm nanoparticles [31], spray coated on glass for hexadecane CA of 147° using 55
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nm nanoparticles [32], and dip coated on polyethylene terephthalate (PET) for

hexadecane CA of 153° using 55 nm nanoparticles [33].

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SiO2 is often used for the nanoparticle material, and other polymers have been

combined with it for superoleophobicity. These binders have included 1H,1H,2H,2H-

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perfluorodecyltriethoxysilane for xylene CA of 141° [34], heptadecafluoro-1,1,2,2-

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tetrahydrodecyltrimethoxysilane for hexadecane CA of 137° [35], and

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trichloro(1H,1H,2H,2H-perfluorooctyl)silane for diiodomethane CA of 141° [36].

Milionis et al. [37] used an acrylic fluorochemical binder with 5-15 nm diameter SiO2
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nanoparticles for hexadecane CA of 159°. Martin and Bhushan [38] obtained hexadecane

CA of 156° using 10 nm diameter nanoparticles combined with methylphenyl silicone

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resin.
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In these techniques, the size of the nanoparticle and particle-to-binder (P–B) ratio
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are of importance. Smaller diameter nanoparticles result in more scales of roughness

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especially when combined with a rough substrate. When nanoparticles and polymer

agglomerate, they can form structures with rough surfaces and using smaller diameter

nanoparticles results in rougher structures with more air pockets. In addition, when

transparency is of interest, smaller diameter nanoparticles lead to greater visible light

transmittance. The P–B ratio affects the wettability and durability of a surface. When P–

B ratio is optimized, a surface will have its ideal CA and TA characteristics. When the P–

B ratio is too low, there will not be enough roughness. When the P–B ratio is too high,

the CA will decrease due to too many particles leading to Wenzel roughness properties

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[32] or the CA will remain constant due to no additional air pocket formation [33]. At too

low or too high of a P–B ratio, a droplet will become pinned leading to a high TA [32].

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2.2. Layer-by-layer technique

The layer-by-layer technique involves layers of oppositely charged species

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deposited separately in order to create a multi-layer coating held together via electrostatic

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interactions. Many different charged species can be used in each layer, which allows for a

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highly flexible coating with many applications in areas such as bioactive coatings [39],

anti-reflective coatings [40,41], and chemical sensors [42]. In addition, the layer-by-layer
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technique was used for superhydrophilicity. Because the components are typically water-

soluble polymers, these coatings are typically hydrophilic and oleophilic. Several
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superhydrophilic layer-by-layer coatings have used poly(sodium 4-styrene sulfonate),

polydiallyldimethylammonium chloride (PDDA), and silica nanoparticles. Using these

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components, Liu and He [43] created an anti-reflective coating using 30 bilayers of

PDDA and nanoparticles. Du et al. [44] created highly transparent coatings with greater
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than 90% visible light transmittance. Lee and Ahn [45] used these materials to coat

microchannels for capillary-driven bioassays.

By changing the top layer also known as the functional layer, Brown and Bhushan

[46] obtained all quadrants of the wettability landscape (Fig. 2) using PDDA and 7 nm

diameter silica nanoparticles. The initial layers of PDDA and nanoparticles result in

superhydrophilic and superoleophilic properties. However, with further treatment with a

silane, superhydrophobic and superoleophilic properties were obtained; with a

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fluorosilane, superhydrophobic and superoleophobic properties were obtained; and with a

fluorosurfactant, superhydrophilic and superoleophobic properties were obtained. For the

first time, this single, facile fabrication method with its flexible functional layer resulted

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in all four possibilities of water and oil repellency and affinity [46].

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2.3. Nanoparticle-encapsulation technique

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The nanoparticle-encapsulation technique involves embedding nanoparticles into a

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surface. Different nanoparticles have been embedded into a surface for anti-bacterial

properties [47,48], increased durability [49], and catalytic capability [50]. In order to
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obtain liquid repellency, embedded nanoparticles need to form nanoparticle agglomerates

with re-entrant geometries.

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Initially, superhydrophobic, polycarbonate (PC) surfaces were created without

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nanoparticles via solvent-induced phase transformation. When PC was immersed in

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acetone, crystallization of the polymer formed hierarchical structures that exhibited

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advancing water CA of 152° [51]. By adding SiO2 nanoparticles during the immersion

process, re-entrant geometries were obtained. The nanoparticles agglomerated forming

micron-sized clusters and acted as nucleation sites for polymer crystallization. After

ultraviolet (UV) activation and fluorosilane deposition, a superoleophobic surface was

demonstrated with water CA of 165° and hexadecane CA of 154° [13].

Another method for nanoparticle-encapsulation involves recrystallization of

polypropylene (PP). Initially, superhydrophobic PP was created by solvent casting a PP

film from a mixture of good (xylene) and bad (methyl ethyl ketone) solvents [52]. Good
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solvents dissolve the polymer, and bad solvents precipitate the polymer. Polypropylene

can also be dipped into a xylene-nanoparticle mixture for superhydrophobicity [53]. A

xylene-nanoparticle-PP mixture spin coated onto a PP substrate results in a

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nanocomposite polymer surface. With subsequent UV activation and fluorosilane

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deposition, superoleophobicity is obtained with water CA of 172° and hexadecane CA of

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159° [14].

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2.4. Liquid-impregnation technique

The liquid-impregnation technique involves adding a non-volatile liquid layer to a

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porous surface. This impregnated liquid has a surface tension lower than the liquid trying

to be repelled. In order to ensure the impregnated, lubricating liquid remains on the

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surface and is not also removed, a porous surface topography is typically created. The

repellency of the surface is dependent upon the miscibility of the liquids and the
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properties of the liquid layer. This technique takes inspiration from the pitcher plant due

to its peristome that becomes extremely slippery when wet by nectar and rainwater.
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It is important to choose a lubricating liquid that is immiscible with the liquid

being repelled. If the two liquids are miscible, then the liquid being repelled could adhere

to the surface or become embedded in the pores. When the liquids are immiscible, the

pores and lubricating liquid form a flat surface for liquid-liquid contact with the liquid

being repelled. This surface results in the repelled droplet sliding on the lubricating film

at a low TA.

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In order to combine the low-surface tension, fluorinated, lubricating liquid with

the porous structure, the chemistry of the porous structure typically needs to be modified.

An untreated, porous structure likely has a much higher surface energy than the

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lubricating liquid. Therefore, when they are combined, there is little interaction between

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the surface and liquid. Trying to repel a liquid droplet with a higher surface tension

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would likely displace the lubricating liquid. In order to keep the lubricating liquid

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adhered to the structure, the chemistry of the porous structure can be modified to more

closely match the fluorinating liquid by adding a fluorosilane coating [54,55]. In this
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case, the lubricating liquid will not be displaced because it has a more favorable

attraction with the porous surface than the liquid being repelled.
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Various liquid-impregnated surfaces have been created using different methods for

creating a porous structure. An early work used Teflon nanofibers or epoxy-molded

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nanoposts as the porous surface [54]. Although it made for a good model surface, its

composition, fragility, and cost made it unsuitable for certain real world applications.
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Other porous structures were created using electrodeposition of highly textured

polypyrrole nanostructures on aluminum [56] and nano-textured alumina gel films [57],

but did not show repellency to oils. Vogel et al. [58] showed repellency to olive oil using

a nanostructured film created using colloidal templating. However, it required glass or

other oxide substrates to form strong, covalent bonds, limiting its application to specific

substrates.

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Another technique involves spray coating wax to form a porous layer [59]. In this

method, the liquid is impregnated in a subsequent spraying step. The durability of the

wax coating remains questionable. A porous structure is more fragile that its solid

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counterpart, but still must have long-term durability. If the durability is compromised, the

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repellency of the liquids of interest becomes threatened.

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A durable structure has been created using porous PP created using a solvent-

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nonsolvent polymer solution [55]. After coupling the structure with fluorosilane and

impregnating the lubricating liquid, the liquid-impregnated surface repelled water,

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hexadecane, shampoo, and laundry detergent. In addition, the structure showed wear-

resistance to abrasive wear via a pin-on-flat test.

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3. Fabrication techniques
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In this section, first the experimental procedures for creating four types of
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superoleophobic samples will be reviewed. Next, surface activation methods and its
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background will be discussed. Lastly, the methods of characterizing the samples will be

presented.

3.1. Four superoleophobic techniques

Four different techniques that show repellency to water, oil, and surfactant-

containing liquids will be presented. Expanded schematics of the fabrication methods are

shown in Fig. 7. The nanoparticle/binder technique falls under the spectrum of

nanoparticle + polymer. It uses a combination of high hardness nanoparticles and durable

resin as a binder in order to create hierarchical, re-entrant roughness with a simple

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manufacturing method of spray coating. The layer-by-layer technique uses charged

components where each component is kept separate and deposited individually in order to

create a highly functional coating. The nanoparticle-encapsulation technique uses

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solvent-induced swelling and subsequent crystallization of the surface to create highly

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durable, rough surfaces. The liquid-impregnation technique uses an immiscible liquid

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immobilized on a porous surface for long-term repellency stability.

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These techniques are presented on two substrates: glass for nanoparticle/binder

and layer-by-layer, and PP for nanoparticle-encapsulation and liquid-impregnation.

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However, these techniques are not limited to these substrates and similar coating

properties were achieved on different substrates by following similar coating procedures.

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Additional substrates for each technique can be found in Table 2 and include additional

polymers such as polycarbonate (PC), polydimethylsiloxane (PDMS), polyethylene

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terephthalate (PET), and nylon 6/6. In order for the layer-by-layer technique to be

deposited on PC, PDMS, and PET, the substrate surface needed to be activated using
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ultraviolet or ultraviolet-ozone treatment, described in Section 3.2. The experimental

procedures for fabricating each technique on glass or PP are now presented.

3.1.1. Nanoparticle/binder technique

The nanoparticle/binder method used a coating of hydrophobic SiO2 nanoparticles

and methylphenyl silicone resin with subsequent fluorination of the coating by vapor

deposition of fluorosilane (Fig. 7a) [38]. Methylphenyl silicone resin was selected

because it is known to be durable and offer strong adhesion between the nanoparticles

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and substrate [60]. Hydrophobic, 10 nm SiO2 nanoparticles were selected because they

have high hardness for wear-resistance and high visible transmittance for transparency

[61].

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For the coating mixture, 150–600 mg of hydrophobic silica nanoparticles (10 nm

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diameter, Aerosil RX300) were dispersed in 30 mL of 40% tetrahydrofuran (THF, HPLC

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Grade, Fisher Scientific) and 60% isopropyl alcohol (IPA, Certified ACS, Fisher

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Scientific) by volume. This mixture was sonicated using an ultrasonic homogenizer (20

kHz frequency at 35% amplitude, Branson Sonifer 450A) for 15 min. Then, 150 mg of
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methylphenyl silicone resin (SR355S, Momentive Performance Materials) was added for

a particle-to-binder ratio of 1.0– 4.0. A particle-to-binder ratio of 2.5 was found to be

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optimal using CA and TA measurements. The mixture was then sonicated for an

additional 15 min to form the final mixture.

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CE

For the coating fabrication procedure, first glass slides (Fisher Scientific) were cut
AC

to dimensions of 25 by 10 mm and used as substrates. Next, the glass substrates were

cleaned in IPA with bath sonication (45 kHz frequency, Model FS5, Fisher Scientific) for

15 min. Then, substrates were rinsed with DI water and allowed to dry. After drying, 1

mL of the coating mixture was deposited via spray gun (Paasche®) from 10 cm away

with compressed air at 210 kPa. The sample was transferred to an oven operating at 70°C

for 5 min to remove the remaining solvent. Next, the sample was irradiated using

ultraviolet-ozone treatment with the samples placed 2 cm underneath the lamp source for

60 min. Lastly, one drop of trichloro(1H,1H,2H,2H-perfluorooctyl)silane (448931, Sigma

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Aldrich) was vapor deposited on the sample using a closed container. The sample was

attached to the top of the container via double-sided sticky tape with the surface facing

down, and the drop was placed on the bottom of the container. This setup allowed the

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fluorosilane gas to uniformly coat the sample, and a vapor deposition time of 30 min was

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used [38].

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3.1.2. Layer-by-layer technique

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The layer-by-layer technique used components of polydiallyldimethylammonium

chloride (PDDA) and hydrophilic, 7 nm SiO2 nanoparticles (Fig. 7b) [28,46,62].

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Polyelectrolyte, PDDA was chosen as the polymer base layer as it has a high cationic

charge density and has been known to bind strongly to glass substrates [44,45] and SiO2
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nanoparticles. The specific molecular weight range (100,000–200,000) was chosen to

balance mechanical properties and ease of deposition (viscosity). Hydrophilic SiO2

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nanoparticles were used to enhance the roughness of the coating and the negatively

charged surface silanol groups would ensure good adhesion to the positively charged
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PDDA layers [28,46,62]. Additionally, SiO2 nanoparticles are known to have high

hardness for wear-resistance and high visible transmittance for transparency [61]. It

should be noted that for non-active substrates, they can be activated using UV or plasma

treatment.

Glass slides (Fisher Scientific) were cut to dimensions of 25 by 10 mm and used

as substrates. PDDA (409014, Sigma Aldrich) was dissolved in distilled water (DS

Waters of America Inc.) at various concentrations. Silica nanoparticles (7 nm diameter,

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Aerosil 380, Evonik Industries) were dispersed in acetone (Certified ACS, Fisher

Scientific) using an ultrasonic homogenizer (20 kHz frequency at 35% amplitude,

Branson Sonifier 450A) at various concentrations. First, a PDDA layer was created by

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submerging the glass substrate in a PDDA solution (52 mg/mL) for 15 min. After

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removal, any excess was removed from the surface via bursts of compressed air from a

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spray gun (Paasche). The spray gun operated with compressed air at 210 kPa and was

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held 10 cm from the glass substrate at all times. Second, the SiO2 nanoparticle solution

(15 mg/mL, 3 mL) was spray coated. Third, a second PDDA layer was deposited (8
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mg/mL, 1 mL). After all the layers were deposited, the sample was transferred to an oven

operating at 70°C for 1 h. Finally, the functional layer was deposited onto the sample. For
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superhydrophobic/superoleophobic (top right quadrant, Fig. 2) coatings, chemical vapor

deposition under atmospheric conditions was used. One drop of trichloro(1H,1H,2H,2H-

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perfluorooctyl)silane (448931, Sigma Aldrich) was deposited next to the samples, which
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were then covered, and left for 6 h to produce a vapor deposited fluorosilane coating
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[28,46,62].

In addition, other quadrants of the wettability landscape could be obtained by

changing the functional layer. By not adding a functional layer, the

superhydrophilic/superoleophilic (bottom left quadrant, Fig. 2) state could be obtained.

By adding a silane treatment using methyltrichlorosilane (M85301, Sigma Aldrich) using

the previously explained chemical vapor deposition, the

superhydrophobic/superoleophilic (bottom right quadrant, Fig. 2) state could be obtained.

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Using a fluorosurfactant solution (Capstone FS-50, DuPont) diluted with ethanol to an

overall fluorosurfactant concentration of 45 mg/mL and spray coated (1 mL), the

superhydrophilic/superoleophobic (top left quadrant, Fig. 2) state could be obtained [46].

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3.1.3. Nanoparticle-encapsulation technique

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The nanoparticle-encapsulation technique creates polymer-nanoparticle composite

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surfaces with re-entrant geometries (Fig. 7c) [14]. Hydrophilic, 7 nm SiO2 nanoparticles

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were used to enhance the roughness of the coating because they have been shown to be

susceptible to irreversible aggregation, resulting in non-spherical, micrometer-sized

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clusters [63]. Additionally, SiO2 nanoparticles are known to have high hardness for wear-

resistance, which will aid in the creation of a mechanically durable coating [61].
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A polypropylene (PP) sheet (ASTM D4101-0112, SPI) was cut to dimensions of

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25 by 10 mm and used as substrates. Hydrophilic, 7 nm SiO2 nanoparticles (NP, Aerosil

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380, Evonik Industries) were dispersed in xylene (Mallinckrodt), known to dissolve PP,
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using an ultrasonic homogenizer (20 kHz frequency at 35% amplitude, Branson Sonifier

450A) at various concentrations. Polypropylene (0.6 g) was then added to the mixture.

The xylene–NP–PP mixture was heated to a temperature of 135°C in a glass flask fitted

with a water-cooled condenser to prevent solvent evaporation. Then, the mixture (1 mL)

was added to the PP surface via spin coating and the surface was allowed to dry in air. To

activate the polymer surface for silane attachment, samples were irradiated with

ultraviolet light for at least 12 h. Samples were fluorinated via chemical vapor deposition

of a fluorosilane, which was required in order to achieve superoleophobicity. One drop of

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trichloro(1H,1H,2H,2H-perfluorooctyl)silane (448931, Sigma Aldrich) was deposited

next to the samples, which were then covered, and left for 2 h to produce a vapor

deposited fluorosilane coating [14].

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3.1.4. Liquid-impregnation technique

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The liquid-impregnation technique creates a porous polypropylene (PP) layer

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using a xylene-cyclohexanone-polypropylene mixture (Fig. 7d). The porous layer is

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treated with fluorosilane and impregnated with an immiscible liquid. This technique was

created for long-term stability of repellency toward water, oils, and surfactant-containing
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liquids [55].
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A PP sheet (ASTM D4101-0112, SPI) was cut to dimensions of 15 by 15 mm and

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used as substrates. 0.2 g of PP was dissolved in 10 mL xylene (Mallinckrodt) heated to

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135°C in a glass flask fitted with a water-cooled condenser to prevent solvent

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evaporation. Once the polymer was fully dissolved, 4 mL cyclohexanone (Sigma

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Aldrich) was added and the mixture was stirred for 1 h. Then, a droplet of the solution

was added to the PP surface and the surface was dried in an oven at 70 °C for 1 h. To

activate the polymer surface for silane attachment, samples were irradiated using

ultraviolet treatment for at least 12 h. Samples were fluorinated via chemical vapor

deposition of a fluorosilane (to lower surface energy), which was required in order to

ensure preferential wetting by the lubricating liquid. One drop of trichloro(1H,1H,2H,2H-

perfluorooctyl)silane (448931, Sigma Aldrich) was deposited next to the samples, which

were then covered, and left for 2 h. The sample was then dipped into the impregnating

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liquid, in this instance a perfluoropolyether (Krytox GPL 102, Dupont) with a chemical

structure of F-(CF(CF3)-CF2-O)n-CF2CF3 where n = 10–60, a surface tension of 16–20

mN/m, and a viscosity of 38 cSt [55].

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3.2. Surface activation

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Surfaces are commonly chemically activated via plasma or ultraviolet (UV)

SC
treatment in order to modify the surface functionality [64,65]. After activation, surfaces

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typically have a higher surface energy and improved adhesion for additional coatings.

Plasma treatment is an effective surface treatment due to its aggressive nature. However,
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there are some disadvantages. It can be difficult to control and can require conditions not

typically suitable for scale-up. Another possible option is UV treatment, which is a

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milder activation that can be applied in ambient environments and is more suitable for

scale-up [65]. Various polymer surfaces have been activated using UV including PC
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[66,67], PP [68,69], PET [68,70] and PDMS [38,71–73]. Coating surfaces have been

activated using UV ([10,13,14]) and UVO [38] in order to deposit fluorosilane coatings.
AC

UV treatment can be broken up into two forms: ultraviolet and ultraviolet-ozone

(UVO) treatment). These two treatments are commonly used to activate surfaces in order

to apply a coating with improved adhesion to the treated surface. The techniques

presented in this overview used UV or UVO treatments in order to modify the surface

functionality. The UV exposure was generated from a compact germicidal lamp (15 W,

Model CFL15/UV/MED, LSE Lighting) with the maximum energy output at the 254 nm

wavelength. The UVO exposure was generated from a U-shaped, ozone-producing,

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ultraviolent lamp (18.4 W, Model G18T5VH-U, Atlantic Ultraviolet Co.) connected to an

electronic ballast (120 v, Model 10-0137, Atlantic Ultraviolet Co.). It is expected that this

lamp outputs a total of 5.8 W of 254 nm light, 0.4 W of 185 nm light, and 1.6 g/h of

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ozone in ambient conditions.

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Also in this section, UV and UVO processes are discussed and are shown

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schematically in Fig. 8. These treatments are photo-sensitized oxidation processes in

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which organic molecules in the surface layer are excited and/or dissociated by the

absorption of UV radiation [38,71,74].

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The UV method uses irradiation at 254 nm, whereas the UVO method uses a
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combination of 185 and 254 nm wavelengths. In the presence of 185 nm light, molecular
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oxygen can be dissociated into atomic oxygen, and atomic and molecular oxygen can be
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synthesized into ozone. In the presence of 254 nm light, ozone is decomposed into atomic
CE

and molecular oxygen [65,67,74]. These chemical reactions are shown in Fig. 8a [38].
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The UV and UVO surface activation processes are shown in Fig. 8b. In the UV

process, 254 nm light breaks up organic bonds in the surface layer, which causes the

surface to attempt to return to a stable condition. When these open bond sites react with

oxygen, oxidation occurs and highly active, polar surface groups are formed. These

groups are commonly hydroxyl, carbonyl, and carboxylic acids and lead to a chemically

active, hydrophilic surface [38,67]. In the UVO process, the combination of 185 and 254

nm light causes atomic oxygen to be continuously produced and ozone to be continuously

synthesized and decomposed. The wavelengths of light excite and/or dissociate

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molecules at the surface and then react with atomic oxygen to form desorbing, volatile

molecules, such as CO2, H2O, and N2. The desorbing molecules create adsorption sites

for oxygen to form highly active, polar surface groups, which lead to a chemically active,

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hydrophilic surface. The UVO process is an order of magnitude faster than the UV

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process due to an extra wavelength that produces highly-reactive atomic oxygen and

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helps excite and/or dissociate molecules [38,71,74].

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3.3. Characterization of samples

In this section, characterization methods for the samples are described. These
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methods include contact and tilt angle measurements, scanning electron microscope

imaging, coating thickness, repellency of surfactant-containing liquids, wear, self-

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cleaning, anti-smudge, anti-fogging, anti-icing, and oil–water separation.

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3.3.1. Contact angle and tilt angle

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Contact and tilt angle data were measured using a standard automated goniometer

( odel 90, am -Hart Inc.) using 5 μL DI water and hexadecane (99%, Alfa Aesar)
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droplets deposited onto the samples using a microsyringe. Contact angle was measured

by taking a static profile image of the liquid-air interface and analyzing it using

DROPimage software. Tilt angle refers to the angle when the droplet just began to roll off

the sample surface. All angles were averaged over at least five measurements on different

areas of the sample and reported as ±σ.

3.3.2. Scanning electron microscope imaging

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Top down, scanning electron microscope (Philips/FEI Sirion) images were taken

to determine the topography of the techniques. To image the re-entrant geometry, SEM

images were taken at a 70–75° angle. Samples were mounted with conductive tape and

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gold-coated prior to imaging.

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3.3.3. Coating thickness

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The coating thickness was measured using a step technique. One half of the

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substrate was covered with a glass slide using double-sided sticky tape before coating and

then removed after the coating procedure resulting in a step. A scanning area of 100 by
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100 μm2 including the step was imaged using a D3000 Atomic Force Microscopy (AFM)

with a Nanoscope IV controller (Bruker Instruments) to obtain the coating thickness. A

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Si, n-type (Si3N4) tip (resonant frequency f = 66 kHz, spring constant k = 3 N/m,

AppNano) was used. The coating thickness was measured in contact mode for the
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nanoparticle/binder technique and tapping mode for the layer-by-layer technique.

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3.3.4. Surfactant-containing liquid repellency

To test the repellency of surfaces towards surfactant-containing liquids, droplets of

shampoo (Head and Shoulders®, Procter and Gamble Co.) and/or laundry detergent

(Tide®, Procter and Gamble Co.) were placed onto surfaces tilted at ~25° for the lotus-

inspired techniques and ~45° for the pitcher plant-inspired technique. The resulting

surface–liquid interaction was photographed. The shampoo primarily contains sodium

lauryl sulfate and sodium laureth sulfate surfactants, while the laundry detergent

primarily contains sodium alcoholethoxy sulfate and sodium alkylbenzene sulfonate

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surfactants. At high concentrations, these surfactants typically have surface tensions on

the order of 25 mN/m. In the products listed, depending upon concentration, the surface

tensions will likely be in the range of 25–60 mN/m with values closer to the higher end

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[16,17].

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3.3.5. Wear experiment

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The mechanical durability of the surface was examined using an established

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macroscale wear test of a ball-on-flat tribometer [61]. A 3 mm diameter sapphire ball was

fixed in a stationary holder. A load of 10 mN was applied normal to the surface, and the
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tribometer was put into a reciprocating motion for 100–200 cycles. Stroke length was 6

mm with an average linear speed of 1 mm/s. The surface was imaged before and after the
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experiment using an optical microscope with camera (Nikon Optihot-2).

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Contact pressure for the tribometer wear experiment was calculated based on
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Hertz analysis [61]. An elastic modulus of 390 GPa and Poisson’s ratio of 0. 3 were used
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for the sapphire ball [75]. For the nanoparticle/binder technique, an elastic modulus of 0.5

GPa and Poisson’s ratio of 0.5 were used as an estimate for the composite coating,

resulting in a mean contact pressure of 4.8 MPa. For the layer-by-layer technique, the

elastic modulus of PDDA (0.16 GPa) was used to estimate the elastic modulus of the

composite coating, and a Poisson’s ratio of 0.5 was used (estimated). This resulted in a

mean contact pressure of 2.26 MPa. For the nanoparticle-encapsulation and liquid

impregnation techniques, the elastic modulus (1.3 GPa) and Poisson’s ratio (0.4 ) of PP

was used as an estimate for the elastic modulus of the composite coatings [76]. This

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resulted in mean contact pressures of 8.6 MPa. Due to the inclusion of SiO2 nanoparticles

in the nanoparticle/binder, layer-by-layer, and nanoparticle-encapsulation techniques, the

elastic modulus of the final coating is expected to be higher, so an underestimated

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pressure will be obtained with the selected modulus.

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With the nanoparticle/binder and layer-by-layer techniques, hexadecane TA was

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recorded before and after the wear test to determine if the coating was still repellent.

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Hexadecane droplets were placed on tilted samples both above the wear scar and directly

on the wear scar. In both cases, the TA at which the droplet could roll across the scar was
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recorded. These results are not presented in this overview, but showed that the surfaces

still repelled hexadecane droplets [38,46,62].

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For the layer-by-layer technique, microscale wear was examined through an AFM
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wear experiment. The nanoparticle/binder and nanoparticle-encapsulation techniques

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were too rough to be imaged by AFM and therefore AFM wear experiments were not
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performed. However, similar microscale durability is expected due to similar hardness of

nanoparticles. For the AFM wear experiment, the surface was worn using a 30 μm

diameter borosilicate ball mounted on a rectangular cantilever with nominal spring

constant of 7.4 N/m (resonant frequency f = 150 kHz, All-In-One). Areas of 50 by 50

μm2 were worn for 1 cycle at a load of 10 μm so as to be later imaged within the scanning

limits of the AFM. To analyze the change in morphology of the surface before and after

the wear experiment, height scans of 100 by 100 μm2 in area were obtained using a Si, n-

type (Si3N4) tip (resonant frequency f = 66 kHz, spring constant k = 3 N/m, AppNano)

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operating in tapping mode. Root mean square (RMS) roughness values before and after

wear experiments were obtained. Using an elastic modulus of 70 GPa and Poisson’s ratio

of 0.2 for the borosilicate ball [77], the mean contact pressure was calculated as 4.87 MPa

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using Hertz analysis [46].

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3.3.6. Self-cleaning

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The self-cleaning characteristics were examined by contaminating the sample with

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silicon carbide and comparing the removal of particles by water droplets before and after

the experiment. Silicon carbide (SiC, Sigma Aldrich) particles of size 10–15 μm were
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dispersed in a glass chamber (0.3 m diameter and 0.6 m high) by blowing 1 g of SiC

powder for 10 s at 300 kPa. After dispersion, the particles were allowed to settle on the
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sample mounted on a 45° tilted stage for 30 min.

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The contaminated sample was then secured to a 10° stage and water droplets (total
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volume of 5 mL) were dropped onto the surface from 1 cm in height. The removal of
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particles by the water droplets was compared before and after tests. The ability for the

water droplets to remove particles was quantified using image analysis software (SPIP

5.1.11, Image Metrology A/S, Horshølm, Denmark).

3.3.7. Anti-smudge

The anti-smudge characteristics were examined by first contaminating the sample

as described for self-cleaning. The contaminated samples were then secured on a stage

and a hexadecane-impregnated micro-fiber wiping cloth was attached to a horizontal

glass rode (diameter of 5 mm) fixed on a cantilever above the sample. As the cloth was
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brought in contact with the sample, the microfiber cloth was set to rub the contaminated

sample under a load of 5 g for 1.5 cm at a speed of about 0.2 mm/s. Images were taken

using an optical microscope with a CCD camera (Nikon, Optihot-2). The removal and

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transfer of particles by the cloth was compared before and after tests.

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3.3.8. Anti-fogging

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The anti-fog characteristics of the surfaces were examined by placing coated

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samples over boiling water for 5 s. The steam condensed on the coatings and was then

photographed to determine the resulting transparency.

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3.3.9. Anti-icing
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The anti-icing characteristics of the surfaces were examined by placing coated

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samples in a freezer set at -18°C for 2 h. The samples were tilted 10° and droplets of
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supercooled water (-18°C) were then dropped onto the samples from a height of 5 cm.
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3.3.10.Oil–water separation
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Superhydrophobic/superoleophilic and superhydrophilic/superoleophobic coatings

were found to be suitable for oil–water separation. The stainless steel meshes (#400) were

first cleaned with acetone and IPA until they were found to be hydrophilic, then the

coatings were deposited onto the meshes via spray coating. The coated meshes were then

placed on top of beakers. Agitated mixtures of hexadecane and water were then poured

onto the coated meshes. In separate experiments, the meshes were inclined at an angle

and the oil–water mixtures were poured over them. To improve contrast, Oil Red O and

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Blue 1 were used as oil and water dispersible dyes respectively. The use of dyes was not

found to have any effect on the performance of the coating.

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4. Discussion of Data

The wettability, surface morphology, repellency of surfactant-containing liquids,

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mechanical durability, transparency, self-cleaning, anti-smudge, and antifouling, and

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other properties for each of the four techniques, nanoparticle/binder coatings on glass,

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layer-by-layer coatings on glass, nanoparticle-encapsulated polypropylene (PP) surfaces,

and liquid-impregnated PP surfaces will now be reported and comparisons drawn

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between them.
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4.1. Wettability
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The CA and TA data using water and hexadecane droplets for the four
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superoleophobic techniques is presented in Table 3. The table presents data on untreated

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glass and untreated PP as well as the data for techniques deposited on these substrates.
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Untreated glass substrates display CA for water and hexadecane of 22±2° and 12±2°

respectively, Table 3. For the nanoparticle/binder and layer-by-layer coatings on glass

substrates, the hexadecane CA were found to be >150°, Fig. 9. In addition, the

hexadecane TA were <5° on both samples, Table 3. Therefore, both could be considered

to be superoleophobic, in addition to superhydrophobic (high CA and low TA for water,

Table 3) [62].

Untreated PP substrates were found to be slightly hydrophobic with water CA of

96±1° but oleophilic with hexadecane CA of 35±2°, Table 3. After treatment with the
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xylene–NP–PP mixture followed by drying in air, UV activation, and fluorosilane

treatment, the surface becomes superhydrophobic and superoleophobic with CA of

172±1° and 159±1° for water and hexadecane respectively, Table 3 and Fig. 9 [13]. Low

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hexadecane TA of 4±1° were also found on the fluorinated PP–NP composite surface. In

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all three of these cases, these high CA and low TA are a product of a composite interface

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with the droplet resting partially on pockets of trapped air.

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Finally, pitcher plant-inspired, liquid-impregnated surfaces comprising porous PP

dipped into a lubricating liquid were found to exhibit water CA of 115±2° and
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hexadecane CA of 70±2°, Table 3 and Fig. 9 [55]. These numbers do not seem as

impressive as the static CA found on the lotus-inspired surfaces. However, due to the
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presence of the lubricating liquid, the surface displays very low TA of 2±1° and 4±2° for

water and hexadecane respectively, Table 3. Because the low TA are a product of the
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homogeneity of the liquid–liquid interface, the surface tension of the liquid being

repelled has little effect on the repellency of the surface. This is in contrast to lotus-
AC

inspired superoleophobic surfaces, where decreasing the surface tension of the oil being

repelled results in an increase in the TA [28,62].

4.2. Surface morphology

In order to achieve superoleophobicity, specific surface topographies are required.

Re-entrant geometries, where local CA of <90° can be supported as demonstrated in Fig.

5, must be incorporated into the coating or surface treatment. In the case of the

nanoparticle/binder and layer-by-layer coatings on glass, hierarchical, re-entrant

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geometries are found as discrete, micron-sized agglomerates as seen in Fig. 10. For

nanoparticle-encapsulated PP surfaces, the rough surface contains a hierarchical surface

morphology with re-entrant, overhanging geometry, Fig. 10. In both cases, once

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fluorinated, these re-entrant structures enable the formation of a favorable liquid-vapor

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interface for lower surface tension liquids and therefore result in high CA for hexadecane.

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Previous work has also demonstrated that these coatings remained repellent towards

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lower surface tension liquids such as octane (Table 1), though an increase in TA was

observed with decreasing surface tension [28,62].

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It is believed that the re-entrant structures are formed due to nanoparticle

agglomeration. The small diameter of a nanoparticle leads to a very high surface-to-

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volume ratio. Since surface energy is inversely proportional to particle diameter, surface

energy is a significant contributor to nanoparticle properties. The large surface energy

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would promote nanoparticle agglomeration and, in order to minimize the surface energy,

these agglomerates would form tightly packed and quasi-spherical shapes [38,78]. In
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addition, smaller particles form agglomerates with a rougher surface that are more likely

to give the re-entrant structure. A larger particle is less likely to form agglomerates and

more likely to become partially embedded in the surface leading to hemispheres or

spherical caps [38].

For the liquid-impregnated surfaces, a porous structure is required to help hold the

lubricating liquid in place to ensure continued repellency. When cast, the presence of the

nonsolvent leads to separation into two phases, one polymer-rich and the other polymer-

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poor [52]. This phase separation results in the crystallization of the polymer into the

porous structure observed after solvent evaporation and drying, Fig. 10.

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4.3. Repellency of surfactant-containing liquids

Oil repellency is now a fairly common property to find in coatings and surface

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modification techniques, and there are many methods capable of producing

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superoleophobic surfaces. A new challenge is creating surfaces that repel surfactant-

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containing liquids. Such surfaces could find use in many applications including consumer

goods packaging, where repellency of surfactant-containing liquids is important in the

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packaging of shampoos and laundry detergents. Surfactant-containing liquids readily coat

the inside of plastic bottles, leading to wasted product and issues with recyclability. To
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determine the applicability of the four different techniques in real world applications such

as consumer packaging, their repellency against shampoo and laundry detergent was
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CE

tested. For the nanoparticle/binder and layer-by-layer coatings, droplets of shampoo and

laundry detergent were found to roll or slide from the surface with no noticeable
AC

contamination, Fig. 11 and Fig. 12. This is in contrast to the untreated glass substrates

where both shampoo and laundry detergent were found to spread and foul the surface.

For the nanoparticle-encapsulated surfaces, shampoo was found to slide across the

surface, Fig. 13. However, it was found that laundry detergent was not repelled and

contaminated the sample surface. This difference is probably due to the different

viscosities of the two surfactant-containing liquids. The laundry detergent is less viscous

and so is potentially more readily able to wet the solid surface and collapse the liquid–air

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interface of the Cassie-Baxter state. Additionally, the surfactant concentration of the

laundry detergent may be higher than that of the shampoo, resulting in a lower surface

tension liquid that was more likely to spread over the re-entrant geometry found on the

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nanoparticle-encapsulated surfaces.

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For the liquid-impregnated samples, both surfactant-containing liquids were able

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to slide over with no contamination, Fig. 14. In the case of shampoo, the highly viscous

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liquid slid from the surface in the shape of a droplet with a pronounced trailing edge. For

the laundry detergent, the liquid was found to spread more due to its lower viscosity.
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Though the main bulk of the liquid quickly vacated the surface, a thin film of detergent

briefly remained before slowly dewetting the surface and leaving the sample clean. It was
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found that these pitcher plant-inspired samples required more tilting than the lotus-

inspired surfaces due to the lower contact angles of the droplets and so a slower sliding
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action on the former compared to the rolling action on the latter. Despite this, both liquids

were successfully repelled by the liquid-impregnated surface [55].

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4.4. Comparing repellency for the four techniques

The four techniques reported here are capable of repelling both water and

hexadecane with very high CA and low TA for both liquids. The lotus leaf inspires three

techniques: nanoparticle/binder coatings, layer-by-layer coatings, and nanoparticle-

encapsulated surfaces. These surfaces achieve liquid repellency by featuring surface

topographic features that are able to trap air between the substrate and liquid, reducing

the solid–liquid interface and therefore increasing droplet CA and reducing TA.

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However, liquids on such surfaces occupy a metastable state that may be collapsed either

over time or by some external action (i.e. applied pressure, vibration, etc.). If this

happens, the composite air–solid–liquid interface underneath the droplet fails and the

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droplet fully wets the surface and the surface loses liquid repellency. This dependency on

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a metastable state could prove troublesome for applications where long-term contact with

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the liquid being repelled is required.

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Repelling surfactant-containing liquids can also prove challenging for lotus-

inspired surfaces. As reported above, the three techniques demonstrate some repellency
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towards both shampoo and laundry detergent (the nanoparticle-encapsulated surface was

only repellent towards shampoo), with droplets of the liquids rolling or sliding over the
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treated surfaces. However, if a droplet of either liquid is allowed to rest on these surfaces

for a significant period of time, surfactant molecules may attach to the surface at the
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liquid–solid interface. These surfactant molecules may alter the surface chemistry of the

solid surface, leading to a decrease in the local (flat) CA and a collapsing of the
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composite interface between the droplet and the surface. The surfactant can also remain

on the surface after the liquid is removed, which may lead to a permanent loss of

repellency.

Pitcher plant-inspired, liquid-impregnated surfaces are repellent due to a

lubricating liquid layer that preferentially wets a porous surface structure. Because of the

smooth liquid–liquid interface, the liquid being repelled is able to slide over the

lubricating liquid with low TA. As long as the lubricating liquid and the liquid being

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repelled are immiscible and the lubricating liquid remains within the porous structure,

these liquid-impregnated surfaces can effectively repel liquids regardless of their surface

tension, unlike lotus-inspired surfaces where repellency decreases with decreasing

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surface tension [28,62]. Furthermore, because this repellency does not rely on metastable

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states, these liquid-impregnated surfaces may possibly remain repellent for longer than

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the lotus-inspired surfaces. Additionally, since the lubricating liquid preferentially wets

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the porous structure, the liquid being repelled remains on top of this liquid layer and has

little contact with the solid surface below. This means that surfactant-containing liquids
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may be repelled with low risk of contamination of the solid surface by surfactant. Finally,

the ability to change the lubricating liquid depending upon the application improves the
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flexibility of this method. For instance, for consumer packaging applications, a food-safe

lubricating liquid would be desirable.

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When comparing the two different types of surface, it is important to note that, in

the case of the lotus-inspired samples, if shampoo is left on the superoleophobic surfaces
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for a significant amount of time, there is some reduction in the repellent nature of the

material. The superoleophobic material reported here could therefore find use in

applications where extended contact with the fouling product is minimal (such as bottle

cap or single-use applications). However, for shampoo-repellent applications where

surfaces are in constant contact with shampoo such as in the inside of a typical consumer

bottle, liquid-impregnated surfaces could be more suitable. The surfactant-containing

liquid has little contact with the substrate and therefore is less likely to adhere and alter

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the surface energy. Furthermore, liquid-impregnated surfaces should display greater

stability compared to traditional liquid-repellent surfaces whose repellency relies on

metastable states and trapped air. Liquid-impregnated surface treatments as reported here

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would therefore be more suited for applications where the contaminant liquid is in

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contact with the surface for long periods of time or is subject to vibration, both of which

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could result in the collapse of the Cassie-Baxter regime in traditional liquid-repellent

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surfaces.

4.5. Mechanical durability

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The mechanical durability of the samples produced by the four techniques was

investigated through tribometer and AFM wear experiments and the resulting optical
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images are displayed in Fig. 15. These experiments show the surface resistance of the

coatings to wear and abrasion. AFM wear is solely presented for the layer-by-layer
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technique because the nanoparticle/binder and nanoparticle-encapsulation techniques

were too rough to be imaged by AFM. However, similar microscale durability is

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expected due to similar nanoparticle hardness.

For the tribometer wear experiments, a portion of the wear track is shown, Fig.

15a. In the case of the nanoparticle/binder and layer-by-layer coatings on glass, the wear

experiments were carried out with a load of 10 mN for 100 cycles. After the wear

experiment, there is some noticeable burnishing to the coatings; however, damage to the

coatings is minimal in both cases. Higher magnification images confirmed that the

nanoparticle/binder and layer-by-layer composite coating morphology is similar before

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and after the wear test and there is no removal of the coating from the substrate [38,46]. It

is likely that the hard SiO2 nanoparticles used in both techniques help improve the

durability of both the coatings. In the case of the layer-by-layer technique, the oppositely

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charged PDDA binder layers anchor the negatively charged particles to the glass

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substrate via an electrostatic bond. In contrast, the nanoparticle/binder technique uses the

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resin binder to adhere the coating to the substrate.

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In the case of the nanoparticle-encapsulated surfaces, there was no noticeable wear

scar, even after 200 cycles, Fig. 15a. It is believed that these surfaces are significantly
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more durable than many current examples of superoleophobic surfaces. Other surfaces

typically rely on poorly adhered coatings, delicate surface structures, or the studies report
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either poor mechanical properties or fail to report any durability data. Finally, for the

liquid-impregnated samples, the images confirm that the surface features are not
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completely destroyed with minimal burnishing of the surface in the wear location. While

not as durable as the nanoparticle-encapsulated samples, it is believed that these surfaces

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are significantly more durable than many other examples of liquid-impregnated surfaces,

which typically rely on poorly adhered wax coatings [59] or delicate surface structures

[54]. The durability of the porous layer is required since it ensures the lubricating liquid

remains in place, impregnated within the pores. The porous structures required for this

liquid repellency technique may be susceptible to higher contact stress than more typical

oil-repellent surfaces and so it is crucial that mechanical durability is reported.

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For the AFM wear experiment on the layer-by-layer technique, a wear region of

50 by 50 μm2 is shown in the center of a 100 by 100 μm2 scan area, Fig. 15b. The layer-

by-layer coating survived the AFM wear experiment with no observable defects [46].

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Similar microscale durability is expected for the other nanoparticle techniques due to

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their incorporation of hard nanoparticles. However, AFM wear experiments were not

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performed due to the surface being too rough to image.

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4.6. Transparency

Many applications of oil-repellent surfaces rely on the transparency of the coating.

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Text remains legible when it is placed behind the nanoparticle/binder and layer-by-layer

coatings, suggesting that the coatings display characteristics of transparency, Fig. 16.
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Further improvement in transparency, potentially by decreasing the thickness of the

nanoparticle layer, may be possible in the future. In the examples of the nanoparticle-
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encapsulation and liquid-impregnation techniques reported here, PP, a translucent

material, is used as the substrate. If these techniques are used on transparent substrates,
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there will likely be a loss of transparency.

4.7. Self-cleaning, anti-smudge, and antifouling

The water- and oil-repellent properties of these surfaces make them suitable for

self-cleaning, anti-smudge, and antifouling applications. When contaminated with silicon

carbide, the vast majority of the contaminants can be removed in a self-cleaning test

where water droplets roll across the repellent surfaces, collecting particles in the process,

Fig. 17. After the self-cleaning test, >90% of the particles are removed on the

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superhydrophobic coatings. On the untreated glass and polypropylene samples, the

majority of the contaminants remain after the self-cleaning test. These coatings are self-

cleaning due to their high water CA and low CAH. Water droplets deposited onto these

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samples are able to roll over the coating with little impediment, collecting less

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hydrophobic contaminants as they go [13,46,62]. The liquid-impregnation technique does

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not exhibit the self-cleaning action because it does not have high water CA and so water

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droplets do not roll over the surface collecting contaminants.

For anti-smudge, the surfaces were contaminated in a similar way and a

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hexadecane-soaked cloth was used to wipe the surfaces [79]. The anti-smudge data for

the nanoparticle/binder, the layer-by-layer, and nanoparticle-encapsulation are shown in

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Fig 18–20. For the oil-repellent surfaces, the particles were transferred to the cloth with

no observable particles remaining on the surfaces. However, on the untreated samples,

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many particles remained on the sample and oil was transferred from the cloth to the

sample. Similar to the self-cleaning experiments with water, the anti-smudge property
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relies on a high CA and low CAH for the oil. The oil in the cloth is able to collect

oleophilic contaminants from the surface of the coating without sticking to the surface

[13,28,46,62]. Because the liquid impregnation technique does not exhibit high

hexadecane CA, the hexadecane-soaked cloth is likely to transfer oil to the surface

making it less suitable for anti-smudge applications.

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Finally, the oil-repellent coatings could be used for anti-biofouling, where

superoleophobicity and nanostructuring can contribute to reducing microorganism

attachment [80].

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4.8. Other properties

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All the techniques here are capable of producing a water- and oil-repellent surface.

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If other properties on the wettability landscape (Fig. 2) are desirable, the layer-by-layer

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technique offers additional flexibility to result in coatings that exhibit all four possible

combinations of liquid repellency and affinity. The coating is comprised of several

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discrete layers, which are deposited individually. The final (top) layer in the coating

contains the desired surface chemistry and can be easily swapped to produce a different
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functionality as shown in Fig. 21. In the case of the superhydrophilic/superoleophilic

coating, no additional functional layer is added, leaving the high surface tension polymer
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layer exposed. For superhydrophobic/superoleophilic coatings, a non-fluorinated silane is

used to repel water but not oils, which have lower surface tensions (Table 1). For
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superhydrophobic/superoleophobic coatings, a fluorinated silane is used to repel both

water and oils. Finally, for superhydrophilic/superoleophobic coatings, a fluorosurfactant

is used to yield the desired “flip-flop” of surface properties required [46]. In all cases, the

inclusion of a nanoparticle layer enhances the surface properties of the functional layer to

result in super-philic/super-phobic surfaces. Water and hexadecane droplet images and

CA for all four coatings are shown in Fig. 22. The superhydrophilic/superoleophilic

coating was instantly wet by both water and oil. The superhydrophobic/superoleophilic

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coating was wet by oil whilst repelling water. The superhydrophobic/superoleophobic

coating repelled both liquids. Finally, the superhydrophilic/superoleophobic coating

repelled oil, but was wet by water. Table 4 provides a summary of all CA and TA data

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[46].

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The oil repellency of the superhydrophilic/superoleophobic coating, in addition to

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wetting by water, is due to the fluorosurfactant containing a low surface tension

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fluorinated tail and a high surface tension head group complexed with a hydrophilic

polyelectrolyte. During spray coating, the polar head group forms an electrostatic
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complex with the polyelectrolyte layer below and the fluorinated tails orient themselves

at the air interface. Large, bulky oil molecules are trapped at this fluorinated interface
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while smaller water molecules can more easily penetrate down through the thin layer (ca.

30 nm) to the hydrophilic region where the surfactant head group complexes with the
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polyelectrolyte layer. The result is a “flip-flop” of surface properties and a coating that

repels oils but is wet by water [46].

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The flexibility of this technique allows one to select the surface properties most

suitable for the application in mind. For instance, anti-fogging surfaces rely on substrates

that have high wettability to water. To examine the anti-fogging properties, all four

coatings were placed directly above a source of boiling water for 5 s. The samples were

then photographed to assess their transparency, shown in Fig. 23. Both the

superhydrophilic coatings were found to retain their transparency with text remaining

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visible through the condensed water layer. In contrast, on the superhydrophobic coatings,

the formation of discrete droplets of water results in samples that are completely opaque.

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For the superhydrophilic/superoleophobic coating, the speed of the water

penetration through the low surface tension fluorinated tail groups to the high surface

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tension head groups is crucial for the condensed droplets to spread out and form a

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continuous water layer and thereby maintain transparency [46]. Previously developed

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coatings would not be suitable for anti-fogging applications because the rate of water

penetration is too low (takes 5–30 min for surface to become superhydrophilic) [81–84].
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Another example of selecting the correct surface properties for a given application
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is anti-icing. For anti-icing experiments, all four coatings were placed in a freezer set at -
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18 °C for 2 h. The samples were tilted and droplets of supercooled water were deposited
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onto them, as shown in Fig. 24. For the superhydrophilic coatings, the droplets spread out
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and froze on the sample surface. For the superhydrophobic coatings, droplets rolled off
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the surface to freeze on the bottom of the freezer. This occurs because the water droplets

are in the Cassie-Baxter state. The formation of a composite interface minimizes the

contact with the cooled substrate and ensures a low hysteresis so droplets can roll from

the tilted surface [46].

Finally, superhydrophilic/superoleophobic coatings exhibit a different response to

water and oil and therefore are suitable for use in oil–water separation. The use of

hydrophilic/oleophobic coatings is preferable over alternative configurations where the

surface is hydrophobic/oleophilic, because surface contamination by oil and other oil-

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based contaminants is common, and the porous material must then be cleaned or

replaced, resulting in a drop in the separation efficiency. It is therefore preferable for the

water phase to be allowed to pass through the mesh and the oil phase be repelled.

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Additionally, water is denser than oil and tends to sink to the bottom of a mixture

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meaning hydrophobic/oleophilic materials are not suitable for certain applications, such

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as gravity-driven separation.

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Agitated oil–water mixtures were poured onto a superhydrophilic/superoleophobic

-coated mesh suspended over beakers, as shown in Fig. 25. The water component passed
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through the mesh while the oil remaining on top, rolling across the top of the mesh to be

collected in a separate beaker. This tilted setup is only possible due to the fast penetration
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by water. There was no degradation of oil–water separation after sitting in ambient for

over a year. Previously developed coatings would not be suitable for this method of oil–
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water separation because the rate of water penetration is too low (takes 5–30 min for

surface to become superhydrophilic) [81–84].

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It should be noted that by using fluorosurfactant in place of fluorosilane, the

nanoparticle/binder technique can also be used for oil–water separation. The benefit of

the nanoparticle/binder technique is that it requires fewer manufacturing steps than the

layer-by-layer technique, although surface activation for the fluorosurfactant layer is

needed. In the layer-by-layer technique, electrostatic attraction between the top

polyelectrolyte layer and the fluorosurfactant may provide greater durability.

5. Summary and outlook

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Four different fabrication techniques have been developed for superliquiphobic

surfaces repellent to water, oil, and surfactant-containing liquids. All four techniques

result in surfaces that are extremely repellent to water and hexadecane. The high contact

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angles and low tilt angles for the nanoparticle/binder, layer-by-layer, and nanoparticle-

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encapsulation techniques result in self-cleaning and anti-smudge properties. Because the

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liquid impregnation is only repellent to these liquids at lower contact angles than the

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other three techniques, it does not exhibit the self-cleaning and anti-smudge properties. In

addition, all techniques demonstrate some repellency toward surfactant-containing

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liquids. The liquid-impregnation method performs well because shampoo and laundry

detergent may not foul these surfaces even after extended contact, so long as the
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lubricating liquid remains within the porous structure. In the other techniques, if a

surfactant-containing droplet is allowed to rest on the surface, eventually surfactant

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molecules can alter the surface chemistry of the solid surface, leading to a decrease in the

local contact angle and a collapsing of the composite interface between the droplet and
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the surface. It should be noted that formation of re-entrant geometry in these techniques

allows repulsion of liquids, which is extremely desirable. Further experiments are needed

to determine if permanent loss of repellency occurs.

The nanoparticle-encapsulation technique exhibited good wear-resistance.

Nanoparticles were directly incorporated into the surface during solvent-induced

softening of the polymer material, resulting in durable surface properties. In contrast, the

nanoparticle/binder and layer-by-layer techniques are applied as a coating. The

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robustness and durability of the surface properties achieved from a coating will be

dependent upon their adhesion to the substrate. Selecting suitable coating materials and

activating the substrate for coating attachment can lead to high wear resistance.

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All four techniques can be easily fabricated. However, the nanoparticle/binder and

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nanoparticle-encapsulation techniques require the fewest steps. The nanoparticle/binder

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method is a one-step spray technique followed by fluorosilane deposition. Similarly, the

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nanoparticle-encapsulation technique involves spin coating or immersion followed by

fluorosilane deposition. However, both the nanoparticle/binder and nanoparticle-

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encapsulation methods require surface activation before fluorosilane deposition. In

contrast, the layer-by-layer technique does not require surface activation for fluorosilane
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deposition, but requires three spray steps and possible surface activation on hydrophobic

substrates for the first layer. The difficulty in fabricating liquid-impregnated surfaces
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arises from forming the porous structure, but the subsequent steps of depositing the

fluorosilane layer and adding the low-surface tension, lubricating liquid are relatively
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straightforward.

The nanoparticle/binder and layer-by-layer techniques have the greatest flexibility

in terms of substrate applicability and modifying the functionality for various

applications. The substrate-independence can be advantageous for applications where

multiple base materials are frequently used or where the same properties are sought

across different products. In addition, by simply modifying the last step of the coatings,

the properties of the coatings can be radically altered. Such an approach could simplify

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fabrication, with different products receiving the same base coatings with only the final

layer differing between products.

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By understanding surfaces in nature and improving upon them by incorporating

synthetic materials and better manufacturing processes, many different techniques have

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demonstrated water and oil repellency. By weighing the strengths and limitations of

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various techniques, the suitability of each for a particular application can be determined.

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New areas can implement these techniques or use them as a foundation for additional

techniques to create surfaces with self-cleaning, anti-smudge, antifouling, and low-

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adhesion properties. The field of superliquiphobicity continues to grow as more surfaces

implement these properties and the number of applications requiring these surfaces
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increases.
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82. Sawada H, Yoshioka H, Kawase T, Takahashi H, Abe A, Ohashi R. Synthesis and

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Colloid Polym Sci 2015;293:65-–73.

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Table 1 Surface tensions of common liquids used to assess liquid-repellency

Surface tension
Liquid

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(mN/m)

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Water 71.99

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Diiodomethane 50.80

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Ethylene glycol 47.70

Rapeseed oil ca. 35

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Peanut oil 32.23
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Olive oil 32.03

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Soybean oil 29.43

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Xylene 28.47

Hexadecane 27.05
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Tetradecane 26.13

Dodecane 25.35

Cyclohexane 24.95

Decane 23.37

Methanol 22.70

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Ethanol 22.10

Octane 21.14

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Hexane 18.43

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Pentane 15.48

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Silicone oils 16–20

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Perfluorohexane (FC-
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Data from [9] and [10]
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Table 2 Substrates upon which the techniques have been successfully implemented

Technique Substrates

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Glass, PP, PC,

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Glass, PC, PDMS,

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Layer-by-layer
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Nanoparticle- PP, PC

encapsulation
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Liquid-impregnation PP, Glass

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Table 3 Comparison of static contact angles and tilt angles for water and hexadecane

droplets on the four superoleophobic techniques

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Contact angle (°) / Tilt angle (°)

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Technique DI water Hexadecane

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Glass substrate

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Untreated 22 ± 2 / n/a 12 ± 2 / n/a

Nanoparticle/binder 165 ± / ≤1 156 ± 2 / 2 ± 1

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Layer-by-layer [46] 163 ± 1 / 2 ± 1 157 ± 1 / 4 ± 1
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Polypropylene substrate
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Untreated [14] 96 ± 1 / n/a 35 ± 2 / n/a

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Nanoparticle-encapsulation [14] 172 ± 1 / 1 ± 1 159 ± 1 / 4 ± 1

Liquid-impregnation [55] 115 ± 2 / 2 ± 1 70 ± 2 / 4 ± 2

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Table 4 Comparison of static contact angles and tilt angles for water and hexadecane

droplets on the layer-by-layer composite coatings

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Contact angle (°) / Tilt angle (°)

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Coating DI water Hexadecane

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Superhydrophilic/Superoleophilic ~0 / n/a ~0 / n/a

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Superhydrophobic/Superoleophilic 161 ± 1 / 2 ± 1 ~0 / n/a

Superhydrophobic/Superoleophobic* 163 ± 1 / 2 ± 1 157 ± 1 / 4 ± 1

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Superhydrophilic/Superoleophobic <5 / n/a 157 ± 1 / 4 ± 1
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Figure Captions

Figure 1 Bioinspiration from lotus leaf and pitcher plant for liquid-repellency and low-

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adhesion properties. A lotus leaf (Nelumbo nucifera) is superhydrophobic, repelling water

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droplets with contact angles of ~164°. SEM micrographs (shown at three magnifications)

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consist of a microstructure formed by papillose epidermal cells covered with 3-D

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epicuticular wax tubules, which create nanostructure (adapted from [4]). The pitcher

plant (Nepenthes) has a slippery rim called a peristome that when wet by nectar or
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rainwater creates a thin lubricating film that causes insects to be unable to adhere to the

surface (adapted from [55]).

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Figure 2 Wettability landscape with four combinations of water and oil repellency and
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affinity and possible applications for each quadrant (adapted from [1]).
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Figure 3 Major ingredients in shampoo (Head & Shoulders®, Procter and Gamble) with

their structural formula and role in the product.

Figure 4 Major ingredients in laundry detergent (Tide®, Procter and Gamble) with their

structural formula and role in the product.

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Figure 5 Liquid interacting with various surface geometries. (a) Liquid droplet sitting on

roughness asperities with air pockets trapped in between, known as the Cassie-Baxter

wetting state, (b-d) θflat angles <90° on non–re-entrant and re-entrant geometries, liquid

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does not fully wet structure if θflat + α ≥ 90° thanks to favorable shape of the liquid–vapor

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interface, (e) geometry with re-entrant curvature supporting a θflat angle of 70°, (f)

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geometry with re-entrant curvature supporting various θflat angles of ≤90° (adapted from

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[10]).
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Figure 6 Schematic of popular techniques for creating superoleophobic surfaces through

combining steps of roughness and fluorination. Roughness methods include etching,

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micropatterning, nanoparticles + polymer, and nanoparticle-encapsulation. These

methods can introduce re-entrant geometries where surface features become narrower at
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the base. Fluorination methods include fluoropolymer, fluorosilane/fluorothiol,

fluoroplasma, and fluorosurfactant.

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Figure 7 Schematic of four superoleophobic techniques: (a) nanoparticle/binder (adapted

from [38]), (b) layer-by-layer (adapted from [46]), (c) nanoparticle-encapsulation

(adapted from [14]), and (d) liquid-impregnation (adapted from [55]).

Figure 8 (a) Irradiation using 185 nm and 254 nm (UVO) light. A wavelength of 185 nm

decomposes molecular oxygen into atomic oxygen and also synthesizes ozone. In the

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presence of 254 nm ultraviolet light, ozone decomposes into atomic and molecular

oxygen. (b) Comparison of ultraviolet and ultraviolet-ozone surface activation processes.

In the UV process, 254 nm light breaks up organic molecules at the surface, and these

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excited and/or dissociated molecular sites attempt to return to a chemically stable

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condition by reacting with oxygen molecules. After oxidation, polar groups are formed,

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which leads to a chemically active, hydrophilic surface. In the UVO process, the

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combination of 185 and 254 nm light causes ozone to be continuously synthesized and

decomposed. Due to the irradiation, surface molecules are excited and/or dissociated, and
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therefore, react with atomic oxygen to form desorbing volatile molecules. These volatile

molecules desorb from the surface. The desorbed sites bond with oxygen to form polar
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groups, which leads to a chemically active, hydrophilic surface [38].

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Figure 9 Hexadecane contact angles and tilt angles for the four superoleophobic

techniques compared to untreated glass and polypropylene substrates. Layer-by-layer

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image adapted from [46]; nanoparticle-encapsulation image adapted from [14]; and

liquid-impregnation image adapted from [55].

Figure 10 SEM images of the four superoleophobic techniques. The top-down view

(shown at two magnifications) shows the microstructure. The nanoparticle/binder, layer-

by-layer, and nanoparticle-encapsulation techniques show agglomerates of nanoparticles

that form micron-sized structures. The liquid-impregnation technique shows pores which

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can be filled by a lubricating liquid. The tilt view shows re-entrant geometries for the

nanoparticle/binder, layer-by-layer, and nanoparticle-encapsulation techniques. The

liquid impregnation technique does not require re-entrant geometries in order to repel oils

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and therefore does not have re-entrant geometries. Nanoparticle-encapsulation images

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adapted from [14] and liquid impregnation images adapted from [55].

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Figure 11 Photographs demonstrating repellency of surfactant-containing liquids by

comparing shampoo and laundry detergent droplets deposited on untreated glass and
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nanoparticle/binder surfaces.
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Figure 12 Photographs demonstrating repellency of surfactant-containing liquids by

comparing shampoo and laundry detergent droplets deposited on untreated glass and
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layer-by-layer surfaces.
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Figure 13 Photographs demonstrating repellency of shampoo (a surfactant-containing

liquid) by comparing shampoo droplets deposited on untreated polypropylene and

nanoparticle-encapsulated surfaces (adapted from [14]).

Figure 14 Photographs demonstrating repellency of surfactant-containing liquids by

comparing shampoo and laundry detergent droplets deposited on untreated polypropylene

and liquid-impregnated surfaces (adapted from [55]).

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Figure 15 Wear experiment using ball-on-flat tribometer and AFM. (a) Images after

macrowear experiment with a 3 mm diameter sapphire ball at 10 mN load. (b) Surface

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height maps and sample surface profiles (locations indicated by arrows) before and after

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AFM microwear experiment on layer-by-layer sample using 30 μm diameter borosilicate

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ball at 10 μN load. Other nanoparticle techniques were too rough to image using AFM

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and therefore are not reported. Layer-by-layer image adapted from [46]; nanoparticle-

encapsulation image adapted from [14]; and liquid-impregnation image adapted from
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[55].
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Figure 16 Photographs of untreated glass compared to nanoparticle/binder and layer-by-

layer techniques to show transparency. Layer-by-layer image adapted from [28].

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Figure 17 Optical micrographs of contaminated coatings before and after self-cleaning

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test. Glass samples include untreated, nanoparticle/binder, and layer-by-layer.

Polypropylene samples include untreated and nanoparticle-encapsulation. Dark spots on

coatings indicate silicon carbide particle contaminants. Image analysis suggests >90%

removal of particles on the techniques. Layer-by-layer images adapted from [46].

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Figure 18 Optical micrographs of contaminated surface and oil-impregnated microfiber

cloth before and after anti-smudge test on untreated glass and the nanoparticle/binder

surfaces. Dark spots on coatings and cloth indicate silicon carbide particle contaminants.

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Figure 19 Optical micrographs of contaminated surface and oil-impregnated microfiber

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cloth before and after anti-smudge test on untreated glass and the layer-by-layer surfaces.

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Dark spots on coatings and cloth indicate silicon carbide particle contaminants. Layer-by-

layer images adapted from [46]. MA

Figure 20 Optical micrographs of contaminated surface and oil-impregnated microfiber
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cloth before and after anti-smudge test on untreated polypropylene and the nanoparticle-

encapsulated surfaces. Dark spots on coatings and cloth indicate silicon carbide particle
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contaminants.
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Figure 21 Chemical composition and charge of each layer for the four layer-by-layer

composite coatings. Each layer is deposited separately. The functional layer is deposited

last and provides the desired surface chemistry (adapted from [46]).

Figure 22 Water and hexadecane droplets deposited on the four layer-by-layer composite

coatings to show adaptability of the technique and its flexibility in achieving the four

regimes of the wetting landscape (adapted from [46]).

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Figure 23 Photographs of the four layer-by-layer coatings after exposure to water vapor

to show anti-fogging properties. The hydrophilic coatings maintain transparency due to

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the formation of a thin water film on the surface. The hydrophobic coatings become

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opaque due to the formation of discrete water droplets on the surface (adapted from [46]).

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Figure 24 Photographs of the four layer-by-layer coatings after freezing and deposition of

supercooled water to show anti-icing properties. The water immediately froze upon
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contact with the hydrophilic coatings whereas the droplets were able to roll off the

hydrophobic coatings before freezing (adapted from [46]).

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Figure 25 Photograph of layer-by-layer technique with superhydrophilic/superoleophobic

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functionality on stainless steel mesh acting as an oil–water separator. By adapting the

functional layer, an oil/water mixture can be separated into its constitutive parts. Water
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passes through the mesh while the oil rolls off the top surface. Water and oil dyes used to

enhance contrast [28].

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Highlights

 Oil- and surfactant-repellency, unlike water, are uncommon to nonexistent in

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nature

 This repellency needs specialized surface structures and low surface energy

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materials

 We present common liquids and fabrication techniques for superliquiphobic

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 Surfaces exhibit self-cleaning, anti-smudge, antifouling, and low-adhesion

properties
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 These surfaces can be applied in plastic packaging and biomedical devices

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