Applied Surface Science 514 (2020) 145838

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Applied Surface Science

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

Full Length Article

A green, maskless, and universal preparation method for patterned surfaces T

on various metal substrates
⁎
Xin Liua,b, , Haiyang Shena, Jiyu Liua, Jichao Zhanga, Yang Chena, Zhongtao Zhanga, Fan Zhanga,
Naiqiao Guana, Danyang Zhaoa,b, Zhuji Jina
a
Key Laboratory for Precision and Non-traditional Machining Technology of the Ministry of Education, Dalian University of Technology, Dalian 116024, China
b
Collaborative Innovation Center of Major Machine Manufacturing in Liaoning, Dalian University of Technology, Dalian 116024, China

A R T I C LE I N FO A B S T R A C T

Keywords: Superhydrophobic surfaces with hydrophilic patterns are widely used in liquid transport, water collection, and
Laser processing cell screening. However, the preparation process of these patterned surfaces tends to be time-consuming and
Fog collection complicated. Here, we apply a simple, efficient and versatile laser processing method. Superhydrophobic sub-
Anisotropic adhesion strates are firstly constructed by laser treatment and fluoroalkylsilane (FAS) solution; then superhydrophilic
Liquid transport
patterns such as dot-shaped or linear grooves are processed by secondary laser treatment. The dot-shaped
grooves have strong adhesive force to droplets, and the linear grooves show obvious anisotropic adhesion be-
havior. On the basis of these features, applications like liquid transport, droplets grabbing and mixing, and fog
collection are successfully achieved. The proposed laser processing method is applicable for various metal
substrates including aluminum, copper, steel and titanium, and is expected to have promising application
prospects in lab-on-a-chip system and chemical analysis domains.

1. Introduction water droplets tend to move along a specific direction on rice leaves
[34,35] and butterfly wings can make the water droplets roll along the
Dust and dirt on lotus leaves [1] can be easily taken away by dew surface in a fixed direction [36]. The anisotropic rolling characteristic
and rain, thus keeping the surface clean. Inspired by this phenomenon, of these surfaces may have promising application prospects in various
scientists have developed superhydrophobic surfaces that are repulsive fields like water collection and liquid transport. To date, many methods
to water. The contact angles of water droplets on the superhydrophobic have been developed to produce extreme wettability patterns on su-
surfaces are greater than 150° [2,3] and water droplets can roll off in a perhydrophobic surfaces, such as ultraviolet light irradiation, ink pat-
spherical shape on these surfaces, so that these surfaces can achieve terning, photo etching and coating, and plasma modification. Zheng
self-cleaning [4,5]. In addition, superhydrophobic surfaces play an et al. [37] obtained wettability patterns on superhydrophobic titanium
important role in antifouling [6,7], antisepsis [8,9], water collection dioxide surfaces by selectively irradiating ultraviolet rays. Zhang et al.
[10–12], oil-water separation [13–15], and chip labs [16], which are [38] produced superhydrophilic micropatterns on superhydrophobic
one of the hot spots of functional materials research. So far, construc- surfaces based on inkjet printing techniques. Zhu et al. [39] prepared
tion of micro/nano structures and modification of low surface energy surfaces with different wettability on silicon wafers by photo-
materials are main steps for preparing biomimetic superhydrophobic lithography and studied the effect of microstructures on two-dimen-
surfaces, such as physical and chemical deposition methods [17,18], sional anisotropic properties. Li et al. [40] reported a new method for
etching methods [19–22], sol-gel methods [23–27], and electrospinning making microfluidic patterns on paper surfaces using plasma treatment
methods [28–30]. Tombesi et al. [31] prepared a transparent silica in combination with masks. The aforementioned methods can construct
coating with superhydrophobicity and excellent stability by aerosol- wettability patterns on superhydrophobic surfaces, but these methods
bound chemical vapor deposition on a glass substrate. Phuong et al. are time-consuming, and are only applicable for one or two metal
[32] used alkali and plasma etching methods to produce super- materials. Therefore, it is of great significance to develop a simple and
hydrophobic cotton fabric with high durability and high contact angle. versatile method that can be used for various materials.
While the otters can move freely on the water surface [33], the As a commonly used physical processing method, laser processing is

⁎
Corresponding author.
E-mail address: [email protected] (X. Liu), [email protected] (N. Guan).

https://doi.org/10.1016/j.apsusc.2020.145838
Received 14 January 2020; Received in revised form 9 February 2020; Accepted 18 February 2020
Available online 19 February 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
X. Liu, et al. Applied Surface Science 514 (2020) 145838

a simple, high-efficient and environmentally-friendly treatment modification process was performed in a petri dish at room temperature
method. Additionally, laser processing [41–45] is a versatile method for and atmospheric pressure, and then metal surfaces were dried at 80 °C.
various metal substrates regardless of material properties. Kostal et al. Then, the surfaces were secondary etched by the laser machine with
[46] prepared superhydrophilic surface on a pyrex wafer using femto- specific control programs to form desired patterns. Dot-shaped grooves
second laser. Wang et al. [47] used nanosecond laser to prepare na- with diameters of 20 μm, 40 μm, 80 μm, 150 μm, 300 μm, and 450 μm
nostructured surfaces and selected appropriate silane reagents to were prepared, and the laser parameters were controlled to ensure that
achieve the desired surface wetting behavior. Jagdheesh et al. [48] the grooves with different diameters were with same depth. Similarly,
fabricated superhydrophobic aluminum surfaces by laser direct writing linear grooves with line widths of 20 μm, 40 μm, 80 μm, 150 μm,
and studied corrosion resistance using polarization and impedance 300 μm, and 450 μm were also constructed, and the grooves depths
spectroscopy. were controlled to be same. The laser parameters of aluminum included
These researches indicate that the laser processing technique can a frequency of 20 kHz, an etching speed of 300 mm/s and a power of
effectively construct micro/nanostructures on different metal surfaces, 6 W. The laser parameters of copper included a frequency of 20 kHz, an
even on non-metallic surfaces. Indeed, since material removal me- etching speed of 200 mm/s and a power of 9 W. The laser parameters of
chanism of laser processing is mainly physical etching, it is promising to steel included a frequency of 20 kHz, an etching speed of 500 mm/s and
employ the technique to firstly construct superhydrophobic substrates a power of 9 W. The laser parameters of titanium included a frequency
and then prepare superhydrophilic patterns. However, construction of of 20 kHz, an etching speed of 400 mm/s and a power of 1.5 W. In
wettability patterns by twice laser processing has been rarely reported. addition, the fixed laser parameters included a pulse width of 100 ns, a
In this paper, we prepared wettability patterns on aluminum, focal diameter of 10 μm (focal length f: 19.45 cm), an optical wave-
copper, steel and titanium substrates by twice laser processing. Firstly, length of 1064 ± 5 nm and a single pulse energy of 1 mJ. Notably, the
superhydrophobic substrates were prepared by laser etching and above laser parameters were same for the first and secondary laser
modification of low surface energy. Then superhydrophilic patterns like processing steps.
dot-shaped and linear grooves were directly constructed on the super-
hydrophobic substrates by secondary laser processing. Finally, appli- 2.3. Characterization
cations like liquid transport, droplets grabbing and mixing, and fog
collection were achieved on the prepared wettability patterns. The Contact angles were measured by an optical angle meter (SL200KS,
proposed laser processing method is high-efficient and versatile, and KINO, USA), sliding angles were measured by a precision rotator. Five
has promising application prospects in various fields. different contact angles and sliding angles were measured on a same
position, and their average values were used for analysis. Surface
2. Experimental part morphology was observed by a scanning electron microscope (SEM). A
camera was used to record anisotropic sliding of droplets on the linear
2.1. Materials grooves, droplets transport, and grabbing behavior. Finally, fog col-
lection experiment was conducted on the prepared patterns, and a high-
Fiber laser marking machine (SK-CX30) was purchased from precision balance was used to measure mass of the collected liquid.
Shanghai Sanke Laser Technology Co. Ltd. (China). 6061 aluminum,
steel, titanium and copper were purchased from Beijing Cui Platinum 3. Results and discussion
Non-Ferrous Metal Technology Development Center Co. Ltd. (China).
Fluoroalkylsilane (FAS) solution was purchased from Degussa Co. Ltd. 3.1. Morphology
(Germany). All chemicals were analytically pure and used as received.
Fig. 2 shows SEM images of aluminum surfaces with dot-shaped and
2.2. Preparation and patterning of superhydrophobic surface linear grooves. The surfaces obtained by first laser treatment and
modification of low surface energy had microstructures with pores
Fig. 1 shows the treatment process of metal surfaces. The surfaces [Fig. 2c1, c2, f1, f2]. The rough structures and modification of low
were firstly etched by a laser machine, and then cleaned by deionized surface energy resulted in the superhydrophobicity. After secondary
water. After drying at 80 °C, the surfaces were modified by 1 wt% laser treatment, the microstructures became looser, but there were still
fluoroalkylsilane (FAS) solution for low surface energy treatment. The rough pore-like structures on the treated surface [Fig. 2a1, a2, d1, d2].

Fig. 1. Treatment process of Al plate and SEM images of untreated Al surface (a), first etched Al surface (b), superhydrophobic Al surface (c), and secondary etched Al
surface (d).

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X. Liu, et al. Applied Surface Science 514 (2020) 145838

Fig. 2. SEM images of Superhydrophilic region (a1), (a2), (d1), (d2); the boundary of the groove area (b1), (b2), (e1), (e2) and Superhydrophobic region (c1), (c2),
(f1), (f2).

Additionally, the other three metals had similar structural properties to the wettability transition from superhydrophobicity to super-
(see Supplementary Material Figs. S1, S2, S3, S4). Thus, the change in hydrophilicity.
wettability of metal surfaces resulted from the variation of surface Fig. 3b is the fitting result for the high resolution C 1s peaks of the
chemical compositions. superhydrophobic surface and the laser secondary etched surface. In
As shown in Fig. 3a, the XPS spectra detected that the super- Fig. 3(b1), the XPS spectra of C 1s were deconvoluted into several
hydrophobic surface contained 28.2% fluorine (F) element and 21.7% components [49]. The peaks at 293.4 ± 0.2 eV, 291.6 ± 0.2 eV,
oxygen (O) element; after secondary laser processing, F disappeared, 290.3 ± 0.1 eV and 286.6 ± 0.1 eV were attributed to the eCF3,
while the content of O element increased to 56.2%. In addition, the eCF2, CF2eCH2 and CF2eCH2 groups, respectively. The peaks at
content of C element of the laser secondary etched surface decreased 284.6 ± 0.1 eV, 286 ± 0.15 eV and 288.3 ± 0.2 eV were attributed
from 21.72% to 15.39%. Therefore, the decrease of the contents of F to the CeH, CeO and C]O groups, respectively. On the other hand, the
and C element and the increase of the content of O element contributed XPS spectra of Fig. 3(b2) showed that the laser secondary etched

Fig. 3. (a) XPS spectra of superhydrophobic surface and secondary etched surface; (b) peak-fitted C 1s XPS spectra of the aluminum surface: (b1) superhydrophobic
surface, (b2) secondary etched surface.

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X. Liu, et al. Applied Surface Science 514 (2020) 145838

Table 1 superhydrophobic substrate on the untreated surface. The dot-shaped

The relative concentrations (%) of the fitted peaks for C 1s of the samples. grooves thus had high adhesion.
Moieties Superhydrophobic surface Secondary etched surface Additionally, it could be found from Fig. 4, as the droplet volumes
increased, the contact angles on dot-shaped grooves with same dia-
CeC/CeH/CeSi 37.4 58.4 meter changed slightly. For example, on the dot-shaped grooves with a
CeO 9.1 14.7
diameter of 150 μm, the contact angle of 5 μL droplets was 151.3°, and
C]O 4.4 27
eCF3 8.6 0
the contact angle of 15 μL droplets was just 153.3°, with little change.
eCF2 25.3 0 By contrast, as the droplet volumes increased, the sliding angles on the
CF2eCH2 9.4 0 dot-shaped grooves with same diameter changed significantly. For in-
CF2eCH2 5.8 0 stance, on the dot-shaped grooves with a diameter of 150 μm, the
sliding angle of 5 μL droplets was more than 90°, while the sliding angle
of 15 μL droplets was only 29°. When the droplet volumes were large
surface contained only CeH, CeO and C]O groups. As could be seen
enough, the interface of the droplets exceeded the limit of the super-
from Table 1, the content of fluorine-containing group on super-
hydrophilic grooves, and the droplets were mainly in contact with the
hydrophobic surface was 49.1%, which caused the superhydrophobicity
superhydrophobic substrate, and the contact angles of the droplets were
of the surface. Additionally, it was found that the content of the oxygen-
not significantly affected by the superhydrophilic grooves. Thus the
containing group on the secondary etched surface was 41.7%, which
contact angles did not change significantly with the increase of droplet
was much greater than that on superhydrophobic surface, and the
volumes. Meanwhile, with the increase of droplet volumes, the ratio of
secondary etched surface showed superhydrophilicity. Therefore, the
the contact area of the droplets to the superhydrophilic grooves and the
superhydrophobicity of the surface was contributed by the fluorine-
adhesion of the droplets decrease at the same time, so that the sliding
containing group, and the wettability transition from super-
angles became significantly smaller.
hydrophobicity to superhydrophilicity was caused by the removal of
As shown in Fig. 5a, as the diameters of the dot-shaped grooves
the fluorine-containing group and the increase of the oxygen-containing
increased, the contact angles of the droplets changed little, while the
group.
sliding angles changed significantly. For example, the contact angle of
15 μL droplets on the groove with a diameter of 20 μm was 159°, while
the contact angle on the groove with a diameter of 300 μm was 152°.
3.2. Controllable adhesion of dot-shaped groove
Conversely, the sliding angle of 15 μL droplets on the groove with a
diameter of 20 μm was 15.7°, while the sliding angle on the groove with
From the contact angles and sliding angles of the dot-shaped
a diameter of 300 μm was 41.7°, with obvious change (see
grooves shown in Fig. 4a, it could be clearly seen that the droplet ad-
Supplementary Material Video S1).
hesion behavior of the dot-shaped grooves changed obviously com-
On the initial superhydrophobic surface, the adhesive force (Foriginal )
pared with the original superhydrophobic surface. As shown in Fig. 4a,
that hinders the slide of the droplets is proportional to the width
the contact angles of droplets with same volume on dot-shaped grooves
(Wdroplet ) of the droplets vertical to the sliding direction [50–52]:
with different diameters decreased slightly compared with that of
droplets on untreated substrates (substrates with first laser and che- Foriginal = Wdroplet γL (cosθR − cosθH) (1)
mical treatment) and still greater than 150°. For example, the contact
angle of 30 μL droplets on the grooves with a diameter of 20 μm was
where γL is the surface tension of the droplets. θR and θH are the re-
161°, which was just slightly smaller than that on the untreated area. By
ceding angle and advancing angle of the droplets on the super-
contrast, it could be seen from Fig. 4b and Video S1 that the change of
hydrophobic surface, respectively.
the sliding angles was more obvious. For instance, the sliding angle of
The superhydrophobic surface is superhydrophilized by laser to
5 μL droplets on the grooves with a diameter of 80 μm was 65°, which
prepare the superhydrophilic dot-shaped grooves. At this time, when
was larger than that on the untreated area. Therefore, the dot-shaped
volumes of the droplets are larger than the volumes of the super-
grooves had high adhesion superhydrophobicity. The adhesion beha-
hydrophilic grooves, the droplets will simultaneously contact the
vior of droplets could be attributed to changes of the contact interface
grooves and the superhydrophobic substrate [Fig. 5b], so the adhesive
of the liquid-solid. For droplets on dot-shaped grooves, the interface of
force (Fdroplet ) of the droplets comes from both the superhydrophilic
the liquid-solid could be divided into two parts: the interface of the
grooves and the superhydrophobic substrate:
droplet-superhydrophilic groove and the droplet-superhydrophobic
substrate. However, the droplets were only in contact with the

Fig. 4. (a) CAs and (b) SAs of droplets with different volumes on dot-shaped grooves with different diameters: (a1–a4) CA images of 20 μL droplets on (a1) the SH
surface and (a2–a4) dot-shaped grooves; (b1–b4) SA images of 15 μL droplets on dot-shaped grooves.

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X. Liu, et al. Applied Surface Science 514 (2020) 145838

Fig. 5. (a) CAs and SAs of 15 μL droplets on dot-

shaped grooves with different diameters: (a1) The
CA image of 15 μL droplets on the groove with a
diameter of 80 μm, (a2) The CA image of 15 μL
droplets on the groove with a diameter of 150 μm,
(a3) The SA image of 15 μL droplets on the groove
with a diameter of 80 μm, (a4) The SA image of
15 μL droplets on the groove with a diameter of
150 μm; (b) Solid-liquid contact image.

Fdroplet = Wdot γL (cosθRdot − cosθH) + (Wdroplet − Wdot ) γL (cosθR − cosθH) vertical to the grooves was 152.6°, while the contact angle in the di-
(2) rection parallel to the grooves was only 92.5°. When the droplets were
on the grooves, the extent of spreading in the vertical direction was less
where γL is the surface tension of the droplets, θR and θH are the re- than that in the parallel direction, so that the contact angles of the
ceding angle and advancing angle of the droplets on the super-
droplets in the vertical direction were greater than that in the parallel
hydrophobic surface, respectively, and θRdot and θH are the receding direction. Similarly, it could be seen from Fig. 7 that the sliding angles
angle and advancing angle of the droplets on the dot-shaped grooves,
of the droplets in the vertical direction were always greater than that in
respectively. the parallel direction on the linear grooves with same width. For in-
Due to the superhydrophilicity of the dot-shaped grooves, the re-
stance, when 15 μL droplets were on the linear grooves with a width of
ceding angle of the dot-shaped grooves is almost 0°. Therefore cosθRdot
80 μm, the sliding angle in the direction vertical to the grooves was
is always greater than cosθR . Thus, the following relationship can be
43.7°, while the sliding angle in the direction parallel to the grooves
obtained [53]:
was only 7.3°. When droplets rolled off along the direction parallel to
Fdroplet − Foriginal = Wdot γL (cosθRdot − cosθR ) > 0 (3) the linear grooves, only two forces needed to be overcome: the viscous
force of water and the force of interface between the droplet and the
As can be seen from equation (3), the adhesion of the grooves to the superhydrophobic surface [53]. However, droplets that slide along the
droplets increases as the diameters (Wdot ) of the grooves increase. Thus, direction vertical to the linear grooves were additionally limited by the
the sliding angles change more obviously. much larger liquid tension, and it was much more difficult for the
droplets to slide in that direction, thereby contributing to the obvious
3.3. Anisotropic adhesion of linear groove anisotropic property.
Additionally, it could be clearly seen in Fig. 8 that as the widths of
The superhydrophilic linear grooves on the superhydrophobic sur- the linear grooves increased, the contact angles of the droplets that
face exhibited different contact angles [Fig. 6] and sliding angles were vertical to the linear grooves and parallel to the linear grooves
[Fig. 7] in the parallel and vertical directions. It could be seen from both decreased. As the widths of the linear grooves increased, the
Fig. 6 that the contact angles of the droplets in the vertical direction spreading degree of the droplets in the direction vertical to the grooves
were always greater than that in the parallel direction on the linear increased, and at the same time, the droplets spread more obviously in
grooves with same width. For example, when 15 μL droplets were on the direction parallel to the grooves, thereby causing the contact angles
linear grooves with a width of 80 μm, the contact angle in the direction of the droplets to decrease in different rates in the vertical and parallel

Fig. 6. (a), (b) CAs of droplets with different volumes on linear grooves with different widths. (a1-a3) CA images in the vertical direction of the droplets with different
volumes on the linear groove with a diameter of 20 μm, (a4-a6) CA images in the parallel direction of the droplets with different volumes on the linear groove with a
diameter of 20 μm; (b1-b3) CA images in the vertical direction of the droplets with different volumes on the linear groove with a diameter of 150 μm, (b4-b6) CA
images in the parallel direction of the droplets with different volumes on the linear groove with a diameter of 150 μm.

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X. Liu, et al. Applied Surface Science 514 (2020) 145838

Fig. 7. (a), (b) SAs of droplets with different volumes on linear grooves with different widths. (a1) SA images in the vertical direction of 15 μL droplet on the linear
groove with a diameter of 40 μm, (a2) SA images in the parallel direction of 15 μL droplet on the linear groove with a diameter of 40 μm; (b1) SA images in the
vertical direction of 15 μL droplet on the linear groove with a diameter of 150 μm, (b2) SA images in the parallel direction of 15 μL droplet on the linear groove with a
diameter of 150 μm.

direction of droplet transport by 90°. Since the sliding angles in the

direction parallel to the grooves were smaller than the sliding angles in
the direction vertical to the grooves, the droplets could gather at the
end of the grooves after sliding parallel to the grooves until the gravity
component was greater than the adhesive force, and the droplets could
roll off from the grooves.
Since the groove widths and droplet volumes we selected were
consistent with those discussed in the previous section, we could use the
sliding angle data measured in the previous section for droplet trans-
port experiment. By controlling the tilt angles of the aluminum surface
under different droplet volumes and different groove widths, numbers
of accumulated droplets before they rolled off at the end of the grooves
could be measured [Fig. 9b]. For example, when the droplet volume
was 15 μL and the groove width was 300 μm, 9 droplets could be col-
lected at the end of the groove before rolling off (see Supplementary
Material Video S3).
Fig. 8. CAs and SAs of 15 μL droplets on linear grooves with different widths.

4.3. Droplet capture and mixing

directions. Interestingly, as could be seen from Fig. 8, the sliding angles
of the droplets increased in the vertical direction as the groove widths
Screening of cells and drugs is a micromanipulation process, based
increased, and decreased in the parallel direction (see Supplementary
on this practical application, we can consider to perform the capture
Material Video S2).
and release of droplets on superhydrophobic surface with super-
hydrophilic grooves (Fig. 10). According to the above analysis, the
4. Applications linear grooves have remarkable anisotropic property. Then a linear
groove with a width of 300 μm could be prepared on the super-
4.1. Preparation of patterned surface hydrophobic aluminum substrate A1 by laser, a dot-shaped groove with
a diameter of 300 μm was prepared on another superhydrophobic
Using the laser etching method described above, we could prepare aluminum substrate B1. A droplet with a volume of 10 μL was dropped
many patterns of extreme wettability on the metal surfaces [Fig. 9a]. on the dot-shaped groove, and captured by the linear groove on su-
The desired area was etched on the superhydrophobic aluminum sur- perhydrophobic aluminum substrate A1. By using the property that a
faces to form superhydrophilic patterns. The liquid droplets were droplet had a large sliding angle in the direction vertical to the linear
dropped on the superhydrophilic patterns, and the liquid droplets ad- groove, the aluminum substrate A1 captured the droplet in the direc-
hered to the patterns without wetting the surrounding super- tion vertical to the linear groove, so that the droplet could be easily
hydrophobic area to form the drawn patterns. grasped. Similarly, the aluminum substrate A1 could be controlled to
release the droplet on the dot-shaped groove of the aluminum substrate
4.2. Droplet transport B1 in the direction parallel to the linear groove (see Supplementary
Material Video S4).
Through qualitative and quantitative analysis of the linear grooves In addition, it is also possible to perform droplets mixing by utilizing
above, we can know that the superhydrophilic grooves on the super- the adhesive force of superhydrophilic grooves. As shown in Fig. 11,
hydrophobic surface have strong anisotropic adhesion to the droplets two dot-shaped grooves with a diameter of 300 μm were prepared on
and can be used for directional transport of droplets. We first prepared the substrate B2. In order to overcome the droplet gravity and the ad-
grooves with widths of 40 μm, 80 μm, 150 μm, 300 μm, and 450 μm on hesive force of the groove, a dot-shaped groove with a diameter of
the superhydrophobic aluminum surfaces. The grooves of this shape 500 μm was prepared on the substrate A2 for quick grasping. Two
[Fig. 9b] not only transported the droplets quickly, but also changed the droplets were dropped on the two grooves on the substrate B2, and one

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X. Liu, et al. Applied Surface Science 514 (2020) 145838

Fig. 9. (a) Patterned metal surfaces; (b) The numbers of droplets with different volumes transported on the grooves with different widths. The mixed images of last
droplet and images of mixed droplets falling off from the Al surface of 15 μL droplet (b1) and 20 μL droplet (b2) on linear grooves with a width of 300 μm.

Fig. 10. Capture (a) and release (b) processes of droplets.

Fig. 11. Capture (a) and mixing (b) processes of droplets.

of the droplets was captured by the groove on substrate A2. Then we patterned hybrid surfaces have higher fog collection efficiency than
moved the droplet to the location of another droplet and mixed them uniform superhydrophilic surfaces, uniform superhydrophobic surfaces
(see Supplementary Material Video S4). and untreated hydrophilic surfaces. On the basis of this phenomenon,
we prepared superhydrophilic/superhydrophobic patterned hybrid
4.4. Fog collection surfaces on Al, Cu, Steel and Ti plates to achieve high fog collection
efficiency [Fig. 12]. Superhydrophobic surfaces were prepared by laser
The Stenocara beetles in the Namib Desert has amazing fog collec- etching and modification of low surface energy, and then super-
tion capacity based on their superhydrophobic structures with hydro- hydrophilic patterns shown in Fig. 12 were prepared by secondary laser
philic arrays on their backs. The superhydrophilic/superhydrophobic etching on superhydrophobic surfaces. The pattern is fan-shaped

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X. Liu, et al. Applied Surface Science 514 (2020) 145838

Fig. 12. Fan-shaped patterned surface.

Fig. 13. Fog collection images on different patterned metal surfaces: (a) Al, (b) Cu, (c) Steel, (d) Ti.

groove, and the upper part is a parallel wedge pattern consisting of improved efficiency of patterned Al surface compared with the other
many 4° wedge angle grooves, which can accelerate droplet transport three Al surfaces was: 16.79%, 17.53%, 15.56%, respectively. Similarly,
and improve efficiency. The droplets merge on the lower triangular the improved efficiency of Cu was: 54.45%, 81.69%, 12.53%; Steel was:
area, and the volume gradually increases until the droplet rolls off. 33.88%, 55.98%, 63.44%; Ti was: 10.48%, 33%, 29.74%.
First of all, we compared the fog collection efficiency of the pat- Based on the comprehensive analysis of the above data, it can be
terned surface, the uniform superhydrophilic surface, the uniform su- found that the improvement of the fog collection ability of the pat-
perhydrophobic surface and untreated surface of each metal. The fog terned Steel surface is the highest, followed is Cu and Ti, and the lowest
collection experiments were carried out for 30 min [Fig. 13] (see is Al. Additionally, It can be seen from Fig. 14 that patterned Steel
Supplementary Material Video S5, S6, S7, S8). The mass of fog collected surface has the highest fog collection efficiency and patterned Cu sur-
on each sample was measured. According to the analysis of the mea- face is the least efficient to collect fog among the four patterned metal
sured data, the fog collection efficiency of the patterned surface was surfaces.
improved to different extents compared with the other three surfaces
[Fig. 14]. The mass of the collected liquid of the patterned Al surface, 5. Conclusions
the uniform superhydrophilic Al surface, the uniform Al super-
hydrophobic surface and the untreated Al surface were 28237.3 mg, In summary, we proposed a versatile laser processing method for
24178.87 mg, 24025.2 mg, 24435.13 mg, respectively. Therefore, the various metals. The superhydrophobic surfaces were prepared by laser

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X. Liu, et al. Applied Surface Science 514 (2020) 145838

Fig. 14. Fog collection results on different metal surfaces: (a) different treated surfaces of Al, (b) different treated surfaces of Cu, (c) different treated surfaces of Steel,
(d) different treated surfaces of Ti.

etching and modification of low surface energy, and the super- influence the work reported in this paper.
hydrophilic dot-shaped grooves, linear grooves and fan-shaped grooves
were prepared by secondary laser etching. The contact angles and Acknowledgment
sliding angles of the droplets on the dot-shaped and linear grooves were
measured and analyzed. The dot-shaped grooves had large adhesive This work was financially supported by National Natural Science
force to the droplets, and the linear grooves had obvious anisotropic Foundation of China (Grant No. 51975092), the Fundamental Research
adhesion. On the basis of the high adhesion behavior, droplets capture, Funds for the Central Universities (Grant No. DUT18JC19,
mixing and transportation were achieved on the prepared patterned DUT19ZD202), and National Basic Research Program of China (Grant
surfaces. Finally, Al, Cu, Steel and Ti were patterned to prepare the fan- No. 2015CB057304).
shaped grooves on the superhydrophobic metal surfaces. The fog col-
lection experiments on the four metal surfaces were carried out, and it Appendix A. Supplementary material
was found that the Steel had a relatively higher collection efficiency of
28237.3 mg/30 min and Cu was less efficient to collect fog Supplementary data to this article can be found online at https://
(26771.5 mg/30 min). The whole experiment process was mainly based doi.org/10.1016/j.apsusc.2020.145838.
on laser processing, which is simple, convenient and efficient. The
proposed laser processing method can be employed for treating various References
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