Recent Advances in Durability of Superhydrophobic Self-Cleaning Technology A Critical Review PDF

Progress in Organic Coatings 138 (2020) 105381
Contents lists available at ScienceDirect
Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat
Recent Advances in durability of superhydrophobic self-cleaning T

technology: A critical review
Sanjeev P. Dalawaia, Mohamed Aly Saad Alyb, Sanjay S. Latthea,c, Ruimin Xinga,
Rajaram S. Sutarc, Saravanan Nagappand, Chang-Sik Had, Kishor Kumar Sadasivunie,
⁎
Shanhu Liua,
a
Henan Key Laboratory of Polyoxometalate Chemistry, Henan Joint International Research Laboratory of Environmental Pollution Control Materials, College of Chemistry
and Chemical Engineering, Henan University, Kaifeng, 475004, PR China
b
Department of Electronics and Information Science, Miami College of Henan University, Kaifeng, 475000, PR China
c
Self-cleaning Research Laboratory, Department of Physics, Raje Ramrao College, Jath 416404, Affiliated to Shivaji University, Kolhapur, Maharashtra, India
d
Department of Polymer Science and Engineering, Pusan National University, Busan, 46241, Republic of Korea
e
Center for Advanced Materials, Qatar University, P. O. Box 2713, Doha, Qatar
A R T I C LE I N FO A B S T R A C T
Keywords: Self-cleaning concept has achieved significant attention because of their distinct features and inclusive range of
Materials probable applications in various fields. Inspired from the lotus effect; the self-cleaning properties showed by the
Surface leaves due to the micro and nanoscopic design which reduces the water droplets adhesion to the surface, self-
Durability cleaning technology (SCT) plays a significant role in the current time in various applications. One of its special
Self-cleaning
features is its ability to keep the surface clean and maintain the self-cleaning property stable under severe
Superhydrophobic
environmental conditions over an intended period of time. This review introduces an overview of the fabrication
techniques for superhydrophobic coating and self-cleaning (SC) applications in various fields. The SCT has
applications in areas such as textiles, cotton-fabrics garments, buildings construction, lavatories, domestic-au-
tomobiles windows, architectural heritage, and photovoltaic and solar cells. As SCT has wide range of appli-
cations, there is a need for a deeper understanding of the resilience and preparation of SC surfaces. Therefore, we
have discussed the major applications of SCT in building, toilet, mineral paints for architectural heritage,
photovoltaic devices or solar cell, fabrics or textile industry in this review. Apart from this, we have also added
information regarding the techniques of SC superhydrophobic surfaces and flexible self-cleaning materials and
their applications. SCT naturally suffers from great issues in their durability and stability. As the durability of
SCT is significant in daily human life, it is intensively reflected in this literature survey. Furthermore, the on-
going progress and potential efforts in the recent innovative applications of SCT along with the critical con-
clusions, forthcoming views, and obstacles on the field of the durability of SCT are discussed in the presented
survey.
1. Introduction improvement of this field for diverse applications. The most basic
principle of self-cleaning (SC) technology is the properties of forming a
Self-cleaning is one of the most discussed topic at present due to spherical water droplet that can remove dirt particles on the surface.
their ability to clean the surface without any external source [1–9]. The The essential conditions for producing self-cleaning are the mixture of
inspiration from the lotus leaf effect due to the micro and nano-hier- surface hydrophobic epicuticular wax, and a hierarchical structure. This
archical surface morphology and low surface energy material covered can contribute to obtain high and low values of water contact angle
on the surface repels the water droplets on the surface [1–4]. Several (CA) and sliding angle (SA), respectively [10]. On the other hand, the
review articles were focused deeply on this subject and also continuous use of photocatalytic materials with hydrophilic or super hydrophilic
research works carried out by the inspiration of lotus leaf self-cleaning surfaces can also add to its excellent self-cleaning property due to easier
property and developed various novel materials for continuous degradation or decomposition of the organic contaminants through the
⁎
Corresponding author.
E-mail address: [email protected] (S. Liu).
https://doi.org/10.1016/j.porgcoat.2019.105381
Received 11 May 2019; Received in revised form 26 September 2019; Accepted 29 September 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.
S.P. Dalawai, et al. Progress in Organic Coatings 138 (2020) 105381
Fig. 1. Self-cleaning technology in various kinds of applications.
photocatalytic activity of the materials [9]. Nanotechnology is playing were tested under harsh conditions such as temperature, pressure, hu-
an important role of developing self-cleaning surfaces because of the midity, and chemical corrosion. The major difficulties faced by SCT is
use of nanoparticles alone can disperse well on various substrates more the ability to withstand the surface property under harsh environmental
uniformly and generate hierarchical morphology [11–13]. The adhe- conditions and also maintain the stability for prolonged time. Hence,
sion of mono disperses or aggregates of nanoparticles with photo- research was done to overcome the drawbacks of SCT by enhancing the
catalytic property can show better self-cleaning property. Likewise, the durability and stability of the coating under severe environmental
combination of micro-nano particles with low surface energy materials conditions by the introduction of novel materials and methodologies.
can enhance the surface roughness and water repellence behavior Designing and construction of durable and chemically stable super-
which lead to perform the self-cleaning nature on the surface. hydrophobic surfaces have become progressively meaningful and
The inspiration from nature gives an idea to produce a non-com- practical [16].
plicated and cost-efficient method to create and fabricate self-cleaning Durability enhancement of superhydrophobic surfaces is important
surfaces that is superhydrophobic and will be used in advanced appli- for SCT it is necessary to develop a good superhydrophobic coating by
cations. We also provided the use of self-cleaning technology (SCT) for using various methods such as hold limited abrasion resistance, corro-
various applications as shown in Fig. 1. A review article written by sion free, efficiency, non-hazardous chemicals, and stability.
Ganesh et al. [14] on SC coatings focused the use of hydrophilic and Researchers endorse the use of environmentally friendly chemical
hydrophobic surfaces for self-cleaning coating and their various fabri- agents such as fluorine-free organic chemical agents, which are not
cation techniques and working mechanism. Xu et al. [15], reported on toxic for humans and environmental [17]. Recently, there have been
SC with and without water on the biomimetic SC surfaces. several studies that enunciated the mechanical integrity of the super-
Fig. 2 illustrate the continuous growth of self-cleaning technology hydrophobic films, and assessed its outdoor robustness and abrasion
from the number of papers published and number of times cited for the resistance. The abrasion resistance was determined by measuring the
last 10 years. The figure also suggests the importance of this technology change in a static contact angle, CA, hysteresis, and the coefficient of
for the industrial applications. SCT is commonly used for daily appli- surface roughness [18].
cations in recent years. Self-cleaning surfaces are prepared by using Seeking for low-cost materials and developing one-step method has
hydrophilic photocatalytic materials or hydrophobic surface finishing gradually become important in fabricating SC superhydrophobic sur-
agents [1–6]. In this review article, we mainly focused on the hydro- faces. For this reason, Sas et al. [19] published a brief overview re-
phobically treated surface and their robustness. Self-cleaning surfaces porting on the idea of SC superhydrophobic surfaces and the
2
Fig. 2. Numbers of papers published (A) and numbers of times cited (B) from 2009 to 2018 under the topics of self-cleaning (Source: Web of Science).
fundamental concepts of the electrospinning procedure, therefore re- vital application requirements [28]. The main application of the su-
vealing the findings of several groups and their results on super- perhydrophobic surfaces is to grow corrosion resistant films that can
hydrophobic behaviors. An alternative approach is necessary to make sustain harsh environments [29]. New synthesis techniques and surface
the preparation of SC surfaces cost-effective as well as environment- modification methods that provide excellent adhesion and strength for
friendly. That will probably reduce time, energy, and the laundry cost the coatings on the substrates were reported [30]. It is worth men-
[20]. The SCT have also applications in medical, textiles, athletic wear, tioning that SCT is powerfully dependent on the availability and the
outdoor fabrics, and military uniform that are often used in daily life. cost of manufacturing techniques. SC materials such as Titanium Oxide
SCT fabrics are beneficial to human life as it effectively conserves water (TiO2) and zinc Oxide (ZnO) should be first identified, using a fabri-
[21]. Much of SCT has been already been reflected in our daily life in cation method, and should be tested for SC superhydrophobicity. The
different uses, such as in clothes, shoes, waterproof umbrellas and efficiency, stability, and durability of the optimized self-cleaning sur-
paints. When consumers buy a high-quality SC superhydrophobic pro- faces are thoroughly checked. Therefore, the optimal efficiency and
duct, it should have a good quality of glass of high efficiency, high durability of SCT are defined throughout this review paper.
durability, high stability and should be cost-effective. Therefore, the SC Several researchers who are interested in SC coatings reviewed the
material efficiency and durability are two most important parameters to work done in SCT [14,18–21,31–33]. Sakhuja et al. [34] thoroughly
be considered at the time of fabrication. Many obstacles faced by SCT examined the planar and nanostructure glass samples for the SC prop-
were recently resolved due to the extensive efforts that were made to erties, and their durability check was considered over an open-air ex-
enhance the SC- superhydrophobic films. As a result of the development posure period of three months; their experiment depicted the SC and
in the field of fabrication and characterization of materials at the nano- anti-reflective performance. Singh et al. [35] established a super-re-
scale, it became possible to design novel materials with special function pellent surface using zirconium dioxide particles of water-soluble si-
parameters. This resulted in strengthening of the building materials loxane emulsion on cotton fabric. They also reported that the stability
making it more flexible with greater electrical resistance. of a coated cotton fabrics (CCF) was detected by the extents of water CA
Researchers mainly focused on studying the properties of SC su- after the usage of CCF with numerous tests such as ultraviolet irradia-
perhydrophobic including durability and efficiency in detail [22–25]. tion stability, chemical stability, sandpaper abrasion test, and adhesion
Previously, scientists conducted research in the field of synthesis, for- tape tear test with recurrences that are presented in Fig. 3A. The sta-
mulation, and testing different types of SC materials and surfaces, and bility of the coating on cotton fabrics to withstand harsh external forces
had developed several technologies that were helpful to the industry. (such as pressure, temperature and bonding) was measured by the re-
Recently, SCT has been studied with a different advanced application current tear test of an adhesive tape. In their study, the cotton surface
for fields like medical, architecture, biology, and environmental en- was fixed onto an adhesive tape, and then it was stripped off as pre-
gineering [26]. The main objective of this review is to overview the sented in Fig. 3B. The synthesized material continued to be extremely
significance of SCT durability. The most relevant research studies of the resistant against all four tested solutions even after the recurrence of the
durability of SCT results were achieved in the last decade. The review tear test with the adhesion test for twenty repeated cycles with
discusses the various routes of fabrication of self-cleaning surfaces and CA > 150°. Hence, the results of the study concluded that CCF has
their applications in various fields. In addition, we also discussed the excellent stability of the covering on cotton fabric [35]. Quiroga et al.
importance of the fabrication of flexible SCT substrate and their use in tested the lasting working conditions and performance of a commer-
different applications. Besides, we delivered some general conclusions cially available SC coating of water-based titanium dioxide solution
of the most suitable fabrication methods and their applications for that was coated on three building materials that had played a sig-
studying the durability, and recommend some future scenarios on how nificant role in the present and ancient European heritage such as
to develop them. concrete, Portland-limestone, and Woodkirk sandstone [36].
The assessment of durability was calculated throughout a year of
outdoor exposure. The trail accelerated aging test was performed in the
1.1. Advances of durability in SCT
cavity with UV irradiation and condensation cycles. The results were
compared with the outcome obtained by Munafò et al. [38] and Dia-
In a 21st century, there is a major significance characteristic ne-
manti et al. [39]. The comparison of the durability studies showed
cessity for the durability of materials [27], which involves the con-
minimal color variations, but even lower for the treated samples when
servation of SC behavior during their service period, proposed at 1–2
compared with the untreated ones. Finally, it was concluded that the
years. The durability of SCT can be governed by the appropriate re-
photocatalytic action remained unaffected by concrete and sandstone,
quirements of high-temperature stability for a SC- superhydrophobic
and ordinarily after artificial ageing. Also, the photocatalytic action was
surface. Apart from this, parameters such as mechanical stability, re-
lowered due to the elimination of nanoparticles from the facial layer.
sistance to corrosion, lightweight and chemical consistency are also few
3
Fig. 3. A) Microscopic images of water (in red) and 1,2-Ethanediol (uncolored) droplets on coated cotton fabrics surface afterward 24 h of dipping in acidic, salty and
alkaline aqueous solution (these images are reproduced from ref. [35], copyright 2014, Elsevier). B) Water CA on superhydrophobic cloth subsequent to recurrent
tear test. The side image shows the tearing procedure (a) a cloth, (b) the piece of cloth was held onto a sticky tape, (c) the piece of cloth stripped off the sticky tape,
(d) H2O droplet on the piece of cloth subsequent to stripping off the sticky tape (these images are reproduced from ref. [35], copyright 2014, Elsevier). C) Dipping of
Fluorine-silicon dioxide incorporated PU − PMMA IPNs into (c) oil and (D) acid for a period 24 h, along with the following loss of plastron films in both, showing
outstanding a quick recovery from damaging and quickly recuperated functionalities (these images are reproduced from ref. [37] copyright 2016, ACS), E) Ethanol
decontamination of oil-immersed superhydrophobic glass slides is reproduced from ref. [37], copyright 2016, ACS. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
Whereas, for limestone, a reduction of Titanium dioxide concentration the tape caused damage to the coated surface. Static CA showed minor
was noted, however, the photodegradation efficacy remained un- changes in angle from 172° to 157° after single annealing at 250 °C,
changed. Wong et al. [37] introduced a cost-efficient and mass-pro- while the SA was not affected significantly. The UV stability of the
duced ultra-durable superhydrophobic films by fast template free superhydrophobic aluminum surfaces was examined by irradiating the
micro-nano texture of integrated polymer structures. UV photo- sample with UV for many hours.
degradation tests were performed for a period of 50 h deprived of any In the durability investigation, the effect of bending on SC super-
significant variations in SAs and wet CAs as presented in Fig. 3C. A hydrophobic surfaces was a crucial property [41]. Latthe et al. studied
study involving 24 h of extended immersions of the PU − PMMA − F- the bending behavior of the superhydrophobic steel surface where the
SiO2 interface into an oil analog and concentrated acid reported that steel was curved to an angle ≥90°. The wetting condition of the curved
there was no significant effect on the superhydrophobicity of the fascial surface is demonstrated in Fig.4B (a–d) [42]. Fig. 4B demonstrates the
layers (Fig. 3D). The contaminants from the oil were effectively re- diverse views of the H2O drop on the curved superhydrophobic steel
moved with a flow of ethanol subsequent to the recovery as presented surface. In the two cases, the curved surface displayed no variation in
in Fig. 3E. the superhydrophobic wetting condition and no sticking of the H2O
Varshney et al. studied the regenerated and durable super- drops on the curved surface was noted. The superhydrophobic steel
hydrophobic coatings with outstanding SC and anti-fogging behavior showed steady wetting quality under severe mechanical curving. The
for aluminum surfaces [40]. The study concluded that these types of wettability changed to sticky superhydrophobicity after the sandpaper
coatings exhibited excellent chemical, mechanical, UV and thermal scrape test and the sticky tape stripping test.
stability and also this method can be used with various size and shape The effect of the liquid–dipping time on the surface morphology and
of the aluminum surface. Moreover, this method has many other in- CA is presented in Fig. 4C. Fig. 4C (a) demonstrates a sporadic flake
dustry-related applications. The diverse phases of the sticky tape structure of 5 min on the surface. The surface was then covered with
stripping off test are demonstrated in Fig. 4A (a–b). Subsequent to countless flake structures after 15 min as demonstrated in Fig. 4C (b).
every stripping off cycle, superhydrophobicity was evidenced. It was After 30 min, the surface was homogeneously covered with the flake
also noted that the coating remain unchanged as the water droplets structures as demonstrated in Fig. 4C (c). Further, after 40 min, the
moved downwards, leaving the surface and this was repeated for 60 surface was still homogeneously covered with flake structures, but the
times of stripping as demonstrated in Fig. 4A (c–e). During the 60 cy- sizes of the flake got enlarged (Fig. 4C (d)). The SEM images showed
cles, the coating lost its superhydrophobicity and became adhesive. The that the flake structures were created progressively as the liquid-dip-
water droplets did not leave the surface, even though when the surface ping time was extending [43]. The SC and anti-fogging super-
was sloped at 90° (Fig. 4A (f)). The several adhering and stripping-off hydrophobic coating on aluminum surface were manufactured by the
4
Fig. 4. A) (a–e) Pictures of diverse phases of sticky tape stripping test and (f) microscopic picture of a H2O droplet on the adhesive superhydrophobic Al surface
subsequent to 60 times of stripping (these images are reproduced from ref. [40], copyright, Elsevier). B) Pictures of water drop on the flexible (90ᵒ) M-430-SS for 8 h
film at diverse views (a) cross view, (b) a front view; flexible M-430-SS for 8 h film > 90ᵒ(c) side view, and (d) top view. [42]. C) SEM images of the coated film
affected with the solution-dipping time periods. (a) 5 min; (b) 15 min; (c) 30 min; (d) 40 min (these images are reproduced from ref. [43], copyright 2015, Elsevier).
D) Pictures of water droplets on a flexible (about 90ᵒ) superhydrophobic aluminum film; (c) picture of H2O droplets on the superhydrophobic aluminum surface
subsequent to curving at 180 ᵒ and let it back to the initial shape (this image is reproduced from ref. [41] copyright 2017, MDPI AG).
chemical etching method. The superhydrophobic surface with water CA Metal corrosion (oxygen and moisture) is causing a serious issue to
of 170° and SA of 4° were achieved. The superhydrophobic surfaces the performance of SCT. The SC-superhydrophobic surfaces are mainly
recoiled from the high-speed water jet, signifying the outstanding used in airplane, vehicles, pipelines and marine ships for a wide range
water-repellent ability of the coated surface. The film preserved its of applications. A fundamental knowledge on how to construct such
superhydrophobicity after undertaking 100 cycles of the sticky tape surfaces using a non-complicated approach and about the surface
stripping test. The superhydrophobic behavior survived 90° and 180° of properties such as morphology, roughness, surface chemistry, surface
curving temperature, and repetitive folding and de-folding (Fig. 4D wetting, and robustness are substantial [46]. Vazirinasab et al. studied
(a–c)). In addition, the coating exhibited a significant SC property [41]. about the corrosion resistance of superhydrophobic coatings for metal
Calia et al. conducted an investigation on the SC efficiency and the surfaces such as Al, Cu, Mg, and steel. The study concluded that such
performance of photobleaching of Rhodamine B [44]. This study on phenomenon causes waste of natural resources and also degrades the
fracture-free and similar films determined an exhibition of a great infrastructure [47]. The development of corrosion immunity among
bonding to limestone and reported that the durability checks of treated these metallic surfaces is a significant application of superhydrophobic
surfaces displayed nearly unaffected Ti/Ca ratios and SC efficacies. The films. Yao et al. [48] showed that the developed superhydrophobic Cu
study also involved large adhesion failures, where the reduced Ti surface exhibits improved resistance against corrosion and durability.
quantities were observed, and coatings were fissure particularly on the Fang et al. reported that superhydrophobic films can efficiently im-
surface of the compressed limestone, together with a decreased SC ca- prove the resistance of the metal surface against corrosion hence, in-
pacity. An effective multidimensional technique has been established to creasing the possibility of utilizing superhydrophobic coating as a re-
produce robust, superhydrophobic surfaces on a wide range of mate- placement for chromate-containing treatment films to immune metallic
rials, including wood, cotton, textiles, metals, and glasses. The mod- surfaces [49]. Under severe operational environmental conditions Al
ification of this method provides a facile and efficient way to manu- undergoes surface destruction. Zheng et al. developed a corrosion-re-
facture mass-producible, mechanically robust, and robust sistant SC with an application of a stable superhydrophobic coated film
superhydrophobic surfaces with diverse applications [45]. on an Al surface that prevents the creation of ice-covering film [50].
Superhydrophobic multilayer coatings are tuned and swapped into film
wettability and redox catalytic corrosion resistance application. The
1.2. Parameters influence the durability studies of SCT
corrosion immunity of the coating remained steady even after 240 h of
contact. This improvement resulted due to the superhydrophobicity and
The durability studies of various materials can be influenced by
the anodic shift in the corrosion potential [51]. Many researchers stu-
many factors. Some major factors that affect the SCT durability are
died the stability, and durability of the superhydrophobic films that are
classified and presented in Fig. 5.
5
Fig. 5. Parameters influence the durability studies on SCT.
coated on diverse metallic surfaces in water and numerous other or- quality films including large and complex shapes of different sizes [58].
ganic-aqueous solutions. The stability of superhydrophobic surfaces A high-quality, cost-efficient, low-thermal energy, low-pressure process
over an extensive pH-range are crucial for different manufacturing that can develop rough surfaces on a diversity of oxides as a sol-gel
applications [52]. Isimjan et al. studied the influence of water, procedure has been investigated and studied. Sol-gel technique is a
chloroform and decane on the CAs of titanium dioxide/Silicon dioxide multi-step process and it has several advantages over other techniques
treated steel substrates where the measurement was done every 24 h for and for which researchers have paid more attention towards the fab-
a period of eight days [53]. It was observed that CAs remained same, rication of superhydrophobic surface using the dip-coating technique.
and the surfaces had a steady state that remained for 8 days. Sundaresan et al. developed a nano TiO2 cotton fabrics by sol-gel
The stability of SC superhydrophobic coatings against UV exposure technique [59]. The technique investigated the significant functional
is crucial, particularly for outdoor surfaces that face exposure to UV activities namely, antimicrobial, UV protection, and SC. The durability
light. This is another problem that needs consideration while in- test was carried out in the range of 32–36 washing cycles for the an-
vestigating the durability of the SC superhydrophobic surfaces. Several timicrobial properties. Kumar et al. synthesized mechanically vigorous
papers were reviewed and it was concluded that most of the SC su- films using TEOS and glycidoxypropyltriethoxysilane by using the sol-
perhydrophobic films remain constant while others required UV ex- gel method [60]. It was reported that these coatings were capable of
posure for stability. Moreover, some SC superhydrophobic films have maintaining hydrophobicity even after the removal of the upper surface
lost their superhydrophobicity under UV exposure for two hours and by accelerating scrape. These films demonstrated approximately about
also the water CA was decreased from 160 to zero degree [52]. Despite 96% SC efficiency. The established deposition method was simple, cost-
their numerous outstanding characteristics comprising chemical re- efficient, and meant for large outdoor applications that require me-
sistance, high resistance to shrinkage, ability to cure at low thermal chanically robust and durable SC properties.
energy without the presence of volatiles, once epoxy resins are sub- Satapathy et al. [61] synthesized SiO2 nanoparticles by using a dip-
jected to UV rays, it gets damaged and their durability is decreased coating technique that entrenched linear low-density polyethylene
significantly [54]. However, Gao et al. reported on the development of (LLDPE) superhydrophobic films on glass surfaces. Durable super-
highly transparent and ultraviolet-resistant superhydrophobic arrays of hydrophobic coatings with excellent SC property were studied and
silicon dioxide-coated with zinc oxide nano-rods [55]. Recent studies fabricated. They reported comparative studies of porous and non-
showed that high temperature generally decreases the durability of porous LLDPE/SiO2 films and their performances. Furthermore; they
superhydrophobic coatings that leads to an irreversible changing from also noticed that porous coatings exhibited better durability than the
hydrophobic to the hydrophilic character [55]. The stability and hu- non-porous coatings, and showed great industrial application potential.
midity of superhydrophobic wood were investigated for moisture and The PBZ/TiO2 modified polyester of non-woven fabrics were prepared
temperature aging conditions. Fractures in superhydrophobic coating by simple dip-coating and subsequent thermal curing technique which
were investigated after aging with 20 cycles [56,57]. Some of the re- resulted in outstanding mechanical durability and strong immunity to
search groups have reported that there was no significant change in UV exposure. These durable superhydrophobic fabric were effective for
superhydrophobicity after 60 or 90 days; this shows strong stability and separating oil/water combinations by gravity with high separation ef-
durability against humidity [52]. ficacy [62]. Lee et al. [63] reported that novel surface roughness and
micro/nano double-scale surface of networks were fabricated by liquid
2. Fabrication of self-cleaning surfaces processed nanoparticle coating. These structures were enhanced and it
achieved greater surface properties in both hydrophobicity and trans-
This section covers a review of the most essential results that were lucency showing a high value of H2O CA and low SA. These features
revealed out from durability studies for SCT, that are rendering the allowed excellent transparency and SC ability as well as a larger wa-
fabrication methods. Different types of material have been used to terproof capability. The feature of SC superhydrophobic and water
prepare SC superhydrophobic surfaces. Moreover, numerous techniques impacts tests are presented in Fig. 7 (a–c).
for the treatment of superhydrophobic surfaces were examined and
reported in recent years. Several fabrication techniques were used for 2.2. Chemical Deposition/Electrodeposition
the treatment of rough films such as mechanical stretching, sol-gel
process, layer-by-layer assembly, chemical and electrochemical de- In the last decade, the electrodeposition and chemical deposition
positions, chemical vapor deposition, etching, and lithography [22–26]. techniques played a significant role in the design and development of
The details of various methods involved for the fabrication of durable novel and advanced superhydrophobic surfaces and devices. The phy-
self-cleaning surfaces were discussed in the further sections (Fig. 6). sical deposition and physical vapor deposition techniques were mainly
used for the SC superhydrophobic surfaces. By using these techniques, a
2.1. Dip-coating technique number of researchers studied the improvement of materials behavior
in nanotechnology to develop and design advanced novel SC applica-
The dip-coating technique can be categorized into five phases, such tion which is supportive for life activities. Graziani et al. studied pho-
as dipping, start-up, deposition, drainage, and evaporation. The out- tocatalytic activities of titanium dioxide (TiO2) films that are used for
come of these stages of the dip-coating technique gives uniform high- clay brick surface subsequent to deposition and aging procedure [65].
6
Fig. 6. Various routes of fabrication of self-cleaning surfaces.
The results of their study showed that, the photocatalytic ability of TiO2 2.3. Layer by layer assembly
continued to be stable after ageing, thus TiO2 displayed acceptable
photocatalytic ability when it is deposited to the clay brick surface. The deposition techniques of fabricating thin film are significant in
Their durability towards organic dye was investigated by producing useful materials for diverse applications in different types of
ultraviolet alone and with wet and dry cycles. Khorsand et al. fabricated fields. The layer-by-layer assembly of nanoscale films established
an excellent hydrophobic Ni film with the micro-nano network by powerful and rising attention to the development in the obtainable
electrodeposition technique and superhydrophobic surface also showed resources and manufacturing technologies [69]. The fabrication of
outstanding lasting durability in 3.5 wt.% sodium chloride solution durable surfaces by using the nano-particle filling method that uses a
[66]. Anderson et al. developed revolutionary research in nano- simple process to make anti-icing polydimethylsiloxane super-
technology which is based on a new inexpensive and high-quality hydrophobic surface on glass [70]. Yong Li et al. invented an en-
technique to synthesize distinctive nanostructures which can degrade vironmentally safe, versatile and efficient method for SC films by using
organic matter when getting in contact with light, and directly onto the self-assembly of reformed porous chain-like silicon dioxide nano-
textiles [64]. Based on such research, it is being made possible to re- particles [71]. The superhydrophobic coatings simply and rapidly re-
place the washing machines with a little bit of sunshine. This devel- stored a few cycles after the damage has occurred; this provides a
opment places a robust basis for the forthcoming creation of fully SC strategy capable of challenging low durability. The antifouling ability of
textiles. The deposition of copper and silver using an electrodeless the superhydrophobic coating was tested and it is presented in Fig. 8A.
process that results in the creation of nanostructure quasi-spherical Qu et al. obtained mechanically durable superhydrophobicity by
copper (a1–a3) and silver (b1–b3) particles coated on single threads of reproducing the lotus leaf's ability of auto restoring μ-networks and
the cotton; representative SEM images of the fabric surface are shown in restoring hydrophobic wax layer [75]. The as-prepared material is not
Fig. 7D. only mechanically durable but also can be developed by the surface
A graded micro/nano-network translucent superhydrophobic poly- scrape. The mechanical adhesion of both dense and mesoporous tita-
tetrafluoroethylene coatings were prepared on the glass surfaces by nium dioxide films are not altered by the local and ecological enduring.
aerosol-assisted chemical vapor deposition (CVD), showing a H2O CA of Though, enduring has effects on the initial CA, efficiency, concentra-
168°, a water SA that was less than 1° and transmittance to visible light tion, the degeneration rate and the surface composition [76]. Cost ef-
that was higher than 90%. The films showed SC and anti-corrosion ficient synthesis of large-scale ultra-durable superhydrophobic films
properties [67]. The CVD technique is mechanically practical as it can was attained by fast template-free micro nanotexturing of IPNs. The
achieve the desired thickness at atmospheric pressure with a well pre- yielded films demonstrated exceptional anti-AR upholding super-
cise controlled stoichiometry. The enhancement, challenges, and pro- hydrophobic water CAs in addition to a virgin lotus effect on SAs of a
spects of CVD at atmospheric pressure on vanadium dioxide structures value lower than 10° for up to 120 continuous scrape cycles. This spray-
were considered [68]. able polyurethane-acrylic solution and surface texture provide a fast
and cost-effective method for the surface-independent manufacture of
ultra-durable, translucent self-cleaning surfaces with a superior scrape,
chemical, and ultraviolet exposure immunity [45]. The micrographs
7
Fig. 7. A) The SC ability of the enhanced non-wetting nano-particles coatings and the multipurpose application of the nano-particle films, images of the SC test with
pristine and nano-particles-treated glass before (blue line) and after (red line) SC. (B) The effectiveness of nano-particles-coated films in transmitting radiant energy
before SC with no C dust (black line), before SC with C dust (blue line), and after SC (red line). (C) Images of H2O droplets on numerous nanoparticles-coated
surfaces: glass, paper, fabric, and plastics (these images are reproduced from ref. [63] copyright 2016, IOP publishing). D) (a1–a3) SEM images of copper@Cotton,
a4) EDX spectrum acquired from scanning area shown in (a1, and a5) layered map image acquired from EDX comprising element mapping of copper and oxygen.
(b1–b3) SEM pictures of silver@Cotton, b4) EDX spectrum acquired from scanning area shown in (b1, and b5) layered map picture acquired from EDX comprising
element mapping of silver and oxygen, (these images are reproduced from ref. [64] copyright 2016, John Wiley and Sons, Inc. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)
showing the result are presented in Fig. 8B. coating deposition procedure. The durability and anti-corrosion feature
of superhydrophobic film was demonstrated by using resistance to
2.4. Spray coating water jet impact and corrosion tests in 3.5% sodium chloride solution
with long dipping time [80]. Photocatalytic silicon dioxide-titanium
Silica nanoparticles and dodecyltrimethoxysilane were coated on dioxide films on polycarbonate were prepared by using the spin-coating
glass and stainless-steel surfaces by using brush-coating, dip-coating technique for SC applications. It was described that a very thin water
and spray-coating approaches for SC and highly effective oil/water film made on the superhydrophobic surface can simply clean-off the
separations [77]. Superhydrophobic - self-cleaning surfaces were ob- dust particles while flying [81].
tained by using a mixture of cool orange-gray paint which was coated
by spraying on the fiber cement boards with white basecoats [78]. The 2.6. Electrospray/electrospinning coating technique
transparent, stable and robust superhydrophobic surfaces were treated
by a simple spray deposition procedure. The superhydrophobic surfaces The polystyrene/Al2O3 nanocomposites superhydrophobic coatings
showed excellent stability under pressurized jet water, ultraviolet ra- were prepared by new electrospinning procedures. The effect of the
diations and abrasion. These unique fabricated surfaces produced a electrospinning factors on morphology, surface roughness, and wett-
promising candidate for outdoors SC applications [79]. ability tests was studied on these coating at different techniques [82].
Superhydrophobic coating was prepared for electro-spun ultrathin fi-
2.5. Spin coating technique bers and electro-sprayed nanostructure silica micro-particles for easy
emptying packaging applications [72]. The step-by-step methodologies
A combination of hydrophobic silica particles and polystyrene were followed to organize the nanostructure multilayer LDPE/PCL/SiO2 film
used for the preparation of superhydrophobic silica coatings by a spin are presented in Fig. 8C.
8
Fig. 8. A) Three conventional solution-like pollutants comprising cloudy H2O, coffee, and orange juice stained on treated superhydrophobic paper, fabric and shoe
surfaces, respectively, to exam the anti-contamination capability of the superhydrophobic film that is reproduced from ref. [71] are reproduced from copyright 2017,
RSC. B) Intermediate cyclic damages of the Pu-PMMA-F-SiO2 coating from the 5th cycles up to the 150th cycle, with negligible damages to the IPN-F-SiO2 (images are
reproduced from ref. [45], copyright 2015 Elsevier), C) Diagram demonstrating (1) an additive manufacturing of the poly(ε-caprolactone) (PCL) fibers which is
electrospun on low- mass per unit volume polyethylene (LDPE) film, (2) fabrication of the silicon dioxide micro-particles that is electrosprayed on the surface of
LDPE/PCL film, and (3) thermal annealing of the LDPE/PCL/SiO2 coat with a hot press with no external force, images are reproduced from ref. [72]. copyright 2015,
MDPI. D) Dampening images of Cu-based materials: (a) freshly-prepared sample, (b) the sample is 10 months old; these are reproduced from ref. [73], copyright 2015
Elsevier. E) Pictures of H2O droplets that were treated with methylene blue dye on numerous surfaces: (a) glass slip, (b) cardboard, (c) a bent thick plastic film and (d)
a free-standing molded superhydrophobic material, these are reproduced from ref. [74], copyright 2015, RSC. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
2.7. Chemical etching technique 2.9. Miscellaneous techniques
The superhydrophobic films on brass surfaces were prepared by a The long-term durability of superhydrophobic is practically sig-
chemical etching technique with an amalgamation of two etchants nificant for SCT [87]. The fabrication of a non-complicated and en-
namely, HCl and HNO3. The durability of these coatings was detected vironmental friendly technique of Cu-based superhydrophobic mate-
by performing chemical, thermal, and mechanical stability tests and rials was produced. A wetting image of one of the freshly prepared Cu-
also the coatings exhibited SC and anti-fogging properties [83]. Actu- based blocks is presented in Fig. 8D a). The H2O droplets continue to
ally, the yellow SC superhydrophobic polycarbonates were manu- display a spherical shape and the CA is 153.1° and the RA has lower
factured by simple HNO3 treatment and MTCS (methyltrichlorosilane) than 8° when the same sample was put in the air for 10 months. Fig. 8D
functionalization, where the yellow superhydrophobic SC was easily b) shows that the superhydrophobic as-prepared Cu-based material
systematized by controlling dipping time in HNO3 and showed me- surfaces have long-lasting durability [73]. Zhi et al. reported a non-
chanical stability and SC properties [84]. complicated manufacturing technique of a durable superhydrophobic
top surface that was strongly attached to the surface via a middle
linking film [88]. The outcomes of scrape test indicated that the surface
2.8. Lithographic patterning technique can bear up to 180 scrape cycles on 1200 CW sandpaper under 2 kPa
applied pressure. Mechanically durable polysiloxane superhydrophobic
A non-complicated and dynamic technique that was developed to surface was prepared effectively by using polymerization of silanes
create distinct graded micro/nanostructures over large areas was fab- blending with particles [89]. The as-prepared polysiloxane surface
ricated by photolithography and reactive ion etching. These coatings displayed stable superhydrophobicity even after the surface experi-
showed a reproducible way to design and manufacture super- enced prolonged friction. The recyclable SC- superhydrophobic mate-
hydrophobic surfaces; these hierarchical structures were applicable to rials were prepared by using surface-functionalized quartz sand parti-
self-cleaning surfaces [85]. Han et al. fabricated and enhanced super- cles implanted into polyvinyl chloride. These materials show good
hydrophobic tungsten hierarchical surfaces that survived 70 scrape superhydrophobicity under 5H pencil hardness test which was main-
cycles, 28 min of solid particle impact or 500 tape stripping cycles to tained even after 500 cm abrasion test loaded into 500 g [74]. The
keep CAs of larger than 150° and SAs of lower than 20° during dur- surfaces of as-prepared superhydrophobic material that was fabricated
ability test [86]. This explains its possibility to accomplish high dur- on numerous surfaces have the static water CAs of 156 ± 1°, as pre-
ability of the superhydrophobic surfaces for practical applications. sented in Fig. 8E (a–d). Table 1 illustrate the various methods used for
SCT and their properties and potential applications.
9
Table 1
Various methods of developing durable self-cleaning surfaces and their properties.
Methods Samples Properties Ref.
Dip-Coating technique 1. Nano TiO2-cotton fabrics antimicrobial, ultraviolet protection, and self-cleaning [59]
2. TEOS and glycidoxypropyltriethox ysilane Durable, hydrophobic, and self-cleaning [60]
3. SiO2 nanoparticles- low-density polyethylene (LLDPE) Durable, superhydrophobic, and self-cleaning [61]
4. PBZ/TiO2-polyester of non-woven fabrics Durable, UV resistance, and self-cleaning [62]
Chemical deposition/ 1. TiO2-clay brick Durable, UV resistance, and self-cleaning [65]
Electrolysis 1. Ni film Durable, superhydrophobic, and self-cleaning [66]
2. Copper fabrics Durable, Organic dye degradation, self-cleaning [64]
3. Polytetrafluoroethylene Transparent, self-cleaning, anti-corrosion [67]
Layer by layer assembly 1. Polydimethylsiloxane Anti-icing, superhydrophobic [70]
2. Porous chain-like SiO2 nanoparticles Durable, Anti-fouling, superhydrophobic [71]
3. Mesoporous TiO2 films Durable, self-cleaning, photo-catalyst [76]
4. Polyurethane-acrylic solution Durable, self-cleaning [45]
Spray coating 1. SiO2 nanoparticles-dodecyltrimethoxysilane Durable, self-cleaning, oil-water separation [77]
2. Cool orange-gray paint Transparent, stable, robust, superhydrophobic [78]
Spin coating 1. Hydrophobically treated SiO2 particles and polystyrene Durable, Anti-corrosion, superhydrophobic [80]
2. SiO2-TiO2 films Superhydrophobic, self-cleaning [81]
Electrospray/ 1. Polystyrene/Al2O3 nanocomposites Superhydrophobic, self-cleaning [82]
Electrospinning coating 1. LDPE/PCL/SiO2 film Superhydrophobic, self-cleaning [72]
Chemical etching 1. HCl-HNO3-Lauric acid Superhydrophobic, anti-fouling, self-cleaning [83]
2. HNO3-MTCS Durable, superhydrophobic, and self-cleaning [84]
Lithographic patterning 1. Tungsten Durable, superhydrophobic, and self-cleaning [86]
3. Durability of SCT with recent applications containing mesoporous titanium dioxide microspheres. According to
the cycling tests, paint containing MTiO2 exhibited good photo-activity
The durability of the photocatalytic property was measured when compared to commercially available paint [100].
throughout a year of outdoor contact test and 2000 h of speeded ageing
in a chamber with ultra-violet exposure and evaporation cycles. The 3.1.1. SC toilets
outcomes demonstrated that, the photocatalytic property has been Maric et al. established and fabricated SC toilets for commercial
unchanged on concrete, however on sandstone subsequent to artificial application [101]. They concluded from their study that, the public
ageing, it was decreased because of the elimination of nanoparticles bathrooms are problematic to be kept uncontaminated and it is also
from the surface [90]. The recent progress of SC superhydrophobic difficult to periodically check the cleanliness of the place. The problem
surfaces was studied with help of strategy, and the development of was solved by developing an intelligent design of a self-operating
materials [91]. This consideration of prospectus was critically reviewed cleaning system that could be retroactively tailored into a diversity of
and the altered types of self-cleaning surfaces, fabrication techniques, toilet seats. The durability examination showed that the device is cap-
working mechanisms, and their applications used globally and studied able of surviving the surroundings of the working environments com-
for different industrial application were highlighted [92]. Jeevahan monly associated with public lavatories.
et al. presented a comprehensive review on some of the recent works in
the preparation of superhydrophobic surfaces, their possible applica-
tions, and the challenges confronted with their new applications [93]. 3.1.2. SC mineral paints for architectural heritage
Recently, more studies concentrating on the investigation of SCT for Pal et al. [102] developed mineral silicate paint to be used in ar-
different advanced applications were revealed by the literature. chitectural heritage, enhancing the durability. In this study, potassium
silicate (K2O3Si) was suggested to serve as a binder agent to provide
strength, adhesion, and durability to the concretes and stone. The SC
3.1. SC building property of the mineral silicate paint was evaluated by the photo-
bleaching of organic dyes after solar light exposure. SC activity was
The nanomaterial of titanium dioxide and silicon dioxide are mostly compared with the organic binder-based paints and commercial es-
used for construction. These are the main challenges to improve tablished paints that are highly operational stable. Fig. 9D shows the
properties like strength, durability, bond strength, corrosion resistance, image of a droplet of rhodamine B dye on three different types of
and AR. Durable SC coatings for architectural surfaces that incorporate painted surfaces. Moreover, the figure shows the dye interaction with
titanium dioxide nano-particles into hydroxyapatite films were studied solar light exposure along with the kinetics of photobleaching. The
as a potential course to provide marble with durable SC aptitude and study of Gupta et al. reported that the mineral silicate paint has seven
mechanical support [98]. It is a great challenge to construct a building times higher efficacy than the resin and commercially available paints
with SC coating activity. Using a simple and inexpensive process, su- like rhodamine B stain, and four to six times higher efficacy than the
perhydrophobic and oleophobic building surfaces have been developed methylene blue [97].
[99]. Andaloro et al. reported on the SC efficiency of titanium dioxide
and silicon dioxide-based films with cladding materials [92]. Primary 3.2. SC photovoltaic devices/solar panel
experimental examinations were accomplished to confirm the hydro-
phobic and hydrophilic behavior proceeding to the outdoor application The SCT was mainly originated from a mixture of photocatalytic
over the water CA measurements. Afterward, outdoor tests are per- oxidative decomposition of organic pollutants and superhydrophilicity
formed to screen color changing over three years confirming product originated over the spreading of the water droplets on a titanium di-
efficiency and its durability. The different cladding materials treated oxide substrate, serving the SC procedure. It was also noticed that most
with the sol product varieties and their SC performance observed over of the photocatalytic influences vanished within 5.5 years of outdoor
three years. Sols that were applied for compressed spray coating contact. For dry (waterless) environment, glass has intrinsically a nano-
methods are presented in Fig. 9A. Recently, Amorim et al. studied the structured surface to avoid settlement of dust particles on the glass
possibility of developing an efficient and durable SC acrylic paint substrate allowing H2O to spread over. Thus, the mixture of SC and
10
Fig. 9. A) Pressurized spray coating on facade cladding panels (image is reproduced from ref. [94], copyright 2015 Elsevier). B) stained PDMS-E-PET textile and (b)
printed superhydrophobic PDMS-E-PET textile [95], Procedure of covalently attaching of titanium dioxide Nanoparticles onto cotton fabric, C) Staining stability test
of the treated cotton fabrics under the ultraviolet exposure (the image is reproduced from ref. [96] copyright 2015. Elsevier). D) Photo-bleaching of rhodamine B
silicate coting, (b) resin coating, (c) commercially available coating with solar light exposure (images are reproduced from ref. [97]. Copyright 2015, Elsevier.
antireflective activities with strong durability is most suitable for SC, dyeability, toughness, thermal stability and electrical conductivity
photovoltaic devices applications [33]. The novel and facile fabrication depending on the type of nanomaterials used internally during the
methods have been invented for future practical application. Besides production such as carbon nanotubes, nano-clays, and silica or titanium
this routine completed fabrication processes of coatings (dip coating, nanoparticle [111]. IITD researchers are currently developing nano-
spray coating, and roll to roll coating) were not suited for mass and composite coatings on textile and nanofibers based on polymer nano-
large-area fabrication [103,104]. The fabrication coatings should have composites for production of functional textiles with improved dur-
high transmittance, superamphiphobicity, and excellent robustness so ability and performance. Simultaneously, Wu et al. predicted that the
as to utilize in a large spectrum of applications [105]. Han et al. es- durability of dry-wash will offer motivation for the use in difficult or
tablished a non-complicated and readily procedure to alter the cover delicate circumstances [112]. Yu et al. reported that titanium dioxide
glasses of the solar panel/photovoltaic system by using the atmospheric nanoparticles were covalently attached to cotton fabrics, initially by
pressure plasma treatment procedure [106]. The photovoltaic system esterification with MAH (maleic anhydride), and then co-grafting with
was evaluated by using a twenty-day outdoor examination that yields HEA (2-hydroxyethyl acrylate) under γ-ray irradiation as depicted in
an average of 12.79% conversion efficacy of the pristine glass-covered. Fig. 9C [96]. They demonstrated the enhancement of washing dur-
ability experiment. This was carried out to assess the adhesion force
3.3. SC fabrics/ textile industry created by the covalent bonds between titanium dioxide nanoparticles
and cotton fabrics, anchored by PHEA graft chains. Further character-
The performance of fabrics/textile goods have an imperative effect izations were carried out showing titanium dioxide nanoparticles at-
in our basic needs and in other fields such as agricultural and health tached to the cotton fiber surface after thirty expedited times of
sectors. This has led an ongoing development and invention in the area washing. Finally, they concluded that the photocatalyzed SC ability to
of nanotechnology related to the textile industry. In the recent years, functionalize cotton fabrics was well-retained [96]. The coating showed
many researchers are concentrating on research that focuses on the an outstanding ability to withstand organic solvents; an aqueous solu-
usage of nanotechnology in the fabrics/textile industry with a high tion of acid and base, and frequent washing. It was evident that this
success rate. Presently, nanotechnology is used to improve textile superhydrophobic coating can be used for development of functional
qualities, such as smoothness, durability, fire retardancy, breathability, fabrics for numerous implementations such as individual protective
yarns and water repellency [107,108]. Researchers mainly concentrate clothing. The coated films were durable to endure a hundreds of
on some of the innovative methodologies that allow the manufacturing washings. Furthermore, they have exceptional reliability against ex-
of high value-added textiles providing consumers with better level of tended soaking times of organic solvents, and acidic/base solutions
safety, aesthetics, comfort, and functional performance [109]. Re- [113]. A multi-operational superamphiphobic cotton fabric was created
searchers have designed and developed a SC cloth combining of na- by immobilizing silica nanoparticles on the surface of the cotton fabric
notechnology and multipurpose chemical finishing. Based on lotus leaf and additionally was modified by 1H,1H,2H,2H-perfluorooctyl tri-
concept, researchers established a new concept about SC and a textile chlorosilane (FOTS) where the interfacial free energy of the fabric
surface with self-cleaned system. Gupta and Gulrajani [97] reported on composite was lowered by incorporating FOTS modifier. They also
the development of self-cleaning surfaces for textiles and cotton fabrics showed the treated cotton fabrics to have high liquid resistance towards
[110]. water, colza oil and n-hexadecane with reduced surface tension, and CA
A group of scientists from the Indian Institute of Technology Delhi of 158°, 152°, and 153°, respectively. The superamphiphobic cotton
(IITD) have developed a Nanocomposite fibers with unique features of fabric possesses controllable outstanding mechanical and chemical
11
durability, SC, self-healing property, and can be used for practical ap- research and the promising efficiency, stability, and durability of SCT.
plications [114]. At present, the drawbacks of having poor mechanical strength and in-
The superhydrophobic polyethylene terephthalate textile surfaces ability to withhold the surface property under severe environmental
with a SC property was formed by preparing the microscale fibers with changes, usage of hazardous chemicals, high cost, and longer proces-
alkali and then subsequently treated with polydimethylsiloxane. sing time could lack the usage of the self-cleaning surface property for
Wettability tests revealed that the superhydrophobic textiles were several applications. The main objective of this literature survey is to
against immune acid/alkaline etching, ultraviolet exposure, and ex- explore the most efficient and durable SC superhydrophobic structures.
tended washing. The dyed or printed superhydrophobic PET (ethylene The techniques developed in the last five years such as dip-coating/sol-
terephthalate) textiles with superhydrophobic surfaces are shown in gel, CBD, CVD, spray coating, electrospray/electrospinning coating,
Fig. 9B (a, b) [95]. spin coating, chemical etching, lithographic patterning, electrolysis,
layer by layer assembly and miscellaneous were reviewed. SC super-
3.4. SC in other applications hydrophobic technology with multifunctional applications has at-
tracted great attention in recent years to various industrial applications
SCT is also used in other various applications such as anti-corrosion such as solar cell, SC toilet, textile industry, cotton fabrics, building
and anti-fouling coatings, Anti-icing in aerospace, wind blades, tur- constructions. Our critical personnel perspective and the need of future
bines, anti-freezing coatings, anti-reflective and transparent substrate development in the field of SCT is to ley by focusing on the develop-
fabrications [115–121]. In addition to these applications, SCT can also ment of reliable methods featuring ease to handle, cost-effective, stable
be applicable for the separation of oil-water and oil-emulsion separa- and durable for SCT applications. SCT still suffer from numerous
tions, cell adhesion and controlled drug release applications complications such as low mechanical stability, high cost raw materials
[116,122,123]. Owing to the excellent self-cleaning nature of the particularly used for multi-functionalities, moderate efficiency, low
coating materials and surfaces, the SCT showed much interest in var- durability, and scalable production stability, and underdeveloped
ious kinds of applications. measurement methods for adhesion to the SC- superhydrophobic. Thus,
developing flexible, bendable, renewable, and efficient responsive SCT
4. Flexible self-cleaning materials and applications is a significant issue for future investigation. A typical applications
based on durability for SCT were summarized and discussed in this
In the very recent days, flexible self-cleaning surface is one of the review.
trending topic due to wide usage of the surface on various applications With due expectations, the SCT development program might get
such as electronic devices, wearable devices and sensors, anti-reflective more attention from the researcher in the near future and also people
coating, anti-fouling and smart drug release, membrane, and super- might not need to wash their clothes because of nano-enhanced textiles
hydrophobic coatings and films [124–128]. Flexible and wearable de- with self-cleaned feature. The preparation methods of self-cleaning
vices with cleaning ability of surfaces for a prolonged time is the most surfaces should minimize the use of organic solvents and fluor-
deserving property for the industrial applications. The major drawback ochemicals, or the use of low volatile organic compounds to avoid any
of flexible self-cleaning is the loss of self-cleaning property over a possible environmental health hazards. The durability of SC techniques
period of usages or post to several bending cycles. The drawbacks can in laundries, textile and building construction is continuously im-
be overcome by enhancing the stability and durability of the flexible proving. The nature will continue to inspire with great ideas for de-
self-cleaning surface [128,129]. Recent researches were focused on velopment of user-friendly and cost-effective methods to construct self-
enhancing the mentioned properties and used for a variety of applica- cleaning surfaces with superhydrophobic for innovative applications
tions. Li et al. developed a novel smart coating material for the fabri- with enhanced durability. The introduction of self-healing or stimuli-
cation of flexible superhydrophobic surface [124]. The coating solution responsive surface property on the SCT would also improve the dur-
was prepared by dispersing the multiwalled carbon nanotubes and ability and stability of the coated materials. The continuous thrust on
magnetic nanoparticles (Fe3O4) in thermoplastic elastomer solution and the development of new technologies and easy curable coating with
spray coated on various substrates such as glass, copper, PET, and cloth superhydrophobic self-cleaning are highly needed for further develop-
followed by ethanol treatment. The fabricated substrate showed ex- ments in this field. In addition, flexible self-cleaning surface property
cellent superhydrophobic and self-cleaning property and maintained also becoming interest in the recent days, so that, more interesting
the flexibility. Moreover, the fabricated substrate also showed excellent applications in the flexible self-cleaning surfaces need to be focused
sensing ability under bending, stretching, and torsion. Following the deeply in the coming years in order to use the surface property for
surface property of cicada wings, a transparent and flexible self- wider industrial applications. It is strongly evident that novel synthesis
cleaning broadband anti-reflective film was developed [125]. Děka- methods with cost-effective and high quality must be a continuous
novský et al. developed a highly flexible PDMS and polypyrrole (PPy) target for researchers and industry.
composite with superhydrophobic and self-cleaning property. The
prepared membrane- film showed excellent flexibility, anti-fouling and 6. Conclusions
drug releasing behavior [126]. Wu et al. fabricated a highly flexible and
robust self-cleaning coatings using a fluorinated silica nanoparticle In this critical review, we have counted the latest achievements
modified with polydimethylsiloxane (PDMS) [127]. The coatings fab- related to durability of SCT, collected by their practical applications
ricated substrate showed excellent drag reduction behavior and main- such as textile industry, toilet, solar cell, cotton fabrics, building con-
tained the self-cleaning behavior under severe mechanical and abrasion struction, and flexible self-cleaning materials and applications, etc. The
test as well as strong acidic and basic conditions. Xu et al. fabricated a improvement in eco-friendly coatings of SCT are enhancing the en-
flexible superhydrophobic biomimetic surface by deposition of mono- vironmental conditions for long periods of durability by reducing time,
dispersed polystyrene (PS) spheres; casted PDMS pre-polymer and UV energy, laundry cost, etc. Here the recent progression in the durability
treated before depositing the silver film on the surface [128]. The of SCT was reviewed and discussed. The importance of the SCT in in-
fabricated substrate expressed the excellent flexibility and maintained dustrial applications needed enhanced stability and durability of the
the superhydrophobic self-cleaning behavior. coating surface. In this regard numerous researches were carried out in
the recent days for developing multi-functional and robust self-cleaning
5. Outline and future views surfaces with highly stable and durable surface properties. On the other
hand, the durability of superhydrophobic surfaces is considered as the
This critical literature survey discusses the recent developments in most important aspect that should be further strengthened in the future
12
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Authors acknowledge the support provided by program carried out veloped by mimicking hierarchical surface morphology of lotus leaf, Molecules 19
under the framework of Postdoctoral Fellowship, Henan University (4) (2014) 4256–4283.
[23] H. Yoon, H. Kim, S.S. Latthe, M. Kim, S. Al-Deyab, S.S. Yoon, A highly transparent
Kaifeng, China. This work is financially supported by DST – INSPIRE self-cleaning superhydrophobic surface by organosilane-coated alumina particles
Faculty Scheme, Department of Science and Technology (DST), Govt. of deposited via electrospraying, J. Mater. Chem. A 3 (21) (2015) 11403–11410.
India. [DST/INSPIRE/04/2015/000281]. We greatly appreciate the [24] S.S. Latthe, C. Terashima, K. Nakata, M. Sakai, A. Fujishima, Development of
sol–gel processed semi-transparent and self-cleaning superhydrophobic coatings,
support of the National Natural Science Foundation of China J. Mater. Chem. A 2 (15) (2014) 5548–5553.
(21776061) and (21950410531), Foundation of Henan province [25] A. Fujishima, K. Nakata, T. Ochiai, A. Manivannan, D.A. Tryk, Recent aspects of
(182102410090). S. Nagappan and C. S. Ha thanks to the financial photocatalytic technologies for solar fuels, self-cleaning, and environmental
cleanup, Electrochem. Soc. Interface 22 (2) (2013) 51–56.
support from the National Research Foundation of Korea (NRF) Grant [26] B.S. Yilbas, O. Keles, A.Y. Toprakli, Surface engineering towards self-cleaning
funded by the Ministry of Science and ICT, Korea applications: laser textured silicon surface, Procedia Eng. 184 (2017) 716–724.
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15

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Progress in Organic Coatings 138 (2020) 105381

Contents lists available at ScienceDirect

Progress in Organic Coatings

Recent Advances in durability of superhydrophobic self-cleaning T

Fig. 1. Self-cleaning technology in various kinds of applications.

Fig. 5. Parameters inﬂuence the durability studies on SCT.

Fig. 6. Various routes of fabrication of self-cleaning surfaces.

2.7. Chemical etching technique 2.9. Miscellaneous techniques

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