Journal of Bioresources and Bioproducts 5 (2020) 1–15

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Journal of Bioresources and Bioproducts

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

Superhydrophobic modification of cellulose and cotton textiles: Methodologies and applications

David W. Wei a , Haiying Wei b , Alec C. Gauthier a , Junlong Song

b , Yongcan Jin

b , Huining Xiao

a , ∗

a Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3, Canada b Joint International Research Lab of Lignocellulosic Functional Materials and Provincial Key Lab of Pulp and Paper Sci & Tech. Nanjing Forestry

University, Nanjing 210037, China

a r t i c l e i n f o

Keywords:

Cellulose Superhydrophobic modification Cotton textile Methodologies Applications

a b s t r a c t

Superhydrophobic cellulose-based products have immense potential in many industries where plastics and other polymers with hydrophobic properties are used. Superhydrophobic cellulose- based plastic is inherently biodegradable, renewable and non-toxic. Finding a suitable replace- ment of plastics is highly desired since plastics has become an environmental concern. Despite its inherent hydrophilicity, cellulose has unparalleled advantages as a substrate for the produc- tion of superhydrophobic materials which has been widely used in self-cleaning, self-healing, oil and water separation, electromagnetic interference shielding, etc. This review includes a compre- hensive survey of the progress achieved so far in the production of super-hydrophobic materials based on cellulose and fiber networks. The methodologies and applications of superhydrophobic- modified cellulose and fiber networks are emphasized. Overall, presented herein is targeting on summarizing some of the aspects that are critical to advance this evolving field of science which may provide new ideas for the developing and exploring of superhydrophobic and green-based materials.

1. Introduction

Cellulose is an abundant biopolymer, which is commonly used as the raw material for paper products and cotton fabrics ( Thomaset al., 2018 ). Cellulose fibres own a great number of surface hydroxyl (OH) groups, which could readily create hydrogen bonds withwater molecules, enabling water to spread over the surface. Cellulose is a hydrophilic and hygroscopic material by nature which iscapable of absorbing water. Water contact angles reported on smooth cellulose films vary between 27° and 47° ( Kontturi et al., 2011 ).The rough and porous surface structures of paper and cotton fabrics further enhance the spreading and absorption ability of waterby capillary action between the cellulose fibers. The liquid transportation driven by capillary is utilized, for example, in paper-basedmicrofluidic devices ( Ballerini et al., 2012 ). Despite its inherent hydrophilicity, cellulose has unparalleled advantages as a substrateof superhydrophobic materials. This is because of its abundance, biodegradability and unique physical, chemical and mechanical properties compared with the typically used non-renewable materials ( Song and Rojas, 2013 ).

The two general rules that superhydrophobic surfaces must fulfill apply to superhydrophobic coatings on cellulose-based mate- rials as well: 1) the coating must have an appropriate surface structure at micrometer scale, and 2) the coating must have at leastmoderately low surface energy chemistry, e.g., from hydrocarbon or fluorine compounds ( Bhattacharyya, 2013 ; Teisala et al., 2014 ).

∗ Corresponding author. Department of Chemical Engineering, University of New Brunswick, Fredericton, NB E3B 5A3, Canada. E-mail address: hxiao@unb.ca (H. Xiao).

https://doi.org/10.1016/j.jobab.2020.03.001

Available online 19 June 2020 2369-9698/© 2020 The Author(s). Published by Nanjing Forestry University. This is an open access article under the CC BY-NC-ND license. ( http://creativecommons.org/licenses/by-nc-nd/4.0/ )

D.W. Wei, H. Wei and A.C. Gauthier et al. Journal of Bioresources and Bioproducts 5 (2020) 1–15

There are various approaches to satisfy the two requirements to obtain superhydrophobic properties for cellulose-based materials such as paper and cotton. There are some criteria to evaluate the superhydrophobic surfaces, including contact angle ( > 150°), lowcontact angle hysteresis, low angle of slide ( < 10°), self-cleaning ability and the elastic collision of liquid droplets ( Eral et al., 2013 ;Bhattacharyya, 2013 ; Wu et al., 2018 ). Only when all the previously listed criteria have been met at certain conditions can a ma-terial be considered as superhydrophobic. The conditions like temperature must be specified since the wettability of the material isaffected by the temperature of the liquid; and the surface tension of a given liquid is also decreased with an increase in temperature( Bhattacharyya, 2013 ). Because of celluloses inherent hydrophilicity, the modification via chemical and physical processes to achieve the superhydrophobicity is essential. Generally, the processes involved in rendering cellulose superhydrophobic include two modi- fications of the cellulose fiber structure. The first is the roughening of the surface, which is achieved through many means such asetching, sizing of micro minerals and coating with microparticles. The second is the surface coating of cellulose with a hydrophobicchemical or polymer. The building of the structural features on the cellulose fibers has been done through several processes, such asspray coating, dip-coating, polymerization techniques, in-situ nanorod/particle growth and the plasma etching via chemical vapor deposition (CVD) ( Wang et al., 2013a ; Wang et al., 2013b ; Yu et al., 2013 ; Deng et al., 2014 ; Lin et al., 2015 ; Liu et al., 2015 ; Wuet al., 2016 ; Nechyporchuk et al., 2017 ; Tursi et al., 2019 ). Many studies achieved a superhydrophobic cellulose surface with contactangles of > 150°and angles of slide < 10°. One study achieved a sticky superhydrophobic surface, which was characterized by highcontact angle ( > 150°) but with strong adhesion to water droplets, or a high angle of slide. The study reporting the highest contactangle was carried out by Quan et al. (2009) , achieving a contact angle of 173° via a novel spray coating method.

An impressive example of (super)hydrophobic surfaces is found in nature, referring to the extreme water repellency and self- cleaning surface effect exhibited by the leaves of the lotus flower ( Shulman, 2008 ). Great efforts were devoted to the understanding ofthe relationship between the structures and super-hydrophobicity of natural creatures and the fabricating artificial superhydrophobic surfaces, as shown in Fig. 1 ( Koch et al., 2009 ). Such superhydrophobic characteristics have been widely explored for self-cleaning,anti-fogging/frosting, oil/water separation, and self-healing applications ( Nyström et al., 2009 ; Farhadi et al., 2011 ; Wang et al.,2011 ; Zhang et al., 2011 ; Zhou, et al., 2013 ; Xu et al., 2018 ). Since then, research interests on super-hydrophobicity have growntremendously, with numerous studies devoted to mimicking natural plants, animals and creatures ( Li et al., 2017 ).

Recently, different micro/nanoscale binary structured superhydrophobic surfaces with high static water contact angle and low

hysteresis opened new possibilities of applications in industrial and biological fields ( Moon et al., 2011 ). Textiles, for example, areintrinsically porous, rough, flexible and hydrophilic. At the as-fabricated state, they absorb both water and oil. For apparent reasons,it is desirable to modify the hydrophilic textile with low surface energy materials in order to overcome the intrinsic weakness ofapplications. The unique micro/nanostructures inspired by nature is required to enable super-hydrophobicity for the textile industry. Cloths with oil-water separation ability are valuable to combat the problems caused by oil spill accidents. Moreover, other novelmultifunctional applications for superhydrophobic textiles started to merge, including ultraviolet (UV)-blocking, photocatalytic,

Fig. 1. Lotus leaves in nature: self-cleaning behavior (a) and the related microstructures as observed by scanning electron microscopy (b), protrusions (c) and the wax tubules on them (d) ( Koch et al., 2009 ). Reprinted from ( Koch et al., 2009 ) with permission from Elsevier.

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flame-retardant, asymmetric superhydrophobic/super-hydrophilic, and stimuli-responsive. These represent potentially high value- added fibers that can be realized by relatively simple chemical treatment. However, there are potential issues for the health andsafety of the workers and consumers during processing and usage. Thus, attracting attention are focused on environmentally friendlypreparation methods, as well as durability and mechanical stability of the textiles.

In this review, the methodology of superhydrophobic modification is discussed in detail. The strategies of modifying the surfaces for cellulose or textiles with superhydrophobic property are categorized and discussed based on the manners of hydrophobic particlesor polymers coated on the cellulose fibers. Such superhydrophobic fiber surfaces are demonstrated with self-cleaning, oil/water separation, self-healing, UV-blocking, photocatalytic, anti-bacterial, and flame-retardant performances. Correspondingly, potential applications have been illustrated for these performances. Finally, the difficulties and challenges for practical application are briefly discussed.

2. Methodologies for Superhydrophobic Modification

There are two significant factors in fabricating a superhydrophobic surface: the appropriate hierarchical structure with durable micro/nanoparticles and a low energy surface. For textiles with a micro-scale fiber structure, a common strategy is to coat nanoscaleparticles onto the fiber surface to achieve the micro/nanoscale structure and subsequently post-fluorinate the hierarchical structure for the low energy. The most common methods for preparing robust superhydrophobic textile surfaces include physical and chemicalapproaches, such as dip-coating, wet chemical deposition, electro-assisted chemical deposition, spray coating, sol-gel, chemical etch- ing, chemical vapor deposition, plasma processing, and polymer grafting ( Wang et al., 2013a ; Wang et al., 2013b ; Yu et al., 2013 ;Deng et al., 2014 ; Lin et al., 2015 ; Liu et al., 2015 ; Wu et al., 2016 ; Li et al.,. 2017 ; Nechyporchuk et al., 2017 ; Tursi et al., 2019 ). Theseavailable fabrication technologies will be separately discussed in the following categories. The most common approaches to fabricate superhydrophobic coatings on cellulose-based materials include various dip-coating methods, spray-coating, in situ nanorod/ particle growth, CVD and plasma processing techniques.

2.1. Polymer grafting

Polymerization techniques use closely controlled chemical reactions to render a cellulose sample hydrophobic. Polymerization techniques are typically limited by the slow efficiency ( Teisala et al., 2014 ). Cellulose (C 6 H 10 O 5 ) n is a long-chain polymeric polysac-charide of glucopyranose repeating units linked together by 𝛽-1,4 glyosidic bond ( Fig. 2 ). It forms the primary structural componentof green plants. The primary cell wall of green plants is made of cellulose while the secondary wall contains cellulose with variableamounts of lignin.

The hydroxyl groups of cellulose can be partially or fully reacted with various species to provide cellulose derivatives withuseful properties. This provides an opportunity to modify the surface of cellulose/lignocellulosic by chemical reactions. Through derivatization reactions, polymers with special structures and functions can be introduced to modify the surface and attain the desiredproperties. This has been the subject of intense studies and well documented ( Cunha and Gandini, 2010 ). Due to the abundance of—OH groups in cellulose, chemicals with low surface energy, such as fluorine-containing substituents ( Cunha and Gandini, 2010 ),silicone and hydrocarbon polymers ( Pasquini et al., 2006 ) can be easily introduced by esterification with acid or anhydride ( Fig. 3 )( Song and Rojas, 2013 ).

The introduction of fluorinated polymer chains endowed cotton with a water contact angle of 155°. Since the fluorinated polymerchains were covalently attached on the surface, the super-hydrophobic cotton fabric possessed high stability and chemical durability. Lin et al. (2017) fabricated cellulose microspheres via sol-gel transition using NaOH/urea/H O as the solvent system. Due to the

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Fig. 2. Chemical structure of cellulose

Fig. 3. Esterification reactions of cellulose. R is a long fluorine-containing or hydrocarbon chain ( Song and Rojas, 2013 ).

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hydrophilic nature of cellulose, contact angle of cellulose microsphere (CM) was lower than 10°, upon modification with Fe 3 O 4

and poly (DOPAm-co-PFOEA) (derived from N -(3,4-dihydroxyphenethyl) acrylamide (DOPAm) and 2-perfluorooctyl)ethyl acrylate (PFOEA))), poly(DOPAm-co-PFOEA)/Fe 3 O 4 /cellulose microspheres (PMCM), water contact angle of the PMCM increased to 154.7°. These results indicated PFOEA moieties containing fluorinated units imparted cellulose-based microspheres a low surface energy, leading to superhydrophobicity development.

2.2. Dip-coating method

The pre-roughening and post-fluorinating technology are the most common methods available to date in the preparation of cellulose-based superhydrophobic textile surfaces. Functionalization with nanoparticles or nanofilaments or a layer of film can usually achieve the required roughness. Nanoparticles (such as SiO 2 , TiO 2 , ZnO ( Zhou et al., 2013 ; Lin et al., 2015 ; Wu et al., 2016 )) areoften used to decorate textiles surfaces to generate a roughness and durable superhydrophobic surface. In addition, some inorganicor organic chemical materials in the form of nanofilaments, nanofibers and even film layers were also reported in the literature tofabricate superhydrophobic cellulose-based surfaces ( Wang et al., 2013c ). In this section, we will discuss the fabrication technologiesin detail based on the formation type (particles, monofilaments, nano-fiber, and film) on the textile surfaces.

Dip coating is the most common method used to induce a hydrophobic surface on cellulose, which exhibits good mechanical dura-bility. It usually includes three process steps. In the first step, the surface was dipped in the coating slurry, then the surface was driedand finally cured. The coating slurry typically has multiple components which often consist of an organic solvent, surface rougheningagent and polymers to increase binding. In some cases, the surface will require additional steps to induce superhydrophobicity.

Wang et al. ( Wang et al., 2013c ) fabricated a superhydrophobic fabric via a two-step dip-coating chemical route. As shown inFig. 4 a, after coating, the fabric surface showed considerable liquid repellence to liquids with various surface tension and the contactangle remained above 150° when the tested liquid has a surface tension higher than 22.1 mN/m ( Fig. 4 b). The dependency of thesliding angle under constant liquid volume (35 mL) and constant liquid weight (0.35 g) over different surface tension was alsoinvestigated, and the results indicated that the sliding angle decreased with the increase of liquid surface tension ( Fig. 4 c). Moreover,the excellent wettability was confirmed by observing the contact angle changes on an extended period of time ( Fig. 4 d). Moreover,Nguyen-Tri et al. (2019) prepared robust superhydrophobic cotton fibers by simple dip-coating approach using chemical and plasma- etching pretreatments ( Fig. 5 ). As is shown in Table 1 , with different input variables and etching techniques, superhydrophobic cottonfabrics with high chemical and mechanical durability were successfully prepared, with contact angles up to 173°.

Fig. 4. Chemical structures of coating materials and procedure for coating treatment (a). Relationship of contact angle (b) and sliding angle (c) with surface tension and CA changes of water, hexadecane and ethanol with time (d). Redrawn from ( Wang et al., 2013c ) .

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Fig. 5. Schematic illustration of preparation of superhydrophobic cotton fabric by alkali or plasma pretreatments

Table 1

Treatment conditions for cotton febrics by one-step (a) and two-step (b–f) procedures

Sample Pretreatment Solution A step1 Solution B step2 Contact angle (°)

a Water/ethanol SiO 2 (8%) + water (300 mL) + acetic acid (2 mL) TEOS (10%) 91 ± 1 b NaOH (0.5 mol/L) SiO 2 (8%) TEOS (10%) 147 ± 1 c NaOH (0.5 mol/L) SiO 2 (10%) TEOS (10%) 152 ± 1 d NaOH (0.5 mol/L) SiO 2 (12%) TEOS (10%) 160 ± 2 e NaOH (0.5 mol/L) SiO 2 (12%) TEOS (10%) 173 ± 2 f NaOH (0.5 mol/L) SiO 2 (12%) TEOS (10%) 173 ± 2 g NaOH (0.5 mol/L) SiO 2 (12%) 2wt% of acrylic resin TEOS (10%) 167 ± 2

Note: Exceptionally, solution B is prepared in benzene instead of toluene ( Nguyen-Tri et al., 2019 ). TEOS, tetraethylorthosilicate.

2.3. Chemical bath deposition

Chemical bath deposition (CBD) technique is a low-cost fabrication process, and includes some of the important parameters such as pH, bath temperature, composition and deposition time which play a decisive role in uniformly depositing thin films by using theCBD ( Enr ı ́quez, 2003 ; Cortes et al., 2004 ; Waldiya et al., 2019 ).

Stanssens et al. (2011) synthesized a series of organic nanoparticles by imidization of poly (styrene-maleic anhydride) copolymers under pure conditions or in presence of palm oil, which can be applied as a top-coating onto cellulosic substrates. Results showedthat surface treatment of paper with organic nanoparticles provides super-hydrophobic surfaces, which are characterized by a static contact angle of 148°.

Wang et al. (2015) prepared a one-way transport oil droplet functional fabric surface by a two-step coating process to apply flower-like ZnO nanorods, fluorinated decyl polyhedral oligomeric silsesquioxane (FD-POSS), and hydrolyzed fluorinated alkylsilane. After the superhydrophobic fabric was exposed to UV light on one side, the treated fabric showed interesting one-way oil transport ability.In addition, the selective oil-transportation depends on the specific surface tension of the liquid, and by changing the UV irradiationtime, different types of oils can be selected. Such a one-way oil fluid transport material has potential application in detecting liquidsurface tension ( Fig. 6 a).

A robust flower-like hierarchically structured cotton fabric surface was prepared in situ via a one-pot hydrothermal technology, in which the cotton piece was immersed into a solution mixture and treated at various temperatures ranging from 120 °C to 200 °C( Fig. 6 b). Subsequently the remarkable superhydrophobic cotton surface was developed by the chemical modification with fluo-roalkylsilane. The flower-like hierarchical TiO 2 micro-nanoparticles were evenly coated on the cellulose fiber surface. Such special wetting superhydrophobic coating showed excellent water-repellent ability with a static contact angle larger than 160° and a dynamic sliding angle less than 5°. The facile strategy for fabricating hierarchical structure superhydrophobic TiO 2 @Cotton is expected to behelpful for designing and developing self-cleaning materials in air and underwater superhydrophobic/super-oleophilic materials.

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Fig. 6. Coating procedure and chemical structures of coating materials (a) ( Wang et al., 2015 ); Schematic diagram of a facile one-pot hydrothermal process to construct TiO 2 particle coating on fabrics (b). Redrawn from ( Li et al., 2015b ).

2.4. Electrostatic layer by layer self-assembly

Layer-by-layer (LbL) assembly is considered as a simple and efficient approach, which could incorporate functional films on substrates and have been widely applied in many fields ( Zhang and Xiao, 2017 ). Specially, owning to the facile and effective features,the electrostatic LbL self-assembly is rather appealing. It is only based on alternating adsorption of oppositely charged polyelectrolyte nano materials onto the surface of substrates without any additional advanced equipment and complex procedures ( Tian et al., 2016 ;Xiao et al., 2016 ; Zeng et al., 2018 ; Fu et al., 2019 ;).

Zhao et al. (2010) successfully prepared a superhydrophobic fabric surface via a versatile electrostatic LbL self-assembly method and a post-fluorinating strategy to construct polyelectrolyte/silica nanoparticle multilayers. Before the electrostatic self-assembly, the pristine cotton fabric was treated with specific solution to form a charged polymer film. Moreover, the surface morphologyand hydrophobicity of cotton fabric were tuned by the number of silica-nanoparticle multilayers. The fabric exhibited a weavestructure and the pure cotton fiber was very smooth ( Figs. 7 a and 7 b). When the surface was assembled with 1 or 3 layers of

Fig. 7. The SEM images of untreated cotton fabric (a and b) and cotton fabrics assembled with (PAH-SiO 2 ) n multilayers: (c) n = 1, (d) n = 3, (e) n = 5, and (f) n = 7 . Reprinted from Zhao et al., 2010 with permission from Elsevier.

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(poly(allylaminehydrochloride)-silica (PAH-SiO 2 ), the silica-nanoparticles were dispersed onto the fiber surface randomly ( Figs. 7 c and 7 d) and such a surface showed sticky property with high contact angle hysteresis. An increasing number of assemble layers couldresult in the homogeneous coverage and aggregation of silica nano-particles coated on cotton fiber surface ( Figs. 7e–7f ). The surfacesexhibited excellent super-hydrophobicity with high static contact angles and low contact angle hysteresis. The superhydrophobic surface can withstand at least 30 cycles of machine washing due to the excellent affinity between the PAH-SiO 2 and cotton fiber.

2.5. In-situ growth processing

In-situ nanorod/particle growth can occur in the gas or liquid phase and is used to assemble nano and micro structures in acontrolled manner on the sample in question. This can be used to induce superhydrophobicity, however it is typically a very time-consuming process ( Teisala et al., 2014 ).

Wang et al. (2013a) reported a general methodology for in situ growth of transition metals and the oxide nanoparticles on fabricand sponge to realize stable surface roughness, which can readily coordinate with thiol, resulting in a special wetting property ( Fig. 8 ).It was also demonstrated that multi-scale surface roughness and the special wettability can be controlled via efficient control of thegrowth of nucleation of Group VIII and IB nanocrystals. The Group VIII and IB metal oxides, as well as simple metallic substances,such as Fe, Co, Ni, Cu, and Ag could enable the fabric/sponge with different colors. The as-selected transition-metal element can notonly strongly bond with thiols, but also possess some special properties that can be utilized to realize multifunctional integration. Themultifunctional applications were mainly derived from magnetic recycling, semiconducting, and antibacterial material properties. Moreover, the as-prepared fabric and sponge via the in-situ growth method followed by thiol modification possess anti-wettabilitytowards water and can selectively absorb and filtrate oils from water with high efficiency ( Li et al., 2017 ).

2.6. Chemical vapor deposition

Chemical vapor deposition (CVD) is a chemical reaction which transforms gaseous molecules, called precursor, into a solid ma-terial, in the form of thin film or powder, on the surface of substrate ( Alf et al., 2009 , Asatekin et al., 2010 ). The CVD approach isregarded as a simple and effective method to deposit super-hydrophobic coatings onto substrates. For vapor deposition, the reac- tion temperature in the chamber is required to be higher than the boiling point of the precursor. For example, silane precursors oftrichloromethylsilane (TCMS) and dimethyl-dichlorosilane (DMDCS) require a temperature higher or close to the boiling point of the precursor, 66 °C, and 68 –70 °C, respectively ( Li et al., 2008 ; Oh et al., 2011 ). Cotton fabrics or filter papers were placed in a sealedchamber for a set time, into which a vapor of precursor was introduced. The precursor adsorbed onto the cotton fibers’ surface andpenetrated into the fibers; and the reaction between halide and hydroxyl groups then took place. An efficient reaction enhanced thecontent of covalently bound silicone to the fibers’ surfaces. After the deposition, condensation of silane polymers was required. Thisstep was conducted in an aqueous solution of pyridine (1 mol/L) at room temperature to hydrolyze the remaining Si–Cl bonds ( Li

Fig. 8. Schematic illustration of preparation procedure of superhydrophobic fabric from in situ growth of transition-metal/metal oxide nanocrystals with thiol modification. Redrawn from ( Wang et al., 2013a ) .

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et al., 2008 ). Finally, subsequent polymerization of Si–OH was accomplished in an oven at 150 °C for 10 min, which resulted in anano-scaled silicone coating tightly attached to the surface. Therefore, this method can be regarded as a special sol-gel process inwhich the precursor attaches to the surface in gaseous phase rather than in solution. One disadvantage of this process is that thewet tensile strength can be reduced, which is caused by the generation of hydrogen chloride during reaction which degrades theacid-sensitive cellulose fibers ( Oh et al., 2011 ).

Wang et al. (2013b) also reported a multifunctional fabric with electrical conductivity and super-hydrophobicity by chemical vapor phase polymerization of 3,4-ethylenedioxythiophene (PEDOT) in the presence of FeCl 3 • 6H 2 O, fluorinated decyl polyhedral oligomeric silsesquioxanes (FD-POSS) and a fluorinated alkyl silane (FAS). The chemical structure and the chemical vapor phase polymerization are illustrated in Figs. 9 a and 9 b. The addition of FD-POSS and FAS endowed the conductive coating with stableand durable super-hydrophobicity with a contact angle of 169° and 156° to water and hexadecane, respectively; however, the fabric surface with only PEDOT coating showed unstable hydrophobic properties and the water droplet will spread into the fabric matrix( Fig. 9 c) ( Wang et al., 2013b ). In addition, the surface exhibited an excellent super-hydrophobicity to liquids with surface tensionhigher than 27 mN/m ( Fig. 9 d). The FD-POSS and FAS were found to play an important role in enhancing the washing and abrasiondurability and self-healing function of the coating; meanwhile it showed little influence on the conductivity of coating. This facile andnovel strategy is expected to move forward the textile industry to durable and smart applications ( Wang et al., 2013b ; Zhou et al.,2013 ).

2.7. Wetting chemical etching

Chemical etching increases the surface roughness of fibers substrates. In case of hydrophobized microscale cellulose membranes, a simple chemical etching can yield the surface super-antiwetting behavior due to the wetting state transition ( Liu et al., 2016 ).Zhou et al. (2015) reported a robust, chemical stable superhydrophobic fabric prepared via a one-pot wetting coating method usinga coating solution containing poly (vinylidene fluoride cohexfluoropropylene) (PVDF-HFP), fluoroalkylsilane (FAS) and a volatile solvent (such as acetone) ( Figs. 10 a and 10 b). The particle-free coating made the coated fabric super-repellent to liquids with asurface tension greater than 21.5 mN/m in acetone solution ( Fig. 10 c). Such a fabric surface showed good stability under continuedliquid dropping with the static contact angle unchanged. Wu et al. (2014) reported an extremely simple solution soaking coatingin fluoropolymers (FPs) process for preparing extremely durable superhydrophobic textiles. The textiles coated under the optimal conditions show excellent superhydrophobicity and chemical stabilities.

Fig. 9. (a) Chemical structures of FD-POSS, FAS and EDOT, (b) illustration of vapor-phase polymerization to form PEDOT/FD-POSS/FAS coating on fabrics, (c) contact angle of the coated fabric changing over time from initial fluid-fabric contact, and (d) dependency of contact angle on surface tension of fluids. Redrawn from ( Wang et al., 2013b ; Zhou, et al., 2013 ).

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Fig. 10. (a) Chemical structures of coating materials and procedure for coating treatment, (b) contact angle change with time when liquid drop evaporated) and (c) dependency of CA and SA on surface tension of liquids. Redrawn from ( Zhou et al., 2015 ).

Fig. 11. Schematic of a Pulsed Laser Deposition system (a) polytetrafluoroethylene (PTFE) deposited on a cotton fiber by pulsed laser deposition (PLD) ( Song and Rojas, 2013 ) and (b) high magnification SEM micrograph showing granular morphology and nanostructure of PTFE film (c). Reprinted from Daoud et al., 2006 with permission from Elsevier.

2.8. Other methods

In addition to the above methods, there are some other methods. Daoud et al. (2006) utilized pulsed laser deposition to fabricatethin polytetrafluoroethylene (PTFE) films on cotton fabrics ( Fig. 11 ). The film deposition was carried out in vacuum at room temper-ature, and the deposition time was about 3 min. The PTFE coated fabrics showed superhydrophobic properties with water contactangle of 151°. The SEM image revealed that the PTFE film on cotton had a granular surface structure where the grain size was about50–70 nm in diameter. This was apparently the first straightforward one-step approach to fabricate a superhydrophobic coating oncotton. That is, any type of chemical modification, drying, or curing steps were not needed after application of the coating ( Daoudet al., 2006 ). Moridi et al. (2018) prepared super-hydrophobic on the fabric by exposing to air corona discharge treatment for 300W-10 min without any extra chemical modification, indicating a static contact angle of 167°. Tursi et al. (2019) grafted cellulose fiberextracted from Spanish Broom by means of low plasma process at a very low input power, which could be simply scaled for industrialpurposes. Results showed that fluorine grafted cellulose has a water contact angle higher than 160° and the adsorption capacity ishigher than 270 mg/g, making it effective adsorbent material for removing hydrocarbons from water. Li et al. (2011) grafted cellulosemicrofibrils with poly (butyl acrylate) (PBA) by atom transfer radical polymerization (ATRP) of butyl acrylate (BA) on the surface of2-bromoisobutyryl-functionalized cellulose microfibril (CMF) generating highly hydrophobic microfibrils (CMF-PBA).

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Zhang et al. (2011) presented a solvothermal synthesis of nano-porous polydivinylbenzene (PDVB) powder and demonstrated an innovative approach to apply the superhydrophobic nano-powder coating on various substrates. The as-prepared PDVB powder took a form of a solid monolith, by which the substrates were simply wiped to paint the superhydrophobic and transparent nano-porouspolymer coating. Attachment of the polymer powder on the rough paper surface occurred by the electrostatic interaction, and averagethickness of the coating was estimated to be approximately 10 𝜇m. Water contact angle on the polymer coated paper was 157° anddroplets could roll off the surface at sliding angle of 6°. The superhydrophobic properties of the coating remained stable and thecontact angle decreased only 3° in 24 h. In addition, the superhydrophobic properties of the coating were reported to remain stablealso in humid conditions. Each category of methods discussed could be carried out using a wide array of chemicals and physicaltechniques. The following discussion focused on the specific applications of superhydrophobic-modified cellulose.

3. Applications of Superhydrophobic-Modified Cellulose and Textiles

Superhydrophobic textiles fabricated by constructing appropriate surface roughness and suitable chemistry have been success- fully demonstrated for a range of applications, such as oil/water separation, self-cleaning, and multifunctional materials containing UV-shielding, flame-retardant, anti-icing, and photocatalytic properties, as well as some smart materials with self-healing, stimuli- responsive, patterning and asymmetric response ( Cao et al., 2009 ; Wang et al., 2013a ; Arslan et al., 2016 ; Peng et al., 2016 ; Shibraenet al., 2016 ; Jiang et al., 2017 ; Chen et al., 2018 ; Gao et al., 2018 ; Mi et al., 2018 ; Schlaich et al., 2018 ). In this section, we willmainly focus on the functional applications of textiles (mainly on cellulose based materials) with special wettability surfaces.

3.1. Self-cleaning application

Superhydrophobic and self-cleaning surfaces are based on the surface micro/nano morphologies ( Lu et al., 2015 ). The self-cleaningproperty of superhydrophobic cellulose is summarized as three types: physical self-cleaning, chemical self-cleaning and biological self-cleaning. Physical self-cleaning is mainly mimicking the lotus leaf surface and characterized by measuring the water contact angleand the sliding angle. Chemical self-cleaning refers to the degradation of the color stain or pollution solution using the photocatalyticeffect. The biological self-cleaning corresponds to antibacterial activity of functional fabric against a Gram-positive bacterium (e.g., Staphyloccocus aureus ) and a Gram-negative bacterium (e.g., Escherichia coli ).

Typically, superhydrophobic surfaces with the water contact angle above 150° and an ultralow sliding angle are endowed with physical self-cleaning properties. Lin et al. (2015) reported a self-cleaning cotton fabric surface coated with a superhydrophobic and super-oleophobic thin composite polymer film consisting of modified SiO 2 nanoparticles and a fluoropolymer. A water droplet and a sunflower oil rolled off from the as-prepared cotton fabric surface and brought away dirt along with it. A clear track was left behindby a spherical water droplet or oil droplet. Similarly, the cotton fabric surface coated with micro/nanoparticles subsequently modified with fluoroalkylsilane exhibited a super-antiwetting property with self-cleaning and oil/ water separation ability ( Li et al., 2015b ). Yuet al. (2013) used a new strategy to covalently immobilize TiO 2 nanoparticles onto the fabric surface by grafting polymerization of 2-hydroxyethyl acrylate (HEA) under X-ray irradiation. The resulting functional fabric showed photocatalytic self-cleaning performance when using oleic acid dyed with oil red as the organic stain. As a comparison, the colors of pristine cotton were always red no matterhow long it was exposed to the UV irradiation. Reversely, the red colors of various cotton-g-TiO 2 gradually disappeared underultraviolet irradiation because of the photocatalytic effect of TiO 2 nanoparticles on the surface.

3.2. Oil and water separation

Based on the principle of separating two different surface tension solution mixtures, the special wettability textile can be dividedinto two types: as a filtration membrane and as an absorption material. The filtration membrane allows only oil or water to permeatethrough and repels the other phase, resulting in a selective separation. The absorption material can selectively absorb water or oil onthe surface, and thus prevent the other phase from permeating into the absorbent. A facile and inexpensively one pot sonochemistryirradiation method was developed for constructing two-side superhydrophobic fabric incorporated with SiO 2 nanoparticles ( Li et al., 2015a ). The resulting fabric exhibited both super-hydrophobicity and superoleophilicity with high water contact angle of 159° and oilcontact angle of nearly 0°, which is suitable for oil/water separation. The fabric can be used for capturing and separating various oilsboth on the water surface and underwater, including toluene, chloroform, kerosene, etc. Furthermore, a superhydrophobic contact angle above 150° and excellent separation efficiency beyond 94.6% were observed after 40 separation cycles. In addition, the obtainedfabric showed stable and robust super-hydrophobicity against hot water, strong acid, alkaline, salt solution and mechanical abrasion. This stable and durable superhydrophobic fabric surface has great potential for practical applications.

Deng et al. (2014) reported a simple and practical route to develop a superhydrophobic SiO 2 -TiO 2 @PDMS hybrid film via asol-gel method, which endows the coated polyester-cotton fabric surface with super-hydrophobicity and photocatalytic effect. The SiO 2 -TiO 2 @PDMS hybrid film can be produced on a large scale and the film has high thermal stability at temperatures up to 400 °C.The as-prepared large-scale superhydrophobic cloth was also used as a filter to separate the oil/water mixture. Besides, the “filtercloth ” exhibited a considerable separation efficiency with a water contact angle above 150° and a sliding angle about 8° after tentimes of the separation experiment.

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Gao et al. (2017) prepared a hybrid polyvinylidene fluoride (PVDF)/SiO 2 microspheres based on electro-spraying and casting for super-hydrophobic coating. It was found that gravity driven oil-water separation was achieved by using the filter paper coatedwith the super-hydrophobic hybrid microspheres. More importantly, the coated filter paper could not only separate the oil withthe pure water droplets but also the corrosive droplets including the salt, acid and alkali solution. Compared with the filter pa-per coated hybrid microspheres, the free-standing membrane composed of hybrid microspheres and ultrathin threads displayed a higher oil-water separation efficiency. In addition, the flexible membrane could be used as the adsorbent for different kinds ofoil.

Cai et al. (2015) reported that highly porous TiO 2 microspheres had been prepared via a template-assisted sol-gel process with cellulose nanofibril aerogel as microsphere template. The modified porous titanium dioxide microspheres showed a typical super-hydrophobic property. The method reported in this study may be applied to fabricate other inorganic materials with desired porous structure ( Cai et al., 2015 ). Xu et al. (2018) synthesized a porous three-dimensional (3D) carbon aerogel by an environmentallyfriendly freeze-drying process and then carbonized of cellulose nanofibers (CNFs), poly (vinyl alcohol) (PVA) and graphene oxide (GO) to yield CNF/PVA/GO carbon aerogels, which had a water contact angle of 156° and high oil absorption capacity (97 times ofits own weight).

He et al. (2018) prepared bacterial cellulose aerogels/silica aerogels (BCAs/SAs) using three-dimensional self-assembled BC skele- ton as reinforcement and methyltriethoxysilane derived silica aerogels as filler through vacuum infiltration and freeze drying, which exhibited super-hydrophobicity with a contact angle of 152° and super-oleophilicity resulting from the methyl groups on the surface of silica aerogel filler. This endows the BCAs/SAs outstanding oil absorbing capability with the quality factor Q (The quality factor ( Q )was calculated with the weight (wt) of BCAs/SAs before and after absorption as following equation: Q = ( wt after – wt before )/ wt before )from 8 to 14 for organic solvents and oils.

Sobhana et al. (2017) reported that cellulose was hydrophobized by ecofriendly stearic acid through inorganic linker/interface/sandwich material namely layered double hydroxides (LDH) since the layers have affinity to both cellulose and stearic acid at molecular level. The novel idea of utilizing the charged centers on the LDH has been effectively materialized to makeconjugation with hydrophobic stearic acid and hydrophilic cellulose simultaneously, which offers not only hydrophobicity but super- hydrophobicity to cellulose network. The oil absorption and tensile strength studies show that the stearic acid -LDH-CE (stearic acidfabricated LDH- cellulose hereafter called as SA-LDH-CEL hybrid fibres) is a mandatory requirement for water-proof packaging, thin films, paper, sorbent and sanitary materials.

Oil-water separation is one of the most widely used superhydrophobic modified fibers. After oil-water separation, we can further adsorb heavy metals from the separated water, so as to further expand its application. Patrick et al. (2019) reviewed on the improvingheavy metal ion removal in wastewater.

3.3. Self-healing applications

The self-healing superhydrophobic surface can restore its water repellent property after being destroyed by acid, base, chemical reagents, and mechanical and laundering abrasion. Generally, the destroyed surface is repaired to original superhydrophobicity by heating treatment, humid environmental conditioning, and ironing treatment and so on.

Zhou et al. (2013) reported a two-step wet-chemistry coating method for durable self-healing superhydrophobic surfaces. The coated fabric exhibited excellent durability to acid, UV light, mechanical and washing abrasion. After being damaged, the fabric canrestore its super liquid-repellent performance by a short-time heating or room temperature ageing. Wang et al. (2013b) described a simple one pot mist copolymerization technology to construct healable superhydrophobic fabric. Moreover, the modified cotton fabric surface can recover its superhydrophobicity by ironing treatment after 60 cycles of laundering or 2000 times of Martindaleabrasion.

A flame-retardant and self-healing superhydrophobic coating was successfully obtained onto the cotton fabric surface via the solution-dipping method ( Chen et al., 2015 ). After etching with O 2 plasma, the resulting cotton surface was superhydrophilic. Thecoating can repetitively and spontaneously restore the superhydrophobicity by placing the damaged cotton fabric in a humid environ-ment with a relative humidity of 35% for about one hour. Similarly, the F-POSS/AgNPs/PEI (fluorinated decyl polyhedral oligomericsilsesquioxane/silver nanoparticles/poly(ethylenimine) coated cotton fabric surface was fully superhydrophilic when exposed to O 2

plasma; however, it can recover its original superhydrophobic state under an ambient environment at 25 °C and a relative humidity(RH) of 55%. The etching/healing process can be repeated for at least 16 cycles without apparent changes, showing a strong healingability of damaged superhydrophobic fabric ( Wu et al., 2016 ).

Most reported self-healing surfaces are achieved by migrating low surface energy molecules into the damaged surface to recover the special wettability. Though much literature reported on self-healing coating with extreme wettability, the usage of fluorine- containing agents is harmful for human body and environment. From this perspective, it is essential to create liquid repellent coatingwith long-term durability, self-healing and non-toxicity, which is believed to be an efficient way to overcome the poor durabilitycaused by physical and chemical damages ( Li et al., 2017 ). Liu et al. (2015) reported a new approach to construct self-healingsuper-wettability without any fluorine-containing agents. In this work, polydopamine@octadecylamine (PDA@OCA) nanocapsules were used as coating materials and added onto fabric surface using an in-situ polymerization method. When the coated fabric wasdestroyed and lost its liquid repellency, the OCA molecules could migrate to fabric surface and restore its wettability only on heatingtreatment ( Zhou et al., 2013 ). The coated fabric was treated with O 2 plasma was hydrophilic with contact angles of almost 0° forany liquids. Interestingly, when the fabric treated by plasma was heated at 80 °C, its liquid repellency was recovered. Moreover, the

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self-healing could be repeated more than 10 times. The contact angles for various liquids (water, juice, coffee and milk) on coatedfabric surface after 10 cycles of plasma and heat curing indicated that its self-healing property could be easily obtained by simpleheating.

3.4. Electromagnetic interference shielding

Recently electromagnetic interference (EMI) shielding fabrics have attracted much attention for their wide use in protecting people from harm by a variety of electromagnetic radiation sources, such as microwave oven, TV set, computer, communication devices andmobile phone.

Zou et al. (2015) reported a superhydrophobic cotton surface with durable electromagnetic interference shielding. The specific process is cotton fabric was deposited on a coating solution containing of Nafion and multiwalled carbon nanotubes (MWCNTs), inwhich Nafion was used as a linker between the pristine cotton fiber and hydrophobic MWCNTs, meanwhile providing a homoge-nous dispersion. After six cycles of the deposition process, the cotton fabric coated with Nafion-MWCNTs exhibited a water contactangle of 154.6° ( Fig. 12 a) and a favorable electromagnetic interference shielding effectiveness of 9 dB ( Fig. 12 b). Moreover, theresultant fabric also possessed good durability in electromagnetic interference shielding after soaking in water for four days or wash-ing with the American Association of Textile Chemists and Colorists (AATCC) standard (61-2013 test no. 2A) due to its excellentsuperhydrophobicity and chemical stability.

3.5. Anti-icing Applications

Another attractive application of superhydrophobic surfaces, in addition to the extraordinary water-repellence, is their excel- lent capability to reduce accumulation of snow and ice, even completely prevent ice formation in a low humidity environment.Recently, numerous studies of superhydrophobic coating on rigid metal substrates demonstrated lower adhesions to both liquid water droplets and ice than bare metals or metals covered with hydrophobic coating ( Farhadi et al., 2011 ). The anti-icing proper-ties of superhydrophobic surfaces have great potential applications in aircrafts, optical lenses, energy transmission system, power lines, wind turbines, and highways as well as building constructions ( Li et al., 2017 ). However, reports on potential anti-icing ap-plication by flexible textile surfaces are very rare. Farhadi et al. (2011) reported the anti-icing property of industrial nonwovengeo-textiles with four different samples ( Table 2 ), which exhibited de-icing and anti-icing properties compared with the controls.It was also found that surface morphologies as well as surface tension of the substrate have a great effect on anti-icing properties( Farhadi et al., 2011 ).

Fig. 12. (a) Water contact angle with various numbers of deposition; (b) Electromagnetic interference shielding effectiveness (EMI SE) of the fabrics with different deposition number at 4.5 GHz. Redrawn from Zou et al., 2015 .

Table 2

Preparation and properties of the samples

Sample Description Preparation CA (°) CAH (°)

A CeO 2 -Zonyl 8740 Spin-coating 152.4 ± 2.6 5.7 ± 2.0

B FAS-13 Etching/dip-coating 153.2 ± 2.4 6.1 ± 1.7

C Ag-Zonyl 8740 Spin-coating/anneal/dip-coating 155.1 ± 1.8 5.3 ± 1.9

D TiO 2 -RTVSR Etching/Spin-coating 154.8 ± 2.1 6.8 ± 1.5

Notes: CA, contact angle; CAH, contact angle hysteresis. Source: Farhadi et al., 2011

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4. Conclusions and Outlook

To date, many innovative methods have been introduced to fabricate superhydrophobic coatings on affordable and versatile cellulose-based materials, ranging from simple one-step processes to sophisticated multistep procedures, which all produce unique coatings with distinct properties. Superhydrophobic coatings on cellulose-based materials offer sustainable and ecological alterna- tive of fossil fuel-based polymers. In addition, superhydrophobic coatings typically possess several functionalities which cannot be achieved by traditional water repellency treatments. In fabrication of superhydrophobic coatings on cellulose-based materials, the wet-chemical methods are advantageous to create excellent durability of the coatings, which is crucial in the applications where thematerials need to stand abrasion and multiple laundering cycles. The advantage of dry methods is the simplicity: straightforwardone-step processes, where organic solvents and any additional drying or curing steps are avoided, the superhydrophobic coatings canbe readily scaled up for high-volume production; whereas the durability of coating is one of the key issues in fabrication of superhy-drophobic fabrics. In case of paper products, the ability to fabricate the superhydrophobic coating effectively in high volumes is moreimportant than the coating durability. As a result of the intensive study, many methods to fabricate superhydrophobic coatings oncellulose-based materials have been developed, and the coating properties and related phenomena are rather well understood. Future work should be increasingly focused on identifying the most suitable practical applications for the superhydrophobic cellulose-based materials. Potential applications include waterproof, stain-resistant, breathable, anti-biofouling, and self-cleaning clothing; filters for oil/water separation; and cheap and disposable products designed for short-term use, for example, water-repellent and gas per- meable packaging materials. In particular, one emerging and globally important field for cellulose-based materials is cost-effective point-of-care diagnostic devices, where superhydrophobic coatings is yet largely unexplored. Future aim is to utilize superhydropho- bic coatings in development of high-quality functional products made from renewable sources, and thus reduce the use of fossilfuel-based polymers. Due to the many inherent profitable properties such as affordability, recyclability, flexibility, breathability, and mechanical strength, superhydrophobic cellulose-based materials have a great potential to be utilized in a variety of applications in different fields. Therefore, it is worth emphasizing the importance of open-minded interdisciplinary to seek new and innovativepractical applications for superhydrophobic cellulose-based materials.

Acknowledgements

This work is supported by NSERC Canada and funding for the Joint International Research Lab of Lignocellulosic FunctionalMaterials at Nanjing Forestry University.

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