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A novel superhydrophilic/superoleophobic nanocomposite

PDMS-NH2/PFONa-SiO2 coated-mesh for the highly efficient
and durable separation of oil and water

Setare Amirpoor, Roozbeh Siavash Moakhar, Abolghasem Dolati

PII: S0257-8972(20)30528-4
DOI: https://doi.org/10.1016/j.surfcoat.2020.125859
Reference: SCT 125859

To appear in: Surface & Coatings Technology

Received date: 14 January 2020

Revised date: 12 April 2020
Accepted date: 27 April 2020

Please cite this article as: S. Amirpoor, R.S. Moakhar and A. Dolati, A novel
superhydrophilic/superoleophobic nanocomposite PDMS-NH2/PFONa-SiO2 coated-
mesh for the highly efficient and durable separation of oil and water, Surface & Coatings
Technology (2020), https://doi.org/10.1016/j.surfcoat.2020.125859

This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
not yet the definitive version of record. This version will undergo additional copyediting,
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version to give early visibility of the article. Please note that, during the production
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that apply to the journal pertain.

© 2020 Published by Elsevier.

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A novel superhydrophilic/superoleophobic nanocomposite PDMS-NH2 /PFONa-SiO2

coated-mesh for the highly efficient and durable separation of oil and water

Setare Amirpoor, Roozbeh Siavash Moakhar, Abolghasem Dolati*

Department of Materials Science and Engineering, Sharif University of Technology, Azadi Ave.,

P.O.Box 11155-9466, Tehran, Iran.

Corresponding Author: dolati@sharif.edu, Tel.: +98 21 66165259, Fax: +98 21 66005717

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ABSTRACT

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A surface to separate oil–water mixtures is a global concern and highly needed particularly in oil industries. The

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present study was conducted to create a novel superhydrophilic/superoleophobic nanocomposite coating on the

stainless-steel mesh for the aim of oil/water separation. Different hydrophilic resins along with PFOA as oleophobic
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agent with 15 flours in its chemical structure and various oxide nanoparticles containing SiO2 and TiO2 at different
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concentrations were studied to achieve superhydrophilic/superoleophobic surface. The fabricated nanocomposites

were fully characterized via field-emission scanning microscopy (FESEM), atomic force microscopy (AFM) and
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Fourier-transform infrared spectroscopy (FTIR). At the optimum concentration of resin and oxide nanoparticles, oil

contact angle (OCA) and water contact angle (WCA) of 144 and 0 were achieved, respectively. The plausible
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mechanism of superhydrophilic/superoleophobic behavior of the coating is mainly associated with the micro-nano
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hierarchical structure of the coating owing to boosted roughness caused by the presence of SiO2 nanoparticles and

their effective embedding into hydrophilic resin PDMS-NH2 and using metallic mesh substrate besides the reduced

surface tension due to the using PFONa, strong bonding of the film to the substrate. Ultimately excellent oil/water

separation efficiency of 96±1% with high stability was attained.

Keywords: superhydrophilic, superoleophobic, stainless steel mesh, silica nanoparticles, separation of oil and water

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1. Introduction

A considerable amount of water-oil waste is produced by petrochemical, metallurgical,

pharmaceutical, food, and other industries. Improper dissipation of such waste leads to serious

environmental pollution problems [1–4]. Also, the extracted oil contains some amounts of water that

is considered an impurity for oil. This impurity should be separated in the purification step.

Therefore, scientists and industrial experts pay considerable attention to the use of new technologies

and materials for efficient and cost-effective separation of water from oil [5–9].

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The traditional technologies used for separation of water from oil such as the use of porous

absorbent materials [10], floatation [11], membranes [12,13], and foam [14], have some
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disadvantages including low separation efficiency, the need for complicated separation equipment,
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high cost process and pollution [15]. Because of the lower surface energy of oil than water, any
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surface wetted with water will also get wet with oil. In this regard, all oleophobic surfaces are

hydrophobic as well [16]. Therefore, effective separation of water from oil requires an engineered
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surface with different wetting properties (i.e., hydrophobic and oleophilic surfaces or alternative
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hydrophilic and oleophobic surfaces) [17]. In superoleophobic/superhydrophilic surfaces oil contact

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angle and water contact angle are comparatively high and low, respectively. Due to the higher

surface tension of water than oil, the contact angle of oil is usually lower than that of water.

Therefore, a superoleophobic surface is superhydrophobic, simultaneously. The CAs of water and oil

can be defined as Eq. 1 and Eq. 2 [18]:

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Eq. 1

Eq. 2

where θo , θw , are the CAs of oil and water, while γo and γw are the surface tensions of oil and water,

respectively. And d and p are the dispersion and polarity force components of the surface tension,

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respectively. Eq. (1) and Eq. (2) imply that a smaller γsd and a larger γsp are vital for a larger θo and

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a smaller θw . Nanoparticles and hydrophilic unit-induced long-chain fluorinated materials are the

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basic components to create superoleophobic/superhydrophilic surfaces. The hydrophilic units
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increase the γsp component, resulting in the attraction for polar water molecules and the fluorine

groups minimize the γsd component, leading to a barrier of permeation of oil molecules. Moreover,
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the long chains lower the barrier of permeation of smaller water molecules [18].
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The ideal condition for the separation of oil from water is simultaneous hydrophilicity and
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oleophobicity, while separating water from oil, concurrent hydrophobicity and oleophilicity should

be taken into account [19,20]. However, the hydrophobic and oleophilic surfaces have some
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limitations: First, due to the higher density water is usually settled below oil and in contact with the

surfaces and thus prevents oil permeation by forming a barrier layer; Second, meshes made of

superhydrophobic and superoleophilic materials are easily contaminated so their holes are filled and

blocked with oil, leading to a significant reduction in the separation efficiency; further it might need

additional equipment, such as pumps to remove the residuals that in turn increase the energy

consumption. Third, the superhydrophobic property can be eliminated by the illumination or

corrosive oil-polluted water, resulting in water permeation [21]. To solve the above-mentioned

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problems, researches proposed nano composite coating with superoleophobic/superhydrophilic

properties instead of superhydrophobic/superoleophilic [22,23]. In addition, anti-fogging films, self-

cleaning surfaces, microfluidic devices and anti-bio adhesion are industrial applications of the

hydrophilic and oleophilic surfaces [24].

For instance, Kota et al [25] mixed 1H, 1H, 2H, and 2H-heptadeca fluorodecyl polyhedral

oligomeric silsesquioxanes (fluorodecyl-POSS) with polyethylene diglycol diacrylate (PEGDA).

Elsewhere, Jin Yang et al.[26] combined chitosan, perfluorooctanoic acid, and SiO2 nanoparticles so

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as to address the problem of water-oil separation. In another effort, Jin Yang et al [27] mixed PDDA,

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perfluorooctanoic acid, and SiO2 nanoparticles in order to solve the same problem. Phillips et al [28].

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used the same PDDA mixture and fluorosurfactant but in a layer-by-layer mode. Sumino et al [29].
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used perfluoropolyether dicarboxylic acid and silica nanoparticles so as to develop coatings with
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superhydrophilic and superoleophilic properties.

Separation efficiency greatly depends on the density, shape, and geometrical specifications of
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surface particles. Thus, reduction of particle size to less than 100 nm will cause a significant increase
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in density of the surface itself and the fluid’s surface energy [30,31]. Thanks to the nanotechnology,
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separation of water from oil could be efficiently performed by using low-energy surfaces in which

water can pass through them. This separation method is successfully performed by using engineered

nanostructured coatings fabricated from hybrid nanoparticles with distinct chemical structure and

composition [30–32]. In this technique water is separated from oil based on the variation of surface

energy and the ultimate separation is done over the accumulation of water particles. In large scale

and using nano based separator tanks, investment costs will be comparable to those of the chemical

ones and up to 20% increase in the cost of mass production is estimated [33]. The current costs of

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these tanks are very low and they do not require daily chemicals consumption. Contrary, the annual

consumption of chemicals in demulsifiers is significantly higher [34].

In the present study, we did a comprehensive study for the aim of fabricating engineered

superhydrophilic/superoleophobic nanocomposite coated-mesh film. Several hydrophilic polymer

resins and nanoparticles with different sizes were used to increase the roughness of the surface and

perfluorooctanoic acid (PFOA) with fifteen fluorine was employed to reduce the surface energy and

ultimately attain superhydrophilic/superoleophobic features. The optimum

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superhydrophilic/superoleophobic coated-mesh film exhibited superb separation efficiency of

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96±1% for oil and water with high durability.

2. Experimental
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2.1. Materials
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In this study, various hydrophilic polymeric resins such as PDMS-NH2 (Poly (dimethylsiloxane), bis
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(3-aminopropyl) terminated, average Mn~2,500, Sigma-Aldrich), PDMS-OH (Poly

(dimethylsiloxane), bis (hydroxyalkyl) terminated, average Mn ~5,600 , Sigma-Aldrich), and

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SILRES BS29 (Wacker) were used to hydrophilize the coating. Dibutyltin dilaurate
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((CH3CH2CH2CH2)2Sn[OCO(CH2)10CH3] 2, Sigma – Aldrich,>>95%) was employed as the hardener.

To attain the suitable surface roughness, we used TiO2 (25 nm, Degussa Aeroxide P25) and SiO2

nanoparticles (fumed silica with average particle sizes of 12 nm, 20 nm, and 100-200 nm,

Aerosil®, Evonik). Perfluorooctanoic acid ((CF3(CF2)6COOH), Sigma-Aldrich) was used for oil

repellency characteristics of the coating. Sodium hydroxide (NaOH, Sigma-Aldrich) was used for

preparing PFONa solution. To avoid cracking during drying and improve amphiphobicity of the

coating, octylamine (OA, CH3(CH2)7NH2, Merck, 99.0%) was used as a surfactant. Acetic acid

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(CH3COOH, Merck, 99.9%) and ammonium hydroxide (NH4OH, Merck, 25%) were utilized in

order to make the solution acidic and basic, respectively. In addition, acetone, ethanol (C2H5OH,

Merck, 99.9%), and distilled water were used for cleaning the substrate. The distilled water was also

used as a solvent. Stainless-steel wire mesh with a different size of holes (200, 300, and 400 µm)

was served as a substrate. The chemical structure of each component of the system is shown in Fig.

1.

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O
F CH3 CH3 CH3
F OH H2N NH2
F O Si O

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F Si O Si O Si
F F n
F F CH3 CH3 CH3
F F

F F
F
F
F PFOA SiO2
-p PDMS-NH2
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O
CH3
C4H9 O
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10 H 3C NH2
Sn
C4H9 O
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CH3 Octylamine
10
O
HDI
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Fig. 1 The chemical structure of components of the system

2.2. Preparation of Oil Repellant and Hydrophilic Solutions

In this study, different solutions were prepared which are listed in Table 1. Typically, in order to

prepare 10 ml of PFONa solution, 0.4 g of PFOA was mixed with 0.04 g of NaOH in the presence of

10 ml of deionized water as a solvent. As a result, an acid-base reaction occurred to yield a totally

uniform solution. Silica powder (4 g/l) and PDMS-NH2 (10 g/l) were mixed in the presence of

deionized water as a solvent and then placed in a sonication apparatus (Sonicator 4000) at the

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frequency of 20 kHz for 15 min, so that the silica nanoparticles have sufficient time to be dispersed

completely (pH 6-7). After the solvent temperature reached 60-80℃, 200 ml/l of the prepared

PFONa was added to the solution dropwise. The mixing continued for 2 h until the product was

completely mixed. Afterward, the surfactant of octylamine (with the aim of obtaining a uniform

coating on the substrate and stability of the solution) and dibutyltin dilaurate (as a hardener for

PDMS-NH2) were added to the solution with a weight percentage of 0.1-0.3 of silica nanoparticles

and PDMS-NH2, respectively. The solution was stirred for 30 min at the ambient temperature. Some

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other hydrophilic resins like PDMS-OH, and SILERS BS 29, and their mixture, TiO2 nanoparticles,

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and a mixture of SiO2/TiO2 nanoparticles have been also used.

2.3. Coating Procedure

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The substrates were degreased in acetone under ultrasonic wave prior to the coating process. The
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pickling was then performed in 20 vol.% sulfuric acid for 20 seconds, followed by additional

ultrasonically degreasing and washing in ethanol and water for another 10 min. Different methods of
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coating including dip coating, brush, sponge, and sonication with a frequency at 10Hz, were applied.
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Then the effect of coating method on the OCA and WCA was investigated and revealed that all

methods demonstrated almost similar results. Nevertheless, we decided to use dip coating as it is a
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cost effective and industrial-friendly method which gave more uniform coating with reproducible

results. To investigate the effect of heat treatment on surface properties, the optimized sample was

heated at different temperatures of 70, 100, 150, and 200℃ in an oven (UNB 400). Scheme 1 shows

the features and performance of the designed superhydrophilic and superoleophobic (PDMS-NH2

/PFONa –SiO2) film.

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Oil/water

Oil

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water

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Scheme 1 Schematic illustration of surface modification of stainless steel mesh with PDMS-

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NH2/PFONa–SiO2 nanocomposite coated-mesh.
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2.4. Characterization
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The static contact angles (OCA and WCA) were measured by olive oil with the surface tension of
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33.00-33.06 mN m-1 [35] and deionized water via sessile drop method and using Data physics

apparatus (Model OCA 15 Plus) from three different points and according to ASTM 7334-08 (2013),
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ASTM 7490-13, and ASTM 5946-09. Then, using a traditional digital camera, the angles were
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analyzed with the “ImageJ” software [36]. The sliding angles of water (WSA) and oil (OSA), were

determined via dropping 10 μL of deionized water and oil droplets on an inclined plane with variable

slopes. The average values of CAs and SAs were calculated by examining five different areas on an

identical sample. It is worth to mention that a good oil-repellent surface is the one with a high CA

and a low SA.

To examine the microstructure and uniform distribution of nanoparticles on the surface, field

emission scanning electron microscopy (FESEM) (Model TESCAN MIRA 3LMU) was used. The

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roughness of the optimized surface was evaluated using a roughness tester apparatus (Model EMD-

1500-311). An atomic force microscope (AFM Model TS 75 TriboScop-NanoScope E) in direct

contact mode was utilized for the purpose of topographic studies.

To study the occurrence of the reaction between the reaction components, Fourier transform infrared

spectroscopy (FTIR) spectroscopy was carried out by FTIR Perkin Elmer apparatus (Model

Spectrum RX I, US) in the range of 400-4000 cm-1. To perform FTIR analysis, at first, solvent was

separated from the obtained nanocomposite using a centrifuge apparatus. The after rinsing, the

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residue was heated at 110℃ for 2 h to completely remove the solvent and obtain the powder.

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Furthermore, the hardness test was carried out according to the standard ASTM D3363-05, with

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pencils of different hardness values ranged from 6B to 6H.
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Eventually, to assess the separation efficiency of the optimal nanocomposite coated-mesh, the

oil/water mixture were used aiming to separate the water from the oil and calculate the separation
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efficiency according to Eq. 3 [21]:

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R (%) = (1-Cp/C0) ×100 Eq. 3

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where Cp and C0 are the water content in the mixture before and after separation (efficiency of water

separation) or the oil content in the mixture before and after separation (efficiency of oil separation),
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respectively. No external load was applied except the one induced by the weight of the water-oil

mixture. For investigating the durability of the nanocomposite coated-mesh, it was used for oil/water

separation for three consecutive times, each time was dried in the oven at 80 ℃ for 1 hour.

3. Results and Discussion

3.1. Fabrication and wettability performance of superhydrophilic and superoleophobic surface

In order to fabricate superoleophobic surface, a coating with superior oil repellency properties and

optimized roughness (micro/nanostructure) is needed [30,37]. This feature can be obtained by using

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an optimized concentration of SiO2 nanoparticles to increase the surface roughness and OCA while

decrease OSA. Thus, at first step we investigated the effect of SiO2 nanoparticle concentration on oil

and water wettability and slip angles with different concentrations of fumed silica (S1-S6, Table 1).

The results showed that by increasing the concentration of nanoparticles, the OCA increases and the

WSA decreases.

Table 1 Sol compositions of for different synthesized coatings at pH 3

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The sol of PDMS-NH2 -PFONa/SiO2

Composition (wt.%) Contact angle (°) Slip angle (°)

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DBTDL hardener
Fumed silica PFONa PDMS-NH2 resin Octyl amine Water Oil Water
Sol ID (g/l) Oil (OCA
(g/l) (ml/l) (g/l) (g/l) (WCA) (OSA) (WSA)

S1 0 200 10
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Effect of Fummed silica

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3

3
0 0 -
No
sliding
No
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S2 2 200 10 0.6 119 0 -
sliding
3 No
S3 4 200 10 1.2 131 0 12
sliding
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3 No
S4 8 200 10 2.4 137 0 10
sliding
3 No
S5 10 200 10 3 144 0 7
sliding
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3 No
S6 12 200 10 3.6 145 0 7
sliding
Effect of PFONA
3 No
S7 10 100 10 3 134 0 12
sliding
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3 No
S8 10 200 10 3 144 0 7
sliding
3 No
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S9 10 400 10 3 131 0 12
sliding
Effect of PDMS-NH2 resin
3 No
S5 10 200 10 3 144 0 7
sliding
6 No
S10 10 200 20 3 137 0 10
sliding
12 No
S11 10 200 40 3 131 0 12
sliding

Increasing the concentration of SiO2 nanoparticles from 8 g/l to 10 g/l efficiently enhanced the OCA

from 137° to 144° and decreased the OSA from 10° to 7°. After adding more SiO 2 nanoparticles

(S6), no significant change occurred in OCA and OSA. Therefore, the solution with a concentration

of 10 g/l (S5) was selected as the optimized solution and the remaining studies continued with this

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concentration. It was also noticed that the oil did not wet the surface at the concentration of 4 g/l of

SiO2 nanoparticles and above. Besides, at the concentration of 2 g/l of SiO2 nanoparticles and below,

the surface clearly became wet by the oil which can be attributed to the inadequate surface

roughness.

We also used the hydrophilic polymeric resin PDMS-NH2 (NH2 is the hydrophilic agent) for the aim

of creating superhydrophilic properties of the surface. From Table 1 it can be seen that all samples

(S1-S6) exhibit zero WCA with no sliding for water droplets, which indicates that we successfully

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fabricated the superhydrophilic surface while preserved the superoleophobic feature.

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After obtaining the optimized concentration of SiO2 nanoparticles (S5), various solutions with

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different concentrations of oleophobic agent (PFONa) were studied (S7-S9, Table 1). It can be seen
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the highest OCA was achieved at the concentration of 200 ml/l PFONa (144), and further increase

in the PFONa concentration did not enhance the oil repellency properties. We hypothesize that at the
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low concentration of PFONa (100 ml/l), the fluorine branches were not sufficiently placed on the
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surface, while at the higher concentration of PFONa (400 ml/l), non-stable nanocomposite was

formed, thus both concentrations led to the less oleophobicity. Nevertheless, at the optimal
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concentration of the oleophobic agent, PFONa reacts with the hydrophilic polymer in a certain
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amount (which will be confirmed by FTIR results in addition to the oil/water repellency performance

of the optimized nanocomposite coating) and forms a stable nanocomposite [21].

In the next step, we studied the effect of hydrophilic polymeric resin (PDMS-NH2) concentration at

the optimized concentrations of SiO2 nanoparticles (10 g/l) and PFONa (200 ml/l) (S5, S10-S11,

Table 1). As it can be expected, increasing the concentration of the hydrophilic resin resulted in a

decrease of OCA and increase of OSA due to the rising of surface energy (The surface incorporates

lower OSA at the concentration of 10 g/l in comparison with the concentration of 20 g/l and 40 g/l).

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Thus, in order to gain superhydrophilicity and superoleophobicity features at the same time, we need

the optimum concentration of the hydrophilic resin, which is 10 g/l in this study.

Therefore, 10 g/l of fumed silica, 200 ml/l of PFONa, and 10 g/l PDMS-NH2 (S5) are the optimized

concentrations for preparing the superoleophobic and superhydrophilic coating. Fig. S1 presents the

OCA and WCA for this film.

The superoleophobic and superhydrophilic nanocomposite coated on a stainless-steel mesh from

optimized solution (S5), demonstrated the hardness of H pencil and strong adhesion strength

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showing the stability of the nanocomposite coating. Noteworthy, without using DBTDL the hardness

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was 6B which clearly depicts the importance of the hardener.

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The effect of heat treatment, type of resin, acidity of the solution and size of the mesh on the surface
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tribology are presented here. First, the coated-mesh produced by the solution S5 was heated at

various temperatures (80, 150, 180, and 200 ℃). As shown in Fig. 2a, an increase in the heat
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treatment temperature does not change the OSA and the OCA which contrary to Yang et al [38].
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results which reported the surface structure was affected by annealing the specimens.
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Fig. 2 (a) The oil contact angles of S5 at different temperatures of heat treatment and (b) The oil contact
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angles of different resins: PDMS-OH (SS1), SILRES BS 29 (SS2) and SILRES BS 29/PDMS-NH2

(SS3). (c) The oil contact angle at pH 3 (S5), pH 7 (SS4) and pH 10 (SS5). (d) The oil contact and oil
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sliding angles of S5 at different mesh size (200, 300, and 400 µm).

Nevertheless, here heat treatment at a temperature of 180 ℃, causes an increase in the hardness to 3H

pencil. So, we did heat treatment mainly to improve the coating adhesion and remove solvent and

other volatile components from the coating. Due to the boiling point of 189℃ for perfluorooctanoic

acid, the heat treatment temperature cannot exceed 180℃ such that when the heat treatment

temperature was set to 200 ℃, the oleophobicity property of the coating was eliminated and the OCA

was drastically decreased to 0°.

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Then, in order to investigate type of the hydrophilic resin and acidity, different sols were prepared

which are listed in Table S1. The CA measurements were repeated for three other solutions

including PDMS-OH (SS1), SILRES BS 29 (SS2) and their mixture (SS3) (Fig. 2b). The results

showed that in all cases, high OCA and low OSA are achieved, with no negative impact on

hydrophilicity mainly due to the presence of hydrophilic agents amine and hydroxide groups in the

structure of resins (SILRES BS29, is a resin with oil repellency and probably hydrophilic agents in

its composition) which reacted with carboxylic group in PFOA.

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Further we evaluated the effect of pH on the stability of OCAs on the coated stainless-steel mesh, by

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preparing various solutions at three different pH values of 3 (SS1), 7 (SS4), and 10 (SS5). The

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variation of OCAs and OSAs versus time at different pH are given in Fig 2c. As it can be observed,
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the samples prepared in acidic solution show the maximum OCA and the minimum OSA for the oil

droplets. It is also seen that the stability of the nanocomposite coating prepared in the acidic
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condition (pH 3) is better than that under the neutral (pH 7) and basic (pH 10) conditions as no
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considerable change occurred in the OCA values, and the oil droplets remained still on the surface

may be deal with the protons involved in the reaction. However, there was a limited reduction in the
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OCA in the basic and neutral conditions during the 10 h duration of the test. Next, the size of
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stainless-steel wire mesh was studied. From Fig. 2d by increasing the mesh size from 200 to 400

µm, the OCA decreased and the OSA increased due to the decrease of roughness.

We also investigated the effect of fumed silica (S5) and different sizes of SiO 2 nanoparticles (SS6,

SS7), and a mixture of nanoparticles (SS8) with 1:1 ratio on the OCA (Table S2). It is observed that

at the same content of the nanoparticles, by decreasing the size, OCA was increased and OSA was

decreased mainly owing to the higher surface roughness. Nevertheless, using the fumed silica

nanoparticles still led to a better performance regarding both OCA and OSA. This result is

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associated with the formation of duplex micro-nano structure in the presence of silica nanoparticles

with finer sizes and higher roughness which eventually demonstrates better oil repellency properties.

Later, to study the effect of nanoparticle’s type on OCAs and OSAs, different solutions were

prepared from fumed silica (S5), TiO2 (SS9) and the mixture of TiO2/SiO2 (SS10) with the same

weight ratio and optimized concentrations of other constituents (Table S2).

According to the obtained results, it is concluded that by implementing TiO2 and TiO2/SiO2 instead

of SiO2, OCA decreases and SA increases. Additionally, the mixture of TiO2/SiO2, showed better oil

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repellency compared with TiO2 nanoparticles alone. These results indicated that TiO2 nanoparticles

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incorporate greater size which formed lower surface roughness (Fig. S2a to Fig. S2d), eventually

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caused higher OSA. The coating prepared from the solutions containing a mixture of TiO2 and
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fumed silica (SS10), had higher surface roughness (Fig. S2e to Fig. S2h), and OCA. Noteworthy, in

case of using only the silica nanoparticles (S5), the contact and sliding angles of the oil droplets were
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superior due to the excessive roughness of the surface.

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3.2. Characterization of superhydrophilic-superoleophobic (PDMS-NH2 /PFONa-SiO2) film

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Chemical properties of the oil-repellent agent (chemical) along with the surface morphology and

roughness (physical) are two key factors in fabricating superoleophobic and oil-repellent coatings.
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The roughened areas on the surface cause entrapment of air bubbles such that the oil droplet will not

be in direct contact with all the surface [39]. Thus, in order to investigate the effect of fumed silica

nanoparticles on the surface morphology and ultimately oil repellency, the FESEM micrographs

were taken from the PDMS-NH2/PFONa–SiO2 nanocomposite coated-mesh surfaces at the

optimized solution (S5) on the stainless-steel wire mesh of 200 μm which are shown at different

magnifications in Fig. 3a to Fig. 3e.

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(a) (b) (c)

500  m 50  m 20  m

(d) (e)

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Fig. 3 (a)-(e) The FESEM micrographs of the coating from the optimized PDMS-NH2/PFONa–
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SiO2 nanocomposite coating (S5) on the stainless-steel wire mesh of 200 μm at different
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magnifications.

The microstructure of the coating surface is covered with voids and clusters of coarse nanoparticles,
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onto which duplex micro/nanometric surface structure air is trapped, avoiding the entrance of oil
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droplets and ultimately lead to superior superoleophobic surface. Furthermore, the hydrophilic and

oil-repellent film is porous with hundreds of spherical nanoparticles. The pores developed between

the particles cause capillary effect thanks to the series of nanometric cavities between the adjacent

nanoparticles and can act as nanocapillaries. These nanocapillaries provide an efficient capillary

effect for the water and contribute to the hydrophilic characteristics.

Moreover, Fig. S3 shows the microstructures of the coated-mesh surfaces at different concentrations

of SiO2. It can be observed that by increasing the concentration of the nanoparticles, greater surfaces

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of the wire mesh are covered with the coating. Further, it is clearly seen that increasing the

nanocomposite content contributed to the complete coating of even the mesh corners and wires

junction area, which usually can be covered difficultly. Moreover, it is seen that the amount of the

nanoparticles accumulated on the surface is increased and the surface is completely covered with

spherical fumed silica particles lead to the enhanced surface roughness.

In order to examine the chemical composition of the nanocomposite coating, EDS analysis was

performed on the surface (Fig. S4). The EDS spectra and elemental mapping results clearly

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demonstrate the presence and homogeneous distribution of silicon, fluorine and sodium over the

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surface of the substrate. The F branches on the surface are responsible to reduce the surface energy

and create excellent oil repellency properties.

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To study the effect of octylamine surfactant on improving oleophobicity and avoiding the film crack

formation, a solution was prepared without the octylamine. The morphology of the coated samples
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without octylamine is shown in Fig. S5. Compared with the presence of octylamine (Fig. 3a), in the
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absence of octylamine, the coating was not formed uniformly with some uncoated areas, caused the

oil droplets stick to them and the oil repellency decreases to a great extent [40] contrary to the
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uniform coating from the optimized solution with the maximum OCA (144) and the minimum OSA
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(7).

To clarify the specific wetting behavior of the modified materials and reactions between the

components, we have depicted FTIR spectra (Fig. 4). As it can be seen, the absorption vibration at

1100 cm−1 is broad and strong that is attributed the overlapping peaks of the Si−O−Si antisymmetric

stretch vibration and C−F absorption. The adsorption vibration at 895 cm−1 is attributed to Si−O

symmetric stretching vibrations [41]. Also, the peak 1208 cm-1 is related to CF2 groups of PFOA

[42]. In addition, the absorption peaks at 1700 and 1560 cm−1 are corresponded to the stretching

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vibration of C=O for the ester carbonyl groups and carboxyl groups, respectively [41,42]. These

spectra demonstrate the successful reaction of fluorinated ester groups onto the Silica nanoparticles

[42]. The combination of SiO2 nanoparticles (high roughness/physical route) and fluorine (low

surface energy/ chemical route) create high oleophobicity. The peaks absorption appeared at 690,

2790, and 2830 cm−1 are related to N−H, −CH3, and −CH2 groups of PDMS-NH2 respectively [42].

There are two peaks with broad band at 3150 and 3440 cm−1 corresponding to the associated −OH

groups in carboxylic acids and free –OH groups potentially generated by the reversible hydrolysis of

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the fluorinated ester groups. Furthermore, the oleophobic material (perflourooctanoic acid) shows

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simul-hydrophilicity [41,42]. There are strong interactions between the carboxyls and the water

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molecules. Furthermore, water passes through the mesh. Oil droplet is unpolar and the interaction is
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weak enough, oil droplets keep their high contact angle and sphere shape on the surface.
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Fig. 4 FTIR spectra of the optimized PDMS-NH2/PFONa–SiO2 nanocomposite coated-mesh

(S5).

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To assess the effect of fumed silica nanoparticles on surface roughness AFM was carried out. Fig. 5

represents the surface topography and AFM micrographs of the optimized PDMS-NH2/PFONa–

SiO2 nanocomposite coated-mesh (S5) with the average surface roughness (Ra) of 45.16 nm.

Furthermore, the micrographs confirm the micro/nanoscale roughness that is the consequence of

packing uniform particles of the coating together tightly. The micro/nano arrangement of the coating

particles is the major reason for the hydrophobic feature according to the Cassie−Baxter state

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[40,43].

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(a)
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(b) (c)
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Fig. 5 The (a) 3D, (b) 2D AFM micrographs and (c) roughness line profile of the optimized

PDMS-NH2/PFONa–SiO2 nanocomposite coated-mesh (S5).

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From Fig. 5, it is clearly observed that the coated surface is completely covered with the fumed

silica nanoparticles, leading to a significant roughness. The fumed silica, making the

micrometric/nanometric structure, provides the required conditions for trapping of the air inside the

rough areas, which enhances the oil repellency properties accordingly.

3.3. Separation of water and oil

Ultimately, oil/water separation efficiency, recyclability of coated mesh, the effect of various

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corrosive aqueous solutions and different oils on separation performances of oil/water mixtures and

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wettability were thoroughly investigated. In order to calculate oil/water separation efficiency, we

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utilized a setup based on a well-established protocol which was also employed by other researchers
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[18,27,44–47]. In order to reduce the error of measurements, slope of the mesh and flow rate of the
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mixture were fixed during the experiment so that the water droplets had enough time to reach and

pass through the mesh before passing through the first chamber. Additionally, we repeated each test
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three times to be confident regards the reported value. The separation efficiency of coated mesh was
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examined according to Eq. 3. The optimized PDMS-NH2/PFONa–SiO2 nanocomposite coated on of

stainless-steel mesh demonstrated highly oil/water separation performance of 96±1% for oil and
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water (Fig. 6a-6b and Movie S1). Moreover, the high separation efficiency of the PDMS-

NH2/PFONa–SiO2 -coated mesh maintained after 15 separation cycles (Fig. 6c). The results

confirmed that the nanocomposite coating can maintain its superhydrophilic and superoleophobic

features for successful long-term stability.

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Fig. 6 (a), (b) The separation of oil from olive oil / water mixture with the ratio of 1:1 (water was
marked with methylene blue) via optimized PDMS-NH2/PFONa–SiO2 nanocomposite coated-
mesh (S5), (c) The recyclability of coated mesh (S5) ,(d) The olive oil/water separation efficiency

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with corrosive aqueous solutions, (e) OCAs and OSAs of various oil droplets on coated-mesh
(S5).

It can be inferred from this separation test that for separating the water from a great amount of the

oil, the utilized coating must incorporate oil repellency and hydrophilic properties because the oil

remains on the top of the liquid mixture due to its smaller density as compared to the water.

Therefore, during the separation test, the oil is placed on the wire mesh and, because of its oil

repellency characteristics, the oil leaves the surface and goes inside the oil beaker. Next, water lies

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under the oil phase and makes the wire mesh wet due to its hydrophilic properties then was poured

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into the water beaker, yielding a superb oil/water separation efficiency mainly due to the: (1) the

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higher roughness and eventually better oleophobicity resulted in the finer size of mesh and formation

of silica; (2) reduction of surface energy and hydrophilic features at the same time by employing the
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optimal values of hydrophilic polymeric resin (PDMS-NH2) and oleophobic fluorine-rich agent
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(PFONa) in the nanocomposite; (3) formation of hierarchical micro-nanometer scale roughness

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structures on the coating surface. Consequently, the nanocomposite coated mesh exhibits high water

affinity (superhydrophilicity) and low adhesion properties for oil (superoleophobicity), which could
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efficiently separate oil/water mixtures with great industrial potentials. Additionally, we investigated
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the oil and water separation efficiency of the PDMS-NH2/PFONa–SiO2 nanocomposite coated-mesh

using various corrosive aqueous solutions. These mixtures including hydrochloric acid (HCl 1 mol

/lit), sodium hydroxide (NaOH 1mol/ lit) and a mixture of oil/water (water pH 7, without any

additives). As shown in Fig. 6d, these corrosive oil/water mixtures can be separated using the

PDMS-NH2/PFONa–SiO2 nanocomposite coated-mesh (S5) with oil/water separation efficiency of

96±1%.

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Further we studied the effect of different oils on wettability. Droplets of various oils, including

octane (surface tension≈21.14 mN m−1), hexadecane (surface tension ≈27.5 mN

m−1),dichloroethane ( ≈31.86 mN m−1), sunflower oil ( ≈32.9 mN m−1), and olive oil ( ≈33.06

mN m−1), castrol oil ( ≈39 mN m−1), exhibit CAs greater than 140and low slide angles (≈7) on

the coated stainless steel mesh, indicating a good oil-repellent properties (Fig. 6e).

3.4. Coating durability

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The stability of the optimized PDMS-NH2/PFONa–SiO2 nanocomposite coated-mesh (S5) was

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investigated by evaluation of contact angles of water and oil during 7 days of immersion in water. As

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shown in Fig. 7, the coating sustained the oleophobicity after 7 days with the slight change in the

OCA from 144º to 137º, while SCA was constant at 7º. Additionally, the coating was still
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completely hydrophile after 7 days. This superb durability is mainly due to the proper bonding
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between carboxylic group of PFONa and the amine group of resin, as well as strong adhesion
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between the resin of coating and the stainless-steel coated mesh substrate.
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Fig. 7 The variation of the oil contact and oil sliding angles with immersion time.

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Conclusion

In the present study, a superhydrophilic-superoleophobic coating was developed by means of a facile

and cost-effective sol-gel method with the purpose of efficient oil/water separation. We fully

investigated and optimized different crucial factors including types and amounts of nanoparticle,

fluorinated hydro/olephobic agent, hydrophilic resin, heat treatment temperature, acidity of

preparing solution and the mesh size of coating substrate. To achieve the enhanced surface

roughness and superoleophobicity, the fumed silica nanoparticles accompanied by the PFONa with

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fifteen flours in its structure, were applied. Hydrophilic polymeric resin PDMS-NH2 was used to

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make the coating hydrophile and more adhesive. Further, we used the DBTDL as a hardener to

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increase adhesion and octylamine surfactant to create a uniform coating on the substrate and improve
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superoleophobicity. At the optimal conditions we successfully produced mechanical durable

superhydrophilic/superoleophobic nanocomposite coating with the OCA and WCA of 144° and 0°,
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respectively. Ultimately, the optimized nanocomposite coating demonstrated excellent oil/water

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separation efficiency of 96±1% for oil and water. Moreover, the high separation efficiency of the

PDMS-NH2/PFONa–SiO2 -coated mesh can be maintained after 15 separation cycles. This research
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will certainly pave the way towards using highly efficient and affordable nanostructured coating for
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the aim of precious oil/water separation in many industries.

References and notes

Supplementary information and the video of oil/water separation are available.

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Credit authorship statement

Manuscript title:
A novel superhydrophilic/superoleophobic nanocomposite PDMS-NH2 /PFONa-SiO2

coated-mesh for the highly efficient and durable separation of oil and water

All persons who meet authorship criteria are listed as authors, and all authors certify that they
have participated sufficiently in the work to take public responsibility for the content, including

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participation in the concept, design, analysis, writing, or revision of the manuscript.

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Furthermore, each author certifies that this material or similar material has not been and will not
be submitted to or published in any other publication before its appearance in the Surface &
Coatings Technology.
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Authorship contributions
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1-Setare Amirpoor: Conceptualization, Software, Validation, Formal analysis, Investigation,

Writing- Original Draft preparation, Visualization, Writing - Review & Editing.
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2-Roozbeh Siavash Moakhar: Software, Formal analysis, Writing- Original draft preparation,
Writing -Review & Editing, Visualization.
3-Abolghasem Dolati: Conceptualization, Validation, Resources, Writing - Review & Editing,
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Supervision, Funding acquisition.

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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Research Highlights

 A novel superhydrophilic-superoleophobic optimized PDMS-NH2/PFONa–SiO2

nanocomposite stainless-steel coated-mesh nanocomposite was successfully fabricated.

 Oil and water contact angles of the coated-mesh were 144° and 0°, respectively.

 The nanocomposite coated-mesh demonstrated an excellent oil/water separation efficiency of

96±1%.

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The nanocomposite coated-mesh had a superb recyclability, mechanical durability and long-term
stability.

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Figure 1
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