Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Preparation of superhydrophobic glass surface with high adhesion

Xiubing Jing a, Yani Xia a, Faze Chen a, *, Chengjuan Yang a, Zhen Yang b, **,
Syed Husain Imran Jaffery c
a
Key Laboratory Equipment Design and Manufacturing Technology, School of Mechanical Engineering, Tianjin University, Tianjin 300054, China
b
Department of Mechanical and Aerospace Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China
c
School of Mechanical and Manufacturing Engineering, National University of Sciences and Technology, Islamabad 44000, Pakistan

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Superhydrophobic glass surfaces with

high adhesion are prepared by laser
ablation and chemical modification.
• Mechanism of changes in wettability
was explored by XPS results from the
reaction of fluorosilane and glass
perspectives.
• Morphologies of glass surfaces ablated
were substantially dependent on laser
energy and significantly affected the
adhesion.
• The number of scans slightly affected
the surface morphologies and the
adhesion.
• Surface adhesion experiments of glass
surfaces ablated at different laser pa­
rameters have been performed.

A R T I C L E I N F O A B S T R A C T

Keywords: This paper prepared the superhydrophobic surfaces on the glass substrate by the ablation of grid microstructures using
Superhydrophobic picosecond laser and subsequence chemical modifications by silanization. The novelties in this research are the
Glass superhydrophobic surfaces prepared with high adhesion and further exploration of the effect of abrasion on its
High adhesion
superhydrophobic and adhesion properties. The surface morphologies were characterized by a scanning electron mi­
Picosecond laser
croscope (SEM) to reveal the effect of laser parameters on micro-nano structure. The water contact angles and surface
roughness values were measured to illustrate the effect laser parameters on surface wettability. The surface energy was
calculated to prove the correlation between lower surface energy and superhydrophobicity. The chemical composition
of the surfaces was detected by an X-ray photoelectron spectroscopy (XPS) to explore the mechanism of changes in
wettability from the reaction of fluorosilane and glass materials perspectives. The surface adhesion experiments were
also performed to reveal the relationship between surface adhesion and laser parameters. The results indicated that the
micro/nano structure by laser-induced were substantially dependent on the laser energy and significantly affected the
adhesion. However, the number of scans slightly affected the surface morphologies and the adhesion. Finally, the
abrasion resistance experiments were conducted to observe the relationship between abrasion cycle to contact angle
and adhesion.

* Correspondence to: Mechanical Engineering, Tianjin University, Tianjin, China.

** Correspondence to: The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China.
E-mail addresses: [email protected] (F. Chen), [email protected] (Z. Yang).

https://doi.org/10.1016/j.colsurfa.2021.127861
Received 25 August 2021; Received in revised form 29 October 2021; Accepted 3 November 2021
Available online 12 November 2021
0927-7757/© 2021 Elsevier B.V. All rights reserved.
X. Jing et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

1. Introduction materials can be processed by picosecond laser system, which making

the use of picosecond processing equipment more widespread [20,21].
Superhydrophobic surfaces have attained broad range of applica­ In this paper, picosecond laser system is used to fabricate the grid
tions due to their distinctive performance, such as self-cleaning [1,2], microstructure on the glass surface firstly, and then the low surface
anti-icing [2,3], anti-fogging [4], oil-water separation [5] just to energy material is used for surface chemical modification to prepare the
mention a few. In nature, there are many surfaces exhibiting super­ superhydrophobic glass surface with high adhesion. An attempt has
hydrophobic properties, for example the lotus leaf and the rose petal. been made to explore the effect of abrasion on superhydrophobic and
However, the lotus leaf and the rose petal are two kinds of super­ adhesion properties. Especially, the relationship between the abrasion
hydrophobic surfaces with distinctly different water adhesion. The lotus cycle to contact angle and adhesion are quantitatively investigated. The
leaf is a typical superhydrophobic surface with low adhesion. The surface morphologies, the surface roughness and the water contact angle
extremely low water adhesion of the lotus leaf surface makes the water are observed by SEM, a 3D measuring laser microscope and a contact
droplets not stay on the leaf surface, but easily roll off taking away the angle measuring instrument, respectively. The effect of laser parameter
dust from the surface. This phenomenon is known as the "lotus leaf ef­ on the micro-nano structure and wettability are discussed. The surface
fect" [6]. While the rose petal is a typical parahydrophobic surface with energy will be calculated based on the contact angle data. The surface
high adhesion surface, which makes the water droplets firmly adhering chemical composition will be explored by XPS. And the water adhesion
to the petal surface and not moving at any angle of tilt. This phenome­ of the superhydrophobic surface will be performed qualitatively on the
non is referred to as the "petal effect" [7]. Most previous studies of contact angle measuring instrument. Finally, the abrasion resistance
superhydrophobic surfaces have focused on the low adhesion, and the experiments are conducted to explore the change in the contact angle
researchers are rarely interested in studying the superhydrophobic and adhesion after abrasion.
surfaces with high adhesion due to higher requirements for micro­
structure. In fact, the surfaces with high water adhesion have potential 2. Experimentation
applications in the no loss transport of water droplets [8,9], microfluidic
devices [10], transport and analysis of microvolume samples [11]. In 2.1. Material preparation
addition to the applications as pointed out above, high-adhesive
superhydrophobic materials have better tribological properties and The material used to prepare superhydrophobic glass surface in this
lower friction coefficient than low-adhesive superhydrophobic materials experiment is ultra-white glass with dimensions of 10 mm × 10 mm × 1
[12]. Therefore, the study of the superhydrophobic surfaces with high mm, purchased from Taiwan Glass Co., Ltd. of China. Its characteristic
water adhesion should also be on the schedule. parameters and main components are shown in Table 1.
To date, several researchers have discovered the promising appli­ Before the laser ablation experiment, the glass samples were first
cations of high adhesion superhydrophobic surfaces and begun to study cleaned with acetone, anhydrous ethanol and deionized water sepa­
its preparation methods. Xiang et al. [13] fabricated superhydrophobic rately in an ultrasonic cleaner for 15 min to remove contaminants from
mild steel surfaces with controllable water adhesion using a combina­ the glass surface. Subsequently, the samples were dried in a drying oven
tion method of alkaline etching, electrochemical deposition and chem­ for 10 min at 100 ◦ C. Finally, the samples were cooled naturally to the
ical modification with myristic acid. The adhesion of the mild steel room temperature in the air. Since glass is an intrinsically hydrophilic
surfaces varied with etching time. The surfaces prepared with high material, based on the strategy of preparing artificial superhydrophobic
adhesion were used for drug delivery while the surfaces with low surfaces [22], the process of modifying rough surfaces with the low
adhesion were used for self-cleaning. Li et al. [14] constructed surface energy materials was chosen to prepare the superhydrophobic
micro-nano hierarchical structures on metallic glass surfaces by silicon glass surfaces with high adhesion in this experiment. Firstly, a pico­
molding and chemical etching, fabricated the metallic glass surfaces second laser system was used to fabricate the grid microstructures on the
with superhydrophobicity and highly water adhesive force, and dis­ glass surfaces, and then the fluorosilane was used to modify the
cussed the possibility of industrial applications as dry adhesives and laser-treated glass surfaces chemically.
"mechanical hands" for grabbing water droplets. Zhu et al. [15] obtained Fig. 1 shows schematic diagrams of the picosecond laser system and
a superhydrophobic surface on glass substrate with tunable adhesion by laser scanning path for fabricating grid microstructures on glass sur­
depositing Silica (SiO2) nanoparticles and modifying with hydrophobic faces. A Sagittar-L picosecond laser system from Daheng New Epoch
polydimethylsiloxane (PDMS). This superhydrophobic surface showed Technology Co., Ltd (China) with a pulse duration of 15 ps and a
high transparency and tunable adhesion that could transform at wavelength of 1064 nm is used to perform the laser machining of the
different temperatures. And the surface also showed good self-cleaning glass surface. As shown in Fig. 1(a), the Gaussian laser beam is generated
property, durability and thermal stability. Basiron et al. [16] produced in the laser generator at first. Subsequently, the diameter of the laser
a superhydrophobic glass surface with improved adhesion by spraying beam is expanded by a laser beam expander. After that, the laser beam
the hydrophobic coating mixture. The superhydrophobic coating was goes through a beam attenuator that can adjust the laser energy and then
chemically stable in both acid and neutral environment. passes through a series of turning mirrors that can change the direction
With the development of the laser technology, the advantages of of laser beam before entering the galvanometer scanner, in which the
single-step processing, high speeds and no pollution [17] have made laser beam is reflected and focused onto the surface of the workpiece
laser machining popular with researchers successfully. Song et al. [18] placed on an X-Y stage with a repeatability of < 0.005 mm. A PC is used
prepared superhydrophobic aluminum surfaces with tunable adhesion
using femtosecond laser ablation in combination with pentadeca­
Table 1
fluorooctanoic acid immersion. The surfaces presented different adhe­ characteristic parameters of ultra-white glass.
sion properties at different laser parameters. The article also conducted
Characteristic Index Parameter
no loss water transportation experiments using the prepared surfaces
with different adhesion. Similarly, Long et al. [19] also fabricated Physical Characteristic Density 2.51 g/cm3
Optical Characteristic Transmittance 91.5%
superhydrophobic copper surfaces with tunable adhesion using a com­
Mechanical Characteristic Hardness 456 kgf/mm2
bination of femtosecond laser ablation and chemical modification, and Thermal Characteristics Thermal expansion coefficient 9.75 × 10− 6 /℃
performed no loss water transportation experiments. However, the Thermal conductivity 1.1 W/(m⋅K)
femtosecond laser devices have disadvantages of high cost and low Softening point 710 ℃
material removal rates. Compared to femtosecond laser systems, pico­ Main components SiO2 72.01%; Na2O 14.02%; CaO 8.86%; MgO 3.8%;
Al2O3 0.81%; K2O 0.14%; others 0.36%
second laser systems have a higher material removal rate. Most

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X. Jing et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

was used to measure the surface roughness. An X-ray photoelectron

spectroscopy (Thermo ESCALAB 250XI) was used to evaluate the
chemical composition of the glass surface.

3. Results and discussions

3.1. Surface morphologies analysis

Figs. 2 and 3 present the SEM images of the glass surface ablated with
different pulse energies and scanning times, respectively, in which,
Figs. 2 and 3(a) are the SEM image of the original glass surface that is
smooth and flat without any defects.
As it can be observed in the figures, compared to the original glass
surface, the grid microstructures with the period of about 100 µm
appear on the glass surfaces after laser ablation, which are consistent
with the distance between adjacent laser beams.
As exhibited in Fig. 2(b) - (d), the microgroove width of the micro­
grid is about 26 µm, which doesn’t show significant difference with the
increase of the pulse energy. While the size of the micro-nano bumps at
the edges of the microgrooves become larger, and the deposited mate­
rials gradually appear on the untreated surfaces. Fig. 2(e) demonstrates
that a large amount of redeposited micro-nano particles exists on the
untreated glass surfaces. This is because the more glass material melted
and then solidified due to the higher laser energy. While as evident from
the Fig. 2(f), there are a lot of cracks on the surface. Due to the extremely
high laser energy, thermal accumulation becomes serious. As a result,
cracks will occur when thermal accumulation and thermal stress inside
the glass are high enough to provide abundant energy to create a new
fracture surface [24]. At the same time, the temperature of the glass
surface turns high with the thermal accumulation occurring, causing the
materials to melt seriously and flow. As a consequence, most of adjacent
Fig. 1. Schematic diagrams for fabricating grid microstructures on glass sur­ microgroove structures are connected together by the molten materials
faces (a) the picosecond laser system; (b) laser scanning path. as seen from the figure.
Due to the lower laser energy, neither micro-nano particles nor
to control the movement of the galvanometer scanner and the X-Y stage. cracks on the glass surfaces can be seen in Fig. 3 like those in Fig. 2(d) -
Fig. 1(b) presents a schematic diagram of the laser scanning path. L in (f). The microgroove width of the microgrid is about 28 µm, which
the diagram is the distance between adjacent laser beam passes. In this doesn’t change significantly with the number of scans increasing. As
experiment, refer to our previous work [23], the scanning speed is set as exhibited in Fig. 3(b), some collapse edges can be found at the edge of
1 mm/s constantly. Both the horizontal and vertical parameters of L are the microstructures. Micro-nano bumps and micro-nano holes structures
100 µm. can be observed obviously on the sidewalls. With the increase of the
The experiments are carried out by the single variable method. The number of scans, the laser pulses generated subsequent ablate the micro-
glass samples are divided into two groups with the variable of pulse nano bumps on the sidewall continuously, so that the scale of the micro-
energy for Group 1 and the variable of number of scans for Group 2. The nano bumps and the micro-nano holes structures gradually decrease in
laser parameters are shown in Table 2. Fig. 3(c) - (f).
After laser ablation, the glass samples were cleaned with anhydrous
ethanol and deionized water in turn for 15 min ultrasonically, dried in a 3.2. Surface wettability analysis
drying oven for 10 min at 100 ◦ C and cooled to room temperature
naturally. Subsequently, the laser-treated glass samples were immersed Fig. 4(a) and (b) demonstrate the water contact angles of the original
in 1H, 1H, 2H, 2H – perfluorodecyltriethoxysilane (fluorosilane) with a glass surface and the surface after the fluorosilane modification,
mass fraction of 2% at room temperature for 2 h and then dried for respectively. As it can be observed in the figure, the water contact angle
30 min at 100 ◦ C. of the original glass surface is 58.0◦ , indicating that the original glass
surface is a hydrophilic surface. After the fluorosilane modification, the
water contact angle increases to 83.2◦ , which indicates that fluorosilane
2.2. Surface characteristics can increase the contact angle and strengthen the water repellency of the
surface.
A SEM (QUANTA FEG 250) was used to observe the surface mor­ Fig. 5 presents the water contact angles and roughness values of the
phologies of glass samples. A contact angle measuring instrument (SZ- glass surfaces ablated with different laser parameters. As exhibited in
CAM) was used to measure the water contact angle and perform the Fig. 5(a), with the increase of pulse energy, the water contact angle
surface adhesion experiments. A 3D laser microscope (OLYMPUS 4100) increases from 152.7◦ , reaching a maximum value of 159.2◦ at the pulse
energy of 66.7 μJ and then decreases to 158.5◦ . Fig. 6 shows the sche­
Table 2 matic diagrams of wetting state [25]. A large amount of micro-nano
Parameters of laser ablation. particles is attached to the glass surface when the pulse energy is
66.7 μJ as seen from Fig. 2(e). In this case, the glass surface is in a
Group Pulse energy (μJ) Number of scans
condition similar to a state called the Cassie-Baxter non-wetting state, as
Group 1 16.7, 33.3, 50.0, 66.7, 83.3 1 shown in Fig. 6(b). The water stays on the redeposited particles [25].
Group 2 16.7 1, 2, 5, 10, 20
Plenty of air is trapped by the micro-nano structure, which enhances the

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X. Jing et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

Fig. 2. SEM images of samples for group 1 (a) original glass surface; (b) 16.7 μJ; (c) 33.3 μJ; (d) 50.0 μJ; (e) 66.7 μJ; (f) 83.3 μJ.

Fig. 3. SEM images of samples for group 2 (a) original glass surface; (b) 1; (c) 2; (d) 5; (e) 10; (f) 20.

superhydrophobicity of the glass surface and makes the water contact wettability, the surface roughness of original glass with and without
angle maximum [26]. While water stays on other blunted surfaces in the silanization are also measured, which is 0.560 nm and 0.500 nm
state of Cassie-Baxter hydrophobic state as shown in Fig. 6(a) [25]. Fig. 5 respectively. Compared to the original glass surface, all surfaces pre­
(b) shows that the water contact angle changes from 152.7◦ to 156.1◦ sented in Fig. 5 become rougher after laser ablation, which indicates that
flatly as the number of laser scans increases, which is consistent with the the roughness glass surface can afford the hydrophobic characteristic. As
fact that there is no significant change of the glass surface morphologies evident in Fig. 5(b) that the trends of surface roughness are similar to
in Fig. 3. To investigate the effect of surface roughness on the that of water contact angle, while the trends have no consistent direction

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X. Jing et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

Fig. 4. Diagrams of water contact angle on glass surface (a) original glass surface; (b) glass surface after fluorosilane modification.

Fig. 5. Water contact angle and roughness images of different laser parameters (a) samples for group 1; (b) samples for group 2.

Fig. 6. Schematic diagrams of wetting state (a) Cassie-Baxter hydrophobic state; (b) Cassie-Baxter non-wetting state.

in Fig. 5(a), meaning that there is no obvious connection between sur­ (

√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
)
face roughness and water contact angle [27]. Similar phenomenon can γSL = γSV + γLV − 2 γSV D γLV D + γSV P γLV P
be found in the previous literature that the surface wettability is mainly
determined by the surface chemical composition not the surface (
γSV D γLV D γSV P γLV P
)
roughness [28]. γSL = γSV + γLV − 4 +
γSV D + γLV D γSV P + γLV P
The surface energy of the solid is divided into the polar component
and the dispersive component (non-polar component). Based on the where θ is the contact angle, γSV is the solid-vapor interfacial energy,
water contact angles, the surface energy of the glass modified with γSL is the solid-liquid interfacial energy, γLV is the liquid-vapor inter­
fluorosilane can be calculated using Owens-Wendt method [29] and Wu facial energy, γSV D is the dispersive component of γSV, γLV D is the
method [30], in combination with Young’s equation [31]. Young’s dispersive component of γLV, γSV P is the polar component of γSV, γLV P is
equation, Owens-Wendt method and Wu method are described as the the polar component of γLV. The surface energy of the glass surfaces is
following equations, respectively: calculated by using two different liquids of deionized water and ethylene
glycol. The results are shown in Table 3.
γSV − γSL
cos θ = Combined with the water contact angle data in Fig. 5, it can be
γLV

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X. Jing et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

inferred from Table 3 that the lower surface energy of the glass makes the maximum volume of the droplets adhere to the glass surface.
the contact angle larger. The surface energy of the material can be To investigate the effect of chemical composition on adhesion,
decreased by fluorosilane. The reaction mechanism of fluorosilane and Fig. 10 shows the adhesion images of the original surface with/without
the glass surface is shown in Fig. 7. Glass is an inorganic material. The fluorosilane modification. Since the original surface is hydrophilic, it
reaction mechanism of fluorosilane and inorganic materials is in can be seen from Fig. 10(a) that the droplet spreads out on the surface,
accordance with Arkles method [32]. The fluorosilane hydrolyzes and and has a wide contact area with the surface. Compared to Fig. 10(a), it
generates siloxane firstly when it contacts with the glass surface. The can be observed from Fig. 10(b) that the contact area between the
chemical formula of SiO2 indicates that the ratio of the atoms number of droplet and surface decreases significantly after fluorosilane modifica­
Si and O is 1:2. While the correspondence between Si and O on the tion, which indicates that low surface energy elements can reduce the
surface of SiO2 crystal does not follow that ratio. Therefore, the valence surface adhesion. Figs. 11 and 12 show the superhydrophobic surfaces
state of SiO2 crystal surface is unsaturated. As a result, there are a certain with microstructures after fluorosilane modification. Compared Figs. 11
number of silicon hydroxyl groups (Si–OH) exposed on the glass sur­ and 12 with Fig. 10, it can be found that the contact area of the super­
face. The high polarity of the silicon hydroxyl groups makes the original hydrophobic surfaces decreases and the surface adhesion reduces
glass surfaces hydrophilic. The siloxane generated by hydrolysis of flu­ further.
orosilane reacts with Si-OH of the glass surface under the dehydration As evident from Figs. 11 and 12, the prepared glass surfaces have a
condensation reaction, resulting in the attachment of CF3(CF2)7(CH2)2 highly water adhesion varying with different laser parameters, as per­
groups on the glass surface and transformation of Si–OH into the formed by the different maximum volumes of droplets on the surfaces. In
Si–O–Si ether bonds. Meanwhile, polycondensation reaction occurs this case, the water droplets on the glass surface are in a transitional
between the adjacent siloxanes, which also generates Si–O–Si ether state called metastable [18] or Cassie impregnating state [34]. Water
bonds. Eventually, the glass surface is covered with CF3(CF2)7(CH2)2 droplets can enter part of the structure, making the surfaces exhibit high
groups, forming a self-assembled hydrophobic molecular film. The sur­ adhesion properties. As seen from Fig. 11, the minimum volume of
face energy can be reduced by CF3(CF2)7(CH2)2 groups and Si–O–Si droplet is 12 μL at the laser pulse energy of 66.7 μJ. This is due to the
ether bonds considerably. presence of micro-nano particles on the glass surface as shown in Fig. 2
The chemical components of the glass surface modified with fluo­ (e). More air can be trapped by the micro-nano particle structure, so that
rosilane are analyzed by XPS as shown in Fig. 8. The results of wide scan the contact area of the droplet and the glass surface is significantly
spectra in Fig. 8(a) indicate that F element appears on the glass surface decreased and adhesion is greatly reduced. Fig. 12 demonstrates that the
after fluorosilane modification, confirming the attachment of different number of laser scans has no significant effect on the adhesion.
CF3(CF2)7(CH2)2 groups on the surface. As exhibited in Fig. 8(b), the C
1s high-resolution spectra show two distinct peaks that can be decom­ 3.4. Surface abrasion resistance analysis
posed to four components. There are –CF2 and –CF3 groups at the
electronic binding energies of 291.1 ev and 293.4 ev, respectively, The abrasion resistance of superhydrophobic surfaces significantly
proving that fluorosilane is successfully attached to the glass surface. influences the results of their applications. Therefore, the abrasion
Apart from that, there are C–C(H) bonds and C– – O bonds located at resistance of the prepared superhydrophobic glass surface was analyzed
electronic binding energies of 284.8 ev and 288.8 ev, respectively. Most by using a sandpaper abrasion test method. As illustrated in Fig. 13, the
groups originate from fluorosilane molecules, and few part may be glass surface fabricated with microstructures was in contact with the
attributed to exposure to carbon contamination during testing [33]. 1000 # SiC sandpaper placed on the table. And a mass of 100 g was put
on the top of glass surface. The glass was moved 20 cm transversely and
longitudinally on the sandpaper respectively, which was defined as an
3.3. Surface adhesion analysis abrasion cycle. The water contact angle and adhesion were measured
after each abrasion cycle.
As exhibited in Fig. 9, the prepared glass surface shows not only Fig. 14 presents the variations curves of contact angle and adhesion
superhydrophobic but also high adhesion to water droplets. The water of glass surface with abrasion cycle. As evident from the figure, the
droplet shows a spherical shape as seen in Fig. 9(a) when the glass contact angle decreases with the increase of abrasion cycle gradually.
sample is placed horizontally. As shown in Fig. 9(b), the water droplet After 3 abrasion cycles, the water contact angle decreases from 152.7◦ to
changes the shape from spherical to elliptical but remains pinned to the 146.1◦ due to the slight destruction of the fluorinated surface, and the
surface without sliding when the glass sample is tilted 90◦ . The key surface no longer shows a superhydrophobic state. After 6 abrasion
parameter for this effect is the volume of the droplet. When the volume cycles, the fluorinated film and microstructure are both destructed,
of the droplet increases until the gravity is sufficient to overcome the resulting in a decrease of the contact angle to 132.1◦ . Although the
adhesion force of the glass surface, the water droplet starts sliding [9]. surface is not in a superhydrophobic state after abrasion, it’s still hy­
Therefore, the glass surface adhesion can be qualitatively analyzed by drophobic, which means the prepared surface possesses a certain abra­
sion resistance. On the contrary, the surface adhesion increases after
Table 3 abrasion, which can be reflected by the result of the increase in volume
Surface energy calculations of glass surfaces modified with fluorosilane. of adhesion droplets. The adhesion isn’t significantly change due to the
Laser parameter Surface energy (mN/m) slight abrasion after 1 abrasion cycle. While from the second abrasion
cycle, the volume of adhesion droplets increases rapidly due to the
Owens-Wendt method Wu method
destruction of both surface fluorinated film and microstructure, indi­
D P
γSV γSV γSV γSV γSVP cating a significant increase in surface adhesion.
Pulse energy (μJ) 16.7 0.266 0.008 0.258 3.078 -2.859 5.937
33.3 0.212 0.013 0.199 2.752 -2.673 5.425 4. Conclusions
50.0 0.099 0.039 0.060 1.700 -1.723 3.423
66.7 0.081 0.011 0.070 1.733 -2.250 3.983
Superhydrophobic glass surfaces with high adhesion were prepared
83.3 0.093 0.012 0.081 1.846 -2.294 4.140
Number of scans 1 0.266 0.008 0.258 3.078 -2.859 5.937 by laser ablation and chemical modification. This paper investigated the
2 0.244 0.009 0.235 2.957 -2.809 5.766 surface morphologies, surface wettability, surface adhesion and surface
5 0.227 0.002 0.225 2.875 -2.981 5.856 abrasion resistance of the glass surfaces. The results of surface mor­
10 0.188 0.005 0.183 2.634 -2.813 5.447 phologies study showed that the grid microstructures with period
20 0.185 0.005 0.180 2.611 -2.803 5.414
consistent with the distance between adjacent laser beams appeared on

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X. Jing et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

Fig. 7. Image of reaction mechanism of fluorosilane and glass surface.

Fig. 8. XPS analysis of glass surface modification with fluorosilane (a) wide scan spectra; (b) high-resolution of the C 1s spectra.

Fig. 9. Shapes of water droplets on superhydrophobic glass surface with different tilt angles (a) 0◦ ; (b) 90◦ .

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X. Jing et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

Fig. 10. Adhesion images of the glass surface (a) original glass surface; (b) glass surface after fluorosilane modification.

Fig. 11. Adhesion images of samples for group 1 (a) 16.7 μJ; (b) 33.3 μJ; (c) 50.0 μJ; (d) 66.7 μJ; (e) 83.3 μJ.

Fig. 12. Adhesion images of samples for group 2 (a) 1; (b) 2; (c) 5; (d) 10; (e) 20.

Fig. 13. Abrasion resistance image.

the glass surface. Micro-nano deposited particles gradually existed on was low. And there is no significant dependence between surface
the glass surface with the increase of pulse energy. Cracks can be roughness and contact angle. The results of surface adhesion experiment
observed on the glass surface obviously at the pulse energy of 83.3 μJ. indicated that the prepared glass surfaces exhibited adhesion charac­
While the number of scans has little effect on the surface morphologies. teristic. The volume of water droplet was the minimum and the adhesion
The results of surface wettability analysis elucidated that there are F was the lowest at the pulse energy of 66.7 μJ. While the effect of number
element and -CF2 and -CF3 groups with low surface energy existed on the of scans on the adhesion was not significant. The results of surface
glass surface modified with fluorosilane. The water contact angles were abrasion resistance proved that the superhydrophobic glass surface was
generally larger than 150◦ , and the surface energy of the glass surface still hydrophobic after 6 abrasion cycles, and the adhesion was

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X. Jing et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 633 (2022) 127861

Fig. 14. Water contact angle and adhesion after abrasion cycle.

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