European Polymer Journal 73 (2015) 374–379

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Stainless steel mesh coated with silica for oil–water separation

Beibei Li, Xiaoyan Liu ⇑,1, Xinying Zhang ⇑,1, Wenbo Chai
College of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, Shanghai 200444, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Stainless steel mesh with its high compressive strength, anti-chemical erosion and not
Received 26 June 2015 readily stained with water properties has been used in the application of oil–water
Received in revised form 25 October 2015 separation. This study describes a facile method for fabricating both highly hydrophobic
Accepted 26 October 2015
and superoleophilic meshes by coating silica particles. After the modification of silica
Available online 27 October 2015
particles, the stainless steel mesh became more hydrophobic and oleophilic. The water
contact angle on the modified mesh was up to 135.3°, while the oil droplets could
Keywords:
penetrate the mesh rapidly. The modified meshes could separate oil from water effectively
Stainless steel mesh
Silica particle
without depending on any extra power or chemical agent. It could be a good potential
Oil–water separation candidate in the employment of oil–water separation.
Highly hydrophobic Ó 2015 Published by Elsevier Ltd.
Superoleophilic

1. Introduction

As is well known, a large amount of oily waste-water is being produced everyday due to the industrial processing as well
as domestic water, such as metal finishing, chemical fuel and restaurant leftovers [1–3]. Apparently, the bad influence of this
kind of waste-water for people and environment is long term and lethal [4,5], which can be evidenced by the consequences
of the oil spill accidents that occurred in recent years. Needless to say, the oily waste-water must be appropriately handled
owing to environmental and health requirements.
Till now, kinds of technologies, such as gravity separation [6], coagulation [7], air flotation [8] and oil absorbents [9,10]
have been applied to separate oil–water mixtures. Among them, some of the materials have been developed for oil–water
separation. For example, due to the flexibility, large surface area and pore volume, as well as commercial availability, porous
materials such as sponges [11,12], graphene foam [13], cotton fabrics [14] and copper meshes [15–19] have been investi-
gated to separate oily water. However, these materials have their limitations in recyclability, firmness and large scale
production, which have reduced their practical applications in oil–water separation.
In this work reported herein, we chose stainless steel mesh as the substrate which is anti-chemical erosion [20,21],
anti-hot aging, firm and easy to obtain. In general, superhydrophobic surface can be achieved by combining proper surface
roughness with hydrophobic materials. Therefore, stainless steel mesh with proper pore size was modified by silica particles
using dip-coating method. The water contact angle about this modified mesh (size of 50 lm) was up to 135.3°, and the
hydrophobicity of modified mesh increased a lot. The oil droplets could penetrate the mesh immediately. What’s more,
the mesh is cheap, facile and fast to process, which can be employed effectively for the separation of oil and water.

⇑ Corresponding authors at: College of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, Shanghai 200444, PR China
(X. Liu, X. Zhang).
E-mail addresses: libeibei2017@126.com (B. Li), lxy999@shu.edu.cn (X. Liu), zhangxinying008@163.com (X. Zhang), 526203314@qq.com (W. Chai).
1
Equal contributors.

http://dx.doi.org/10.1016/j.eurpolymj.2015.10.031
0014-3057/Ó 2015 Published by Elsevier Ltd.
 B. Li et al. / European Polymer Journal 73 (2015) 374–379 375

2. Experimental

2.1. Materials

Stainless steel meshes (180, 150, 75 and 50 lm) were obtained from Shanghai Hongxiang Metal Mesh Co., Ltd. Ethanol
(95%), ammonia (28%), acetone, tetraethoxysilane (TEOS, 98%), tetrahydrofuran (THF) and polystyrene (PS) were all pure
analytically and purchased from Sinopharm Chemical Reagent Company, Ltd. (Shanghai, China). Methyltrichlorosilane
(MTS) used for surface hydrophobic modification was purchased from Aladdin Industrial Co., Ltd. (Shanghai, China). All of
the chemicals were used as received without further purification. Diesel (density at 20 °C = 0.8170 g/cm3, viscos-
ity = 6.51 mm2/s) was obtained from Minghe petrol station of Sinopec in Baoshan district (Shanghai, China). Pumping oil
(density at 20 °C = 0.7881 g/cm3, viscosity = 47–57 mm2/s) was obtained from Shanghai Hasitai lubricating oil Company,
Ltd. (Shanghai, China). Soybean oil (density at 20 °C = 0.9275 g/cm3, viscosity = 8.5 mm2/s) was purchased from Wal-Mart
supermarket (Shanghai, China).

2.2. Fabrication of silica particles

With the condition of magnetic stirring, TEOS (5 ml) as well as NH4OH (5 ml, as the catalyst) was added into the absolute
ethanol (50 ml) at ambient temperature [22]. Keep the stirring for one hour. Later, the mixture solution was stalled and aged
at room temperature for 12 h. Then MTS reagent (0.3 ml) was mixed into this solution via 12 h of magnetic stirring. Finally,
the modified silica particles were collected and purified by repeated centrifugation for three times in absolute ethanol, and
then dried in a vacuum oven at 60 °C for 12 h.

2.3. Preparation of highly hydrophobic stainless steel

First of all, different sizes of stainless steel meshes were cut into square shape (5 cm both in width and in length). Then
they were cleaned with acetone and distilled water for 30 min successively by using an ultrasonic cleaner. After that, they
were dried in an oven at 60 °C for several minutes to remove the moisture completely. In the typical process, PS (0.1 g) was
completely dissolved in THF (5 ml), and soon afterwards, the as-prepared modified silica particles (0.1 g) were ultrasonically
dispersed in THF solution at ambient temperature. Followed the stainless steel meshes were dip-coated by the mixture for
several minutes, and then dried at 75 °C for about 2 h. Finally, the highly hydrophobic stainless steel meshes were obtained
by this one-step dip-coating procedure.

2.4. Oil–water separation experiment

The prepared stainless steel meshes were fixed between two glass tubes. The oil–water mixture (about 100 ml of diesel
oil and 100 ml of water were mixed through a shake process) was poured into the upper glass tube. The photos were
recorded on a camera (Nikon, D7100).

2.5. Instrumentation and characterization

Water contact angles (WCAs) were measured with 8 lL droplets of deionized water using a JC 2000D5 (provided by
Shanghai Zhongchen Digital Technology Apparatus Company, Ltd.) apparatus at ambient temperature. The final contact
angle values were attained by averaging at least three results at different positions on the same surface. The surface
morphology of different meshes of stainless steel before and after modification was observed with the use of scanning
electron microscopy (SEM, HITACHI SU-1500, HITACHI Company, Ltd., Japan). Energy dispersive X-ray spectrometer (EDS)
analysis was also carried out on the same machine to determine the chemical composition of the modified stainless steel
meshes. X-ray photoelectron spectroscopy (XPS) data was obtained by using an electron spectrometer from Thermofisher
Scientific Company, Ltd., China.

3. Results and discussion

3.1. Fabrication process of silica particles

According to the well-known Stober method [23,24], the silica particles were prepared by a typical sol–gel process, which
included the hydrolysis of TEOS and the condensation of hydrolyzed silica particles [22]. What’s more, the reaction time and
the concentration of NH4OH were all strictly controlled based on the Stober method. The fabrication process of silica
particles is shown in Fig. 1. When the silica particles were synthesized, they were modified by the MTS. The modified silica
particles were then ultrasonic dispersed into the PS and THF solutions. Afterwards, cleaned stainless steel meshes with dif-
ferent sizes were dip-coated with the above mixed solution for several minutes. The highly hydrophobic and superoleophilic
oil–water separation membranes were obtained.
376 B. Li et al. / European Polymer Journal 73 (2015) 374–379

Fig. 1. Illustration of the preparation procedure of the modified stainless steel meshes.

3.2. Characterization of SiO2 modified stainless steel meshes

As is well known, surface roughness is an indispensable factor in determining the superhydrophobicity of the surface. The
hydrophobicity of the surface can be increased by increasing the surface roughness. The morphology of different sizes of
stainless steel meshes was observed though the scanning electron microscopy (SEM), which is displayed in Fig. 2. From
the images, we can see that the surfaces of original stainless steel meshes (Fig. 2(a), (c), (e), (g)) with different sizes (180,
150, 75 and 50 lm, separately) are all purely smooth. However, after treatment with silica particles, the stainless steel
meshes are all becoming rough, as is shown in Fig. 2(b), (d), (f) and (h). This phenomenon proves the loading of silica
particles. In addition, with the pore size of the mesh decreasing, the amount of the silica particles loaded onto the mesh
is increasing. The loading capacities of silica particles on the meshes with sizes of 180, 150, 75 and 50 lm were 0.04,
0.06, 0.10 and 0.13 g respectively. This result explains that stainless steel meshes with small sizes of are much easier and
more firm for the loading of silica particles. Meanwhile, the energy dispersive X-ray spectrometer (EDS) analysis was also
carried out on the same machine, which was used to determine the chemical composition of the modified stainless steel
meshes. The spectrum of EDS analysis is shown in the supplementary material section (supplementary Fig. 1). The Si element
appears in the analysis, which further proves the loading of silica particles on the stainless steel meshes. Also, we can see
clearly from the figure that the weight percentage of Si element increases with the pore sizes of the meshes decreasing,
which is agreed with the SEM images.
To characterize the hydrophobicity of the modified stainless steel meshes, the static water contact angles were investi-
gated. The different sizes of original and modified (coated with SiO2) stainless steel meshes were all tested with water
droplets (8 lL) for at least three times of each test. The average water contact angles of the meshes are shown in Fig. 3.
The coating of the silica particles increased the water contact angles for all the stainless steel meshes after modification.
The original stainless steel meshes with pore dimensions 180, 150, 75 and 50 lm have static water contact angles of
86.8°, 94.7°, 99.9° and 100.1° respectively (Fig. 3(a), (c), (e), (g)). The modified stainless steel meshes (Fig. 3(b), (d), (f),
(h)) all have higher water contact angles than their corresponding original ones, with average water contact angles of
100.6°, 117.9°, 123.2° and 135.3° respectively. It can be observed obviously that the water contact angles increase more with
the pore sizes of the meshes decreased, and the maximum water contact angle is improved up to 35.2°. This phenomenon is
consistent with the SEM and EDS characterizations. What’s more, the water contact angle of the as-prepared silica particle is
150.5° which is superhydrophobic (>150°). The property also contributes to the overall hydrophobicity of the meshes.
Therefore, the roughness of the microstructure of the meshes with silica coating as well as the superhydrophobicity of silica
particles induces the increase of the water contact angles.
The largest water contact angle is shown on the 50 lm mesh (135.3°, Fig. 3(h)) which had the largest original water
contact angle. The reason for this is that the ideal mixture of the surface roughness from the mesh and the introduction
of air beneath the droplets contribute it [23], while the mesh is still able to support the water droplet on the surface and
prevent it from sinking down into the pores of the mesh. This suggests that the larger pore sizes with low water contact
angles cannot support the water droplet well enough, and the water droplet could sink into the pores resulting from a lower
loading of silica particles as well as the inferior structure of themselves. Therefore, we chose the modified stainless steel
mesh with the pore size of 50 lm to do the following characterizations.
To prove the hypothesis and the hydrophobicity as well as the oleophilicity of SiO2 coated meshes, X-ray photoelectron
spectroscopy (XPS) was further performed to probe the local surface composition. The survey spectra are presented in Fig. 4.
From the figure, we can see that the presence of Si element with binding energies at about 101 eV, which suggesting the
 B. Li et al. / European Polymer Journal 73 (2015) 374–379 377

Fig. 2. SEM images of different sizes of original ((a), (c), (e), (h)) and modified ((b), (d), (f), (h)) stainless steel meshes.

Fig. 3. Water contact angle of different sizes of original ((a), (c), (e), (g)) and modified ((b), (d), (f), (h)) stainless steel meshes.

Fig. 4. (a) XPS spectra of stainless steel mesh; (b) core-level of Si2p; (c) core-level of C1s.

coating of silica particles on the stainless steel mesh. Moreover, the intensity of C, O elements of the modified mesh is higher
than that of the original mesh. The C1s spectrum reveals the presence of three components of carbon, such as C@O (282.9 eV)
and C@C (284.6 eV), which are all hydrophobic groups. The results along with those from XPS data further confirm the
existence of SiO2 on the stainless steel mesh.
Fig. 5 displays the hydrophobicity and oleophilicity of the original (Fig. 5(a), (c)) and modified (Fig. 5(b), (d)) stainless
steel meshes, in which the water droplets were dyed with water blue and the oil droplets were dyed with Sudan I (red).
Obviously from the pictures, the shape of the water droplets on the modified stainless steel meshes is like a ball (Fig. 5
(b), (d)), while the water droplets on the original ones (Fig. 5(a), (c)) are flat. This is caused by the coating of silica particles,
which increases the roughness of the surface and then increases the hydrophobicity of the mesh. The inset (Fig. 5(e)) is the
378 B. Li et al. / European Polymer Journal 73 (2015) 374–379

Fig. 5. Photographs of water (dyed blue) and diesel oil (dyed red) dropped onto the original ((a), (c)) and modified ((b), (d)) stainless steel meshes, (e) the
top-view of (b). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 6. Studies of the silica modified mesh for oil–water separation.

top-view of Fig. 5(b), which is more intuitive to see the shape of the water droplets. After the oil droplets were dipped onto
the meshes, they penetrated the meshes rapidly. In order to evaluate the influence of the silica coating, we also measured the
oil contact angle of the original and modified meshes. The oil contact angles of original meshes with sizes of 180, 150, 75 and
50 lm were 40.6°, 38.8°, 16.9° and 0°, respectively. After modification with silica particles, the oil contact angles changed
into 0° for all sizes of meshes. This phenomenon apparently indicates that the coating of the SiO2 particles has increased
the meshes’ superoleophilicity. In addition, the result proves the good selectivity for oil over water of the modified mesh.
To further demonstrate the selectivity and the separation capabilities of the as-prepared meshes, a series of studies were
investigated, which are shown in Fig. 6. As presented in Fig. 6(a), the modified mesh is fixed between the glass funnel and
conical flask. About 200 ml oil–water mixture, with oil dyed red using Sudan I and water dyed blue using water blue, was
poured onto the sample surface in the device (Fig. 6(b)). Oil permeated through the mesh and dropped into the conical flask
quickly, which is because of the superoleophilicity of the modified mesh. In the meantime, water was repelled and stayed on
the mesh due to the highly hydrophobicity of the mesh, which can be seen in Fig. 6(c). No colored water is observed in the
collected oil in conical flask, which indicates a very high separation efficiency of the mesh. Additionally, there is no extra
force on the separation process but the gravity of the solution itself, which demonstrates the simplification of the separation
of oil–water mixture.

4. Conclusion

On the whole, we have successfully fabricated a highly hydrophobic and superoleophilic oil–water separation membrane
using stainless steel mesh as the substrate. The maximum water contact angle of the modified stainless steel mesh coated
 B. Li et al. / European Polymer Journal 73 (2015) 374–379 379

with silica particles has increased 35.2°. While, oil droplets can be absorbed instantly by the modified meshes, for the silica
coating has improved the oleophilicity of the meshes. The modified meshes can separate oil–water mixture within a few
seconds without losing its highly hydrophobic and superoleophilic properties. We believe that this kind of mesh is a
promising candidate for the application of oil–water separation.

Acknowledgements

The work was funded by the National Natural Science Foundation of China (No. 41373097), China Postdoctoral Science
Foundation funded project (No. 2013M541506), Program for Innovative Research Team in University (No. IRT13078). The
SEM and XPS experiments were conducted under the approval of Test Center of Analytical Instrument, Shanghai University.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.eur-
polymj.2015.10.031.

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