Fabrication of robust and sustainable superhydrophobic cotton fabrics via surface micro-dissolve methode for oil/water separation

Fabrication of robust and sustainable superhydrophobic cotton fabrics via surface micro-dissolve methode for oil/water separation | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Fabrication of robust and sustainable superhydrophobic cotton fabrics via surface micro-dissolve methode for oil/water separation Wanli Ji, Shaofeng Zhong This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4356473/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 18 Dec, 2024 Read the published version in Cellulose → Version 1 posted 4 You are reading this latest preprint version Abstract The preparation of durable super-hydrophobic cotton fabrics (CFs) poses a significant challenge for oil-water separation, primarily due to nanoparticle loss and the utilization of toxic auxiliaries. This study proposes a sustainable method for creating superhydrophobic CFs. Initially, CFs are treated with a mixture of NaOH and urea at low temperatures to enhance surface roughness while preserving mechanical integrity. Subsequently, hexadecyl trimethoxysilane (HDTMS) and butane tetracarboxylic acid (BTCA) are applied to reduce fiber surface energy. This combined approach results in CFs with outstanding superhydrophobic properties, boasting a water contact angle of up to 155°, surpassing nanoparticle-based surfaces. Furthermore, these fabrics exhibit remarkable mechanical and chemical stability, along with enduring washing durability. Notably, they demonstrate effective self-cleaning abilities in the presence of liquid contaminants and excellent oil/water separation performance with a high separation efficiency. The developed CFs hold promise for diverse applications in both household and industrial settings. superhydrophobic cotton fabrics nanoparticle-free NaOH/urea etching durability self-cleaning Oil/water separation Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction The indiscriminate discharge of oily industrial wastewater and frequent offshore oil spill accidents contribute to water pollution, posing a serious threat to the ecological balance crucial for human survival. Addressing the efficient and rapid separation of oil-water mixtures has become a global priority. Inspired by the "lotus leaf effect," researchers have leveraged biomimicry to develop superhydrophobic materials with unique structures, offering a straightforward and effective approach to wastewater separation (Yan et al., 2020 ; Xue et al., 2023 ; Zheng et al., 2022 ). Typically, superhydrophobic materials exhibit varying wettability towards different liquids due to the significant surface tension disparity between oil and water at the material interface, enabling selective repulsion or wetting of water and oil to achieve efficient separation of oil-water mixtures (Sam et al., 2019 ; Zhang et al., 2019 ; Xu et al., 2020 ). Cotton fabric, as a natural material, boasts advantages such as affordability, accessibility, environmental friendliness, ease of modification, good mechanical properties, and natural degradation. In light of environmental concerns, the development of fluorine-free superhydrophobic fabrics using CFs as the substrate has garnered considerable attention (Xu et al., 2022 ; Meng et al., 2020 ). Typically, finishing agents are applied to textile surfaces through dipping or spraying, incorporating inorganic nanoparticles and specialized coatings onto cotton fibers to establish micro-nanostructured roughness and low surface energy, thus achieving superhydrophobicity (Han et al., 2020; Ahmad et al., 2020 ; Xiong et al., 2019 ; Wang et al., 2013 ; Wang et al., 2023 ; Li et al., 2023 ; Cheng et al., 2018 ; Xu et al., 2023 ; Li et al., 2022 ; Song et al., 2017 ; Xu et al., 2023 ; Mohamed et al., 2021; Li et al., 2021 ; Ji et al., 2019 ). However, nanoparticle detachment compromises their efficacy and lifespan, while shed nanoparticles also pose environmental concerns, limiting their application scope. To ensure the enduring presence of nanoscale roughness on superhydrophobic CFs, employing physical or chemical techniques to micro-etch the cotton fibers' surfaces and subsequently introducing low-surface-energy substances can confer upon CFs both durability and remarkable superhydrophobicity (Xu et al., 2023 ; Xu et al., 2022 ; Li et al., 2022 ; Xu et al., 2020 ; Yang et al., 2022 ; Shanmugavelayutham et al., 2021 ). Cheng et al. ( 2019 ) treated cotton fibers with a 7.5% mass fraction of sulfuric acid, followed by the introduction of a crosslinker, epoxy soybean oil resin, combined with stearic acid to create superhydrophobic cotton fibers devoid of nanoparticles. These fibers exhibited outstanding mechanical stability and chemical properties, maintaining excellent superhydrophobicity even after undergoing tape stripping, ultrasonic treatment, solvent corrosion, and exposure to low/high temperatures. Additionally, using cellulase to etch cotton fiber surfaces yielded similarly impressive results in mechanical properties and resistance to various treatments (Cheng et al., 2019 ). However, such treatments may lead to a decrease in CFs' mechanical properties. Yao et al. ( 2021 ) utilized oxygen plasma to etch cellulose fiber surfaces, enhancing their roughness and activating hydroxyl groups to undergo condensation reactions with trisilanol butyl polyhedral oligosiloxane (TS-POSS), thereby grafting it onto the fiber surfaces. The resulting superhydrophobic cellulose/TS-POSS material exhibited a static water contact angle of 152.9°. Nguyen-Trig et al. ( 2019 ) achieved superhydrophobic CFs via dip-coating with NaOH and plasma etching treatments, followed by deposition of silica nanoparticles and tetraethyl orthosilicate (TEOS), yielding a water contact angle of 172°. Nonetheless, the use of plasma equipment proves costly and impractical for large-scale application. Cai et al. successfully dissolved low-polymerization cellulose in an aqueous NaOH/urea solvent system at low temperatures (-10℃), enhancing the stability of the cellulose solution (Cai et al., 2005; Lue et al., 2009). Alkali/urea chemical etching treatment resulted in the formation of concave-convex structures and grooves on the cellulose material surface, altering the fibers' mechanical properties (Zhang et al., 2016 ; Lu et al., 2018 ). In this study, we present a green, nanoparticle-free, fluorine-free, and sustainable approach to fabricating superhydrophobic CFs. CFs were etched using a NaOH/urea solution under low-temperature conditions to create micro-nano rough surfaces. Subsequently, the modified CFs were impregnated with a solution of hexadecyltrimethoxysilane (HDTMS) and butane tetracarboxylic acid (BTCA) to reduce the fibers' surface energy and enhance superhydrophobic durability. These superhydrophobic CFs exhibited exceptional mechanical robustness, durability, and self-cleaning properties. Most importantly, these sustainable superhydrophobic CFs demonstrated outstanding efficiency and reusability in oil/water separation applications. Experimental section Materials Sodium hydroxide, urea, sulfuric acid, butane tetracarboxylic acid (BTCA), sodium hypophosphite (SHP), and cetyltrimethoxysilane (HDTMS) were procured from Sinopharm Medicine Holding Co., LTD. (China). Dichloromethane, n-hexane, and toluene were obtained from Guangzhou Reagent Co., Ltd. (China). Cotton fabrics (CFs), petroleum ether, and crude oil were sourced from a local store in Shaoxing (China). All chemicals used were of analytical reagent grade and were utilized without further purification. Deionized water served as the solvent for all experiments. Fabrication of superhydrophobic cotton fabric The CFs were first cleaned using ultrasound in a solution of distilled water and ethanol for 30 minutes, followed by drying. A NaOH/urea aqueous solution was then prepared and cooled to -10 ℃ for 30 minutes. Subsequently, the cleaned CFs were immersed in this solution (with a bath ratio of 1:20) at low temperature for a specified duration and padded (with a wet pick-up of 80%) to micro-dissolve the superficial zone of the CFs (referred to as E-CFs). Next, the E-CFs were immersed in a coagulating bath containing 5 wt% H 2 SO 4 and 5 wt% Na 2 SO 4 for 5 minutes to remove residual sodium hydroxide and coagulate the cellulose molecules on the surface of the E-CFs. The treated E-CFs were then washed with deionized water and dried at 80 ℃. Subsequently, the E-CFs were immersed in a mixed solution (with a bath ratio of 1:20) of HDTMS, BTCA, and SHP for 20 minutes and padded (with a wet pick-up of 80%). This dip-padding process was repeated several times. Finally, the treated samples were dried at 100 ℃ and cured at a high temperature for 3 minutes to obtain the superhydrophobic CFs. Characterization The surface morphologies were examined using scanning electron microscopy (SEM, Quanta250, FEI) and atomic force microscopy (AFM, SPM9700, Shimadzu). The chemical structures of the samples were analyzed using X-ray photoelectron spectrometry (XPS, Escalab 250Xi, Thermo Fisher Scientific) and attenuated total internal reflectance Fourier transform infrared spectrometry (ATR-FTIR, Nicolet iS10, Thermo Scientific, America). Water contact angles (CAs) were measured using a contact angle meter (CAM, JC2000D2, Shanghai Zhongchen Digital Technology Equipment Co., Ltd, China) with 5 ml of deionized water at room temperature. Average CAs from five different positions on the fabric surface were reported for each sample. The washing durability of the coated cotton samples was evaluated according to AATCC Test Method 61-2006 under condition 2A. Abrasion durability was assessed following AATCC 165–2007 standard. Breaking tenacity was measured using the raveled strip method as per IS-1969-1985 specification with a universal material testing machine (Instron 3365, USA). Bending length was determined following GB/T 3923.1.1–2013 standard using an electronic fabric stiffness tester (Ningbo Textile Instrument Co., Ltd., China). The whiteness index of the samples was directly evaluated using the Hunter LabScale formula with an X-Rite COLOR i7 computer color matching instrument (USA). Moisture permeability was investigated using a digital moisture permeability measuring instrument (YG501D-II) following GB/T 14704.2–2009 standard: textile fabric moisture permeability test, using the positive cup method. Results and discussion Preparation and surface morphology of superhydrophobic fabrics The sustainable superhydrophobic CFs were fabricated through a mild and eco-friendly two-step process, outlined in Fig. 1 . Initially, a NaOH/urea solution was employed to dissolve the surface of cotton fibers in an aqueous solution at -10 ℃, without the introduction of any non-fiber bulk materials. This process facilitated the creation of a stable micro-nano rough structure on the cotton fiber surface, referred to as E-CFs. Subsequently, the E-CFs were immersed and heat-cured using HDTMS, BTCA, and SHP aqueous solutions. HDTMS, a silane compound, served as the hydrophobic agent, while BTCA functioned as a crosslinking medium. BTCA's carboxyl group underwent conversion into an unstable intermediate with the aid of sodium hypophosphite (SHP) acting as a catalyst. This intermediate then reacted with the hydroxyl group of HDTMS and the cotton fibers to form ester bonds, resulting in the formation of durable superhydrophobic fibers. To simplify, the modified E-CFs treated with HDTMS/BTCA were denoted as HDTMS/BTCA/E-CFs. The surface roughness of CFs was induced through NaOH/urea etching at -10℃ for 1 hour, as depicted in Fig. 2. Initially, the surface morphologies and roughness of CFs after etching with different NaOH concentrations were assessed using SEM and AFM. Initially, the pristine CF surface appeared smooth, with corresponding root mean square (RMS) and arithmetic average roughness (Ra) values of 3.4 nm (Fig. 2a,e). Upon treatment with a 6 wt% NaOH solution, numerous grooves formed on the fiber surfaces, resulting in an increased Ra value of the E-CF to 6.5 nm (Fig. 2b,f), indicating successful integration of nanoscale and microscale roughness on the fiber surfaces. With higher NaOH concentrations, both the depth and number of gaps on the fiber surfaces increased, leading to further elevation in surface Ra values. Interestingly, the Ra value of CF treatment with a 6 wt% NaOH solution was 12.7 nm. Notably, upon further increasing the NaOH concentration to 14 wt%, the Ra value decreased to 12.1 nm, accompanied by the formation of a new morphology resembling insect phagocytosis (Fig. 2d,h). This phenomenon can be attributed to the ineffective encapsulation of a large number of dissolved flocculent chain segments by urea, resulting in their adsorption onto the fabric surface and subsequent formation of a cluster-like "insect phagocytosis" structure (Cuissinat et al., 2008; Zhang et al., 2016 ). Figure 2 SEM images and AFM topography images of CF (a, e) and E-CFs obtained after treatment with NaOH and urea solution for 6% NaOH/9% urea solution (b, f), 10% NaOH/13.5% urea solution (c, g) and14% NaOH/21% urea solution (d, h), respectively To further refine the experimental conditions for developing hydrophobic surfaces, the impact of NaOH concentration on the surface wettability of HDTMS/BTCA/E-CFs was investigated. In this study, the concentration of HDTMS was maintained at 4 wt%, while the concentrations of BTCA and SHF were fixed at 3%. As depicted in Fig. 3 a, when utilizing a 4% NaOH solution, HDTMS/BTCA/E-CFs exhibited only modest hydrophobicity with a contact angle (CA) value of 144°. Elevating the NaOH concentration from 6–10% resulted in an increase in CA from 151° to 155°. However, further escalation of the NaOH concentration to 14% did not enhance the hydrophobicity of HDTMS/BTCA/E-CFs. This phenomenon can be attributed to the deposition of flocculent cellulose, which covered the surface of the initially deep and dense gap structure, thus creating a rough surface resembling "insect phagocytosis." This surface topology was relatively flat and exhibited lower roughness (Cuissinat et al., 2008; Zhang et al., 2016 ). Etching processes can introduce inherent roughness to fabric surfaces, but traditional chemical etching methods often compromise the mechanical properties of fabrics. Hence, the mechanical properties of various E-CFs were investigated. In Fig. 3 b, the relationship between the breaking strength of the samples and NaOH concentration is illustrated. Unlike conventional chemical etching methods for fabrics, the breaking strength of fabrics increased from 354 to 416 N with an increase in NaOH concentration from 2 to 14 wt%. This enhancement in breaking strength can be primarily attributed to the contraction and tightening of fabrics induced by fiber swelling. Simultaneously, some fibers underwent reduced twisting and further splitting, contributing to the overall increase in fabric breaking strength (Zhong et al., 2016 ). Surface Composition The chemical structures of the original and treated CFs were analyzed using XPS. In Fig. 4 a, the pristine fabric surface exhibited characteristic peaks of O1s (531 eV) and C1s (284.7 eV) (Xu et al., 2022 ; Kang et al., 2019 ). Conversely, the modified fabric displayed new characteristic peaks of Si 2s (153 eV) and Si 2p (101 eV) (Rahman et al., 2021 ), indicating successful incorporation of HDTMS onto the fabric surfaces. FTIR spectroscopy was employed to further examine the chemical composition of the coated CF, as illustrated in Fig. 4 b. Relative to the pristine fabric, a shoulder peak emerged around 1722 cm − 1 , attributed to the characteristic C = O stretching of BTCA (Schramm et al., 1997 ; Rilda et al., 2019 ). It's worth noting that the distinction between the binding of BTCA and HDTMS was challenging due to the overlap of ester peaks (Hernández-Padrón et al., 2004 ). The absorption peak at 2840 cm − 1 corresponded to the stretching vibration peak of CH in the long chain of the hydrophobic compound HDTMS (Xu et al., 2022 ; Rahman et al., 2021 ). Simultaneously, the vibration absorption peaks representing the Si-O bond appeared at 894 cm − 1 and 463 cm − 1 (Xu et al., 2016 ; Wang et al., 2021 ), further confirming the grafting of HDTMS onto the fibers. Mechanical durability and chemical stability In practical applications, the durability of superhydrophobic materials is paramount. To assess the mechanical robustness and environmental durability of superhydrophobic CFs, their wettability after exposure to various harsh conditions was investigated. In this study, the effective strategy of constructing inherently rough structures through surface micro-dissolve treatment of CFs and forming covalent bonds between CFs and HDTMS using BTCA was employed to enhance the durability and robustness of the superhydrophobic surface. Here, the mechanical damage and chemical stability of the superhydrophobic CFs were evaluated by measuring water contact angles (CAs), as depicted in Fig. 5 . The resistance against mechanical damage of superhydrophobic CFs was assessed, as illustrated in Fig. 5 a. The CAs of the superhydrophobic CFs experienced a slight decline after 800 abrasion cycles, with further decreases as the number of abrasion cycles increased. Nevertheless, even after 4000 cycles, the CAs remained as high as 148°, indicating remarkable resistance against abrasion. Furthermore, the laundering durability of HDTMS/BTCA/E-CF was evaluated using a standard laundering method (AATCC 61-2006, condition 2A). Figure 5 b illustrates the change in CAs of the modified fabrics after repeated washing. After 30 washing cycles, the CAs of the superhydrophobic CFs gradually decreased from an initial 154° to 149°, suggesting that BTCA effectively facilitated firm binding between HDTMS and the fabrics, rendering the coating difficult to peel off. It is noteworthy that the CA of HDTMS/BTCA/E-CFs slightly increased after five washes. This could be attributed to the dissolution of SHP crystals embedded in the fiber surfaces during the washing cycles, resulting in increased surface roughness (Isobe et al., 2005 ). In addition to physical abrasion, the chemical stability of HDTMS/BTCA/E-CFs was evaluated by immersing modified fabrics into water solutions with pH values ranging from 1 to 14 for 48 hours. Figure 5 c demonstrates that superhydrophobic fabrics exhibited satisfactory durability across the pH range, with contact angles exceeding 150°. Furthermore, the CAs of HDTMS/BTCA/E-CFs were tested at different droplet temperatures. It was observed that the CAs changed only slightly when the droplet temperature was below 70°C (Fig. 5 d). Unfortunately, beyond 70°C, the CAs decreased from 150°C to 121°C. This can be attributed to the decrease in water surface tension with increasing temperature, leading to enhanced wetting ability of droplets on fiber surfaces and consequently, decreased CAs (Liu et al., 2009 ; Zhang et al., 2023 ). Water-proofing, anti-fouling and oil/water separation The stain resistance and self-cleaning properties of the prepared superhydrophobic carbon fibers (CFs) were evaluated, with results presented in Fig. 6 (a-f). When the superhydrophobic fabric was exposed to a flowing faucet, the water droplets were completely repelled from the fabric's surface, leaving no trace or moisture behind (Fig. 6 a). Additionally, common liquids such as milk, coffee, and dyed water were applied to the treated white fabric, as depicted in Fig. 6 b. The droplets on the superhydrophobic surface maintained a spherical shape and did not soak into the fabric, indicating the material's excellent stain resistance. To further demonstrate the stain resistance abilities of HDTMS/BTCA/E-CFs, methylene blue dye was applied to an inclined superhydrophobic fabric, which was then rinsed with water. As the water droplets rolled down the inclined surface, they carried the dye away, leaving the fabric unstained (Fig. 6 d-f). These results confirm that the transparent superhydrophobic coating provides effective self-cleaning and stain-resistant protection for fabrics. Though the HDTMS/BTCA/E-CFs exhibited excellent water repellency, they had extremely poor oil repellency, a property that proved beneficial for oil-water separation applications. The oil-water separation capacity of HDTMS/BTCA/E-CFs was tested, using the superhydrophobic fibers as a filter in an oil-water mixture containing 10 mL of dichloromethane (dyed red) and 10 mL of water (dyed blue). As the mixture was poured through a funnel, the oil droplets quickly penetrated the superhydrophobic surface and passed into the bottom container, while the water droplets remained on top (Fig. 7 a). Further investigations examined the separation efficiency and flux of various oil-water mixtures, including n-hexane-water (H-W), toluene-water (T-W), petroleum ether-water (P-W), and crude oil-water (C-W). Figure 7 b shows that the separation efficiencies for all mixtures exceeded 98%. As for flux, low-viscosity organics like dichloromethane, n-hexane, toluene, and petroleum ether had high fluxes ranging from 60 to 70 kLm − 2 h − 1 , whereas the flux for high-viscosity crude oil was only 5.8 kLm − 2 h − 1 due to its high adhesion. To assess the reusability of the prepared fibers, their separation efficiencies and contact angles were measured after 20 consecutive uses with dichloromethane-water and crude oil-water mixtures. Figures 7 c and 7 d demonstrate that the separation efficiencies remained above 98% and the contact angles above 150°, indicating remarkable reusability. The experimental results confirm that the superhydrophobic HDTMS/BTCA/E-CFs exhibit high oil-water separation efficiency, good flux, and sustainable reusability, attributes that stem from their robust mechanical durability and chemical stability. physical properties Other physical properties of the pristine and treated cotton fabrics were tested, the results are shown in Table 1 . Table 1 Physical properties of raw and modified fabrics Treatments break strength(N) Moisture permeability (mg/(cm 2 ·h)) whiteness index (hunter) CFs 357 1.139 86.1 E-CFs 423 0.993 85.3 HDTMS/BTCA/E-CFs 326 0.914 85.7 As depicted in Table 1 , chemical corrosion led to a notable enhancement in fabric strength, reaching approximately 118%. Subsequent treatment with HDTMS and BTCA resulted in a relatively significant loss of fiber strength. This can be attributed primarily to the cross-linking effect of BTCA, which restricts the relative sliding of cellulose macromolecular chains, particularly under high temperature and acidic conditions (Huang et al., 2011 ). However, when compared to conventional CFs, HDTMS/BTCA/E-CFs exhibited lesser damage. Although the moisture permeability of the superhydrophobic fabrics experienced a slight decrease, the whiteness remained largely unchanged. This can be attributed to the formation of a network structure on the fiber surface due to the coating, which partially closed the gaps between fibers. Additionally, the low film density of the small HDTMS molecule layer resulted in a minor reduction in moisture permeability. However, the decrease in strength was more pronounced. Conclusion We have successfully developed fully sustainable, nanoparticle-free, and fluorine-free superhydrophobic cotton fabrics (CFs) through a process involving NaOH/urea pretreatment, which had no detrimental effect on the mechanical properties of the fabrics. This was followed by surface modification using the low-energy substrate HDTMS, crosslinked with BTCA. The resulting cotton fabric exhibited outstanding superhydrophobic properties, with a water contact angle reaching up to 155°. Moreover, these superhydrophobic CFs demonstrated remarkable durability, maintaining their surface superhydrophobicity even after exposure to mechanical abrasion, laundering, chemical agents, and high temperatures. Furthermore, the superhydrophobic CFs exhibited excellent self-cleaning properties when subjected to liquid pollutants. Most notably, they demonstrated exceptional oil/water separation performance, achieving high separation efficiency. Additionally, these CFs displayed impressive reusability, with the surface contact angles remaining unchanged even after 20 cycles of reuse. Overall, the nanoparticle-free, fluorine-free, and robust nature of these superhydrophobic CFs presents them as promising candidates for eco-friendly and efficient oil/water separation applications. Declarations Acknowledgments This research was supported by the Basic Public Welfare Research Program, funded by Department of Science and Technology of Zhejiang Province, China, under award No. LGG20E030001. Key Investment Plan for High-level Talents is supported by Zhejiang Industrial Polytechnic College under award No. 112709010921621119. Functional Textile Dyeing and Finishing Technology Innovation Team is funded by Shaoxing City government, Zhejiang, China under award No. 222709010921621502. The authors acknowledge the support in part through services provided by Analysis Test Management Platform of Zhejiang University, China, and College of Bioresources Chemical & Materials Engineering, Shaanxi University of Science and Technology, China. Funding The Basic Public Welfare Research Program is supported by Zhejiang Provincial Natural Science Foundation, China under award No. LGG20E030001. The research was supported by Key Investment Plan for High-level Talents of Zhejiang Industrial Polytechnic College under award No. 112709010921621119. Functional Textile Dyeing and Finishing Technology Innovation Team is supported by Shaoxing City government, Zhejiang, China under award No. 222709010921621502. Ethics declarations Conflict of interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Ethical approval Not applicable, no animal or human studies. References Yan XJ, Zhu XW, Ruan YT, Xing TL, Chen GQ, Zhou CX (2020) Biomimetic, dopamine-modified superhydrophobic cotton fabric for oil-water separation. Cellulose 27(13):7873-7885. https://doi.org/10.1007/s10570-020-03336-x Xue QW, Wu JQ, Lv ZS, Lei Y, Liu XG, Huang YF (2023) Photothermal Superhydrophobic Chitosan- Based Cotton Fabric for Rapid Deicing and Oil/Water Separation. 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Prog Org Coat 146:105727. https://doi.org/10.1016/j.porgcoat. 2020.105727 Yang X, Su J, Xiong JJ, Wang HB (2022) A self-healing fluorine-free superhydrophobic cotton fabric under heat stimulation. Text Res J 92(17-18): 3049-3059. https://doi.org/10.1177/00405175211037189 Shanmugavelayutham G, Anupriyanka T, Bhagyashree P, Premasudha P (2021) Plasma Surface Modification of Cotton Fabric by Using Low Pressure Plasma, IEEE Trans Plasma Sci 49(2):497-501. https://doi.org/10.1109/TPS.2020.3015709 Cheng, QY; Zhao, XL; Li, YD; Weng, YX; Zeng, JB. (2019) Robust and nanoparticle-free superhydrophobic cotton fabric fabricated from all biological resources for oil/water separation. Int J Biol Macromol 140:1175-1182. https:// doi.org/10.1016/j.ijbiomac.2019.08.216 Cheng QY, Zhao XL, Weng YX, Li YD, Zeng JB (2019) Fully sustainable, nanoparticle-free, fluorine-free,and robust superhydrophobic cotton fabric fabricated via an eco-friendly method for efficient oil/water separation. ACS Sustain Chem Eng 7(18): 15696-15705. https://doi.org/10.1021/acssuschemeng.9b03852 Yao MZ, Liu Y, Qin CN, Meng XJ, Cheng BX, Zhao H, Wang SF, Huang ZQ (2021) Facile fabrication of hydrophobic cellulose-based organic/inorganic nanomaterial modified with POSS by plasma treatment. Carbohydr Polym 253: 117193. https://doi.org/10.1016/j.carbpol.2020.117193 Nguyen-Trig P, Altiparmak F, Nguyen N, Tuduri L, Ouellet-Plamondon CM, Prud'homme RE (2019) Robust superhydrophobic cotton fibers prepared by simple dip-coating approach using chemical and plasma-etching pretreatments. ACS Omega 4: 7829-7837. https://doi.org/10.1021/acsomega.9b00688 Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5(6): 539-548. https://doi.org/10. 1002/mabi.200400222 Lue A, Zhang LN (2009) Advances in Aqueous Cellulose. ACS Sym Ser 1033:67-89 Zhang H，Zhong Z，Feng L (2016) Advances in the performance and application of hemp fiber. Int J Simul Model Syst Sci Tech 17(9):181-185. https://doi.org/10.5013/ IJSSST.a.17.09.18 Lu M, Hu RM, Zhao ZY, Zhou J, Liu YP (2018) Surface micro-dissolve treatment of cotton fabrics with sodium hydroxide/urea to impart crease-resistance properties. Text Res J 88(14): 1671-1676. https://doi.org/10.1177/0040517517708534 Cuissinat C, Navard P (2008) Swelling and dissolution of cellulose, Part III: plant fibres in aqueous systems. Cellulose 15(1):67-74. https://doi.org/10.1007/s10570- 007-9158-4 Zhang JM, Luo N, Zhang XY, Xu LL, Wu J, Yu J, He JS, Zhang J (2016) All-Cellulose Nanocomposites Reinforced with in Situ Retained Cellulose Nanocrystals during Selective Dissolution of Cellulose in an Ionic Liquid. ACS Sustainable Chem Eng 4(8):4417-4423. https://doi.org/DOI10.1021/acssuschemeng. 6b01034 Zhong ZL, Liao ZD, Lu LL (2016) The Influence of LiCl/DMAc Microdissolution Treatment on Tensile Property of Hemp/Cotton Blended Yarn. J Nat Fibers 13(5):578-584. https://doi.org/10.1080/15440478.2015.1083927 Kang HX, Zhao BW, Li LX , Zhang JP (2019) Durable superhydrophobic glass wool@polydopamine@PDMS for highly efficient oil/water separation. J Colloid Interface Sci 544:257-265. https://doi.org/10.1016/j.jcis.2019.02.096 Rahman MA, Lee S, Park CH (2021) A Facile and Non-toxic Approach to Develop Superhydrophobic Cotton Fabric Using Octadecylamine and Hexadecyl- trimethoxysilane in Aqueous System. Fiber Polym 22(1):131-140. https://doi.org/ 10.1007/s12221-021-9645-5 Schramm C, Rinderer B, Bobleter O (1997) Kinetic data for the crosslinking reaction of polycarboxylic acids with cellulose.J. Soc. Dye. Colour., 113: 346-349. Rilda Y, Safitri R, Putri YE, Refinel R, Agustien A, Leaw WL, Nur H (2019) Hexamethyldisiloxane-modified ZnO-SiO 2 -coated superhydrophobic textiles for antibacterial application. J Chin Chem Soc 66(6):594-599. https://doi.org/10.1002/ jccs.201800324 Hernández-Padrón G, Rojas F, Castaño VN (2004) Ordered SiO 2 -(phenolic- formaldehyde resin) in situ nanocomposites. Nanotechnology 15(1):98-103. https://doi.org/10.1088/0957-4484/15/1/019 Xu LH, Wei ZH, Shen Y, Zou Ｒ, Li Q (2016) Preparation of Flexible Superhydrophobic Cotton Fiber Surfaces Using Modified SiO 2 Sol. Bull Chin Ceram Soc 35 (4):1254-1259 Wang ZX, Ji JY, Nie YP, Wang J, Zhang D (2021) Preparation of super-hydrophobic cotton fabric using polydopamine/folic acid. Polym Mater Sci Eng 37(12):103-110 Isobe H, Utsumi S, Yamamoto K, Kanoh H, Kaneko K. (2005) Micropore to macropore structure-designed silicas with regulated condensation of silicic acid nanoparticles. Langmuir 21:8042-8047. https://doi.org/10.1021/la0509192 Liu YY, Chen XQ, Xin JH (2009) Can superhydrophobic surfaces repel hot water?. J Mater Chem 19(31): 5602-5611. https://doi.org/10.1039/b822168e Zhang BB, Qiao MY, Ji GJ, Hou BR (2023) Durable corrosion resistant and hot water repellent superhydrophobic bilayer coating based on fluorine-free chemicals. J Ind Eng Chem 119:346-356. https://doi.org/10.1016/j.jiec.2022.11.055 Huang WQ, Xing YJ, Yu YY, Shang SM, Dai JJ (2011) Enhanced washing durability of hydrophobic coating on cellulose fabric using polycarboxylic acids. Appl Surf Sci 257(9): 4443-4448. https://doi.org/10.1016/j.apsusc.2010.12.087 Additional Declarations No competing interests reported. Supplementary Files GraphicalAbstract.png Cite Share Download PDF Status: Published Journal Publication published 18 Dec, 2024 Read the published version in Cellulose → Version 1 posted Editorial decision: Revision requested 05 May, 2024 Submission checks completed at journal 03 May, 2024 Editor assigned by journal 03 May, 2024 First submitted to journal 01 May, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4356473","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":298904577,"identity":"7cac5843-9571-4415-a5a0-10a835541e4d","order_by":0,"name":"Wanli Ji","email":"","orcid":"","institution":"Zhejiang Polytechnic Industry College","correspondingAuthor":false,"prefix":"","firstName":"Wanli","middleName":"","lastName":"Ji","suffix":""},{"id":298904578,"identity":"9354dba4-c187-46f3-b453-c493120a3d9f","order_by":1,"name":"Shaofeng Zhong","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAzklEQVRIiWNgGAWjYDAC5gNsIKq+n72x8eEHorSwJYC1MM7sOdxsLEGSlg0z0tsEeIjRId/G/uzBxx21zAaSD9sYJBjs5HQbCGgxOMaQbjjzzHE2c+nEtgcFDMnGZgcIaZFvOCbN23aMx3J2YruBBMOBxG2EtMi3MbaBtEgY3DzYJsFDjBaGY8xsQC01BgY3GInUYnCMjU1yZtuBBMmeRGAgGxDhF1CISXxsq0vgZz/+8OGHCjs5glqg4DDMUuKUg0Ad8UpHwSgYBaNg5AEARMpBbYDZbBgAAAAASUVORK5CYII=","orcid":"","institution":"Zhejiang Polytechnic Industry College","correspondingAuthor":true,"prefix":"","firstName":"Shaofeng","middleName":"","lastName":"Zhong","suffix":""}],"badges":[],"createdAt":"2024-05-02 02:40:21","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4356473/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4356473/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10570-024-06336-3","type":"published","date":"2024-12-18T15:56:57+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":56193996,"identity":"1ec57cc8-b9df-4e8c-998b-dcb2bea24043","added_by":"auto","created_at":"2024-05-09 17:43:23","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":246759,"visible":true,"origin":"","legend":"\u003cp\u003eGraphic illustration for fabrication of the superhydrophobic cotton fabrics\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/1de24dd18eb6177e418c000b.png"},{"id":56194366,"identity":"2ff6f0c7-a365-4ef3-a431-09e41eac7219","added_by":"auto","created_at":"2024-05-09 17:51:26","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":308356,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images and AFM \u0026nbsp;topography images \u0026nbsp;of CF(a, e) and E-CFs obtained after treatment with NaOH and urea \u0026nbsp;solution for \u0026nbsp;6% NaOH/9% urea solution (b, f), 10% NaOH/13.5% urea solution (c, g) \u0026nbsp;and14% NaOH/21% urea solution (d, h), respectively\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/0d900ab0307240a80a6bb31a.png"},{"id":56194007,"identity":"34e388c5-41ce-4ea8-bf3f-ff1628c10864","added_by":"auto","created_at":"2024-05-09 17:43:25","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":279828,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of NaOH concentration on CAs (a) and breaking strength (b) of the superhydrophobic CF\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/a1c0fd8e4ffbf15ac8831576.png"},{"id":56194005,"identity":"0fff44ab-c350-4e21-8910-eab95fe3f63c","added_by":"auto","created_at":"2024-05-09 17:43:24","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":198191,"visible":true,"origin":"","legend":"\u003cp\u003e(a) XPS and (b) FTIR spectra of the CF \u0026nbsp;and superhydrophobic CF\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/71cc917dba5cac77d00dddb0.png"},{"id":56194364,"identity":"901e4c41-c74c-4b4d-9d3f-c2e3dadb10b2","added_by":"auto","created_at":"2024-05-09 17:51:23","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":222464,"visible":true,"origin":"","legend":"\u003cp\u003eEffects ofabrasion cycle (a), laundry cycles (b), after immersed in water solutions with different pH value for 48 and droplets with different temperature on CAs of superhydrophobic CF\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/73f64de498b3eb72b6407ee4.png"},{"id":56195073,"identity":"e62f2e4d-17e1-4304-af34-043ff2a31589","added_by":"auto","created_at":"2024-05-09 17:59:27","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":321670,"visible":true,"origin":"","legend":"\u003cp\u003ePicture of modified \u0026nbsp;CF under a faucet running water (a); \u0026nbsp;Digital images (with water , coffee and milk drops) of the superhydrophobic CF (b);\u003cstrong\u003e \u003c/strong\u003e\u0026nbsp;Digital images photograph of \u0026nbsp;CF submerged in water and superhydrophobic CF \u0026nbsp;floated on the surface of water with droplets (c); \u0026nbsp;the evolution process of the self-cleaning behavior (d–f\u003cstrong\u003e ) \u003c/strong\u003eand separation process of ( g–i ) with superhydrophobic CF\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/e5413959eb2fe5a0eec36db0.png"},{"id":56195074,"identity":"27e0c845-b8d7-40ee-ab6e-e8ba1e61c325","added_by":"auto","created_at":"2024-05-09 17:59:27","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":34985,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Separation efficiency and (b) flux of toward water mixture with different oils; Separation efficiency for (c) dichloromethane-water mixtures and (d) crude oil-water for 20 cycles and the corresponding CAs.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/6a15335a1b00c9a10c27dd7e.png"},{"id":72201461,"identity":"7d3f5f09-552a-4704-8461-4a2b2aaede07","added_by":"auto","created_at":"2024-12-23 16:06:44","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2071041,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/dff14a29-6976-45f6-a435-8ce466ee56a6.pdf"},{"id":56194006,"identity":"c3b94bb9-bdbe-4daa-b289-f2e74e925eeb","added_by":"auto","created_at":"2024-05-09 17:43:24","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":119126,"visible":true,"origin":"","legend":"","description":"","filename":"GraphicalAbstract.png","url":"https://assets-eu.researchsquare.com/files/rs-4356473/v1/4da645efeea2dbcb747b5fee.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Fabrication of robust and sustainable superhydrophobic cotton fabrics via surface micro-dissolve methode for oil/water separation","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe indiscriminate discharge of oily industrial wastewater and frequent offshore oil spill accidents contribute to water pollution, posing a serious threat to the ecological balance crucial for human survival. Addressing the efficient and rapid separation of oil-water mixtures has become a global priority. Inspired by the \"lotus leaf effect,\" researchers have leveraged biomimicry to develop superhydrophobic materials with unique structures, offering a straightforward and effective approach to wastewater separation (Yan et al., \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Xue et al., \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Zheng et al., \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). Typically, superhydrophobic materials exhibit varying wettability towards different liquids due to the significant surface tension disparity between oil and water at the material interface, enabling selective repulsion or wetting of water and oil to achieve efficient separation of oil-water mixtures (Sam et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Zhang et al., \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Xu et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2020\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eCotton fabric, as a natural material, boasts advantages such as affordability, accessibility, environmental friendliness, ease of modification, good mechanical properties, and natural degradation. In light of environmental concerns, the development of fluorine-free superhydrophobic fabrics using CFs as the substrate has garnered considerable attention (Xu et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Meng et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Typically, finishing agents are applied to textile surfaces through dipping or spraying, incorporating inorganic nanoparticles and specialized coatings onto cotton fibers to establish micro-nanostructured roughness and low surface energy, thus achieving superhydrophobicity (Han et al., 2020; Ahmad et al., \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Xiong et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2019\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Li et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Cheng et al., \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Xu et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Li et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Song et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Xu et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Mohamed et al., 2021; Li et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Ji et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). However, nanoparticle detachment compromises their efficacy and lifespan, while shed nanoparticles also pose environmental concerns, limiting their application scope.\u003c/p\u003e \u003cp\u003eTo ensure the enduring presence of nanoscale roughness on superhydrophobic CFs, employing physical or chemical techniques to micro-etch the cotton fibers' surfaces and subsequently introducing low-surface-energy substances can confer upon CFs both durability and remarkable superhydrophobicity (Xu et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Xu et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Li et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Xu et al., \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Yang et al., \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Shanmugavelayutham et al., \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Cheng et al. (\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2019\u003c/span\u003e) treated cotton fibers with a 7.5% mass fraction of sulfuric acid, followed by the introduction of a crosslinker, epoxy soybean oil resin, combined with stearic acid to create superhydrophobic cotton fibers devoid of nanoparticles. These fibers exhibited outstanding mechanical stability and chemical properties, maintaining excellent superhydrophobicity even after undergoing tape stripping, ultrasonic treatment, solvent corrosion, and exposure to low/high temperatures. Additionally, using cellulase to etch cotton fiber surfaces yielded similarly impressive results in mechanical properties and resistance to various treatments (Cheng et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). However, such treatments may lead to a decrease in CFs' mechanical properties. Yao et al. (\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e2021\u003c/span\u003e) utilized oxygen plasma to etch cellulose fiber surfaces, enhancing their roughness and activating hydroxyl groups to undergo condensation reactions with trisilanol butyl polyhedral oligosiloxane (TS-POSS), thereby grafting it onto the fiber surfaces. The resulting superhydrophobic cellulose/TS-POSS material exhibited a static water contact angle of 152.9\u0026deg;. Nguyen-Trig et al. (\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2019\u003c/span\u003e) achieved superhydrophobic CFs via dip-coating with NaOH and plasma etching treatments, followed by deposition of silica nanoparticles and tetraethyl orthosilicate (TEOS), yielding a water contact angle of 172\u0026deg;. Nonetheless, the use of plasma equipment proves costly and impractical for large-scale application.\u003c/p\u003e \u003cp\u003eCai et al. successfully dissolved low-polymerization cellulose in an aqueous NaOH/urea solvent system at low temperatures (-10℃), enhancing the stability of the cellulose solution (Cai et al., 2005; Lue et al., 2009). Alkali/urea chemical etching treatment resulted in the formation of concave-convex structures and grooves on the cellulose material surface, altering the fibers' mechanical properties (Zhang et al., \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Lu et al., \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). In this study, we present a green, nanoparticle-free, fluorine-free, and sustainable approach to fabricating superhydrophobic CFs. CFs were etched using a NaOH/urea solution under low-temperature conditions to create micro-nano rough surfaces. Subsequently, the modified CFs were impregnated with a solution of hexadecyltrimethoxysilane (HDTMS) and butane tetracarboxylic acid (BTCA) to reduce the fibers' surface energy and enhance superhydrophobic durability. These superhydrophobic CFs exhibited exceptional mechanical robustness, durability, and self-cleaning properties. Most importantly, these sustainable superhydrophobic CFs demonstrated outstanding efficiency and reusability in oil/water separation applications.\u003c/p\u003e"},{"header":"Experimental section","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eMaterials\u003c/h2\u003e \u003cp\u003eSodium hydroxide, urea, sulfuric acid, butane tetracarboxylic acid (BTCA), sodium hypophosphite (SHP), and cetyltrimethoxysilane (HDTMS) were procured from Sinopharm Medicine Holding Co., LTD. (China). Dichloromethane, n-hexane, and toluene were obtained from Guangzhou Reagent Co., Ltd. (China). Cotton fabrics (CFs), petroleum ether, and crude oil were sourced from a local store in Shaoxing (China). All chemicals used were of analytical reagent grade and were utilized without further purification. Deionized water served as the solvent for all experiments.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eFabrication of superhydrophobic cotton fabric\u003c/h2\u003e \u003cp\u003eThe CFs were first cleaned using ultrasound in a solution of distilled water and ethanol for 30 minutes, followed by drying. A NaOH/urea aqueous solution was then prepared and cooled to -10 ℃ for 30 minutes. Subsequently, the cleaned CFs were immersed in this solution (with a bath ratio of 1:20) at low temperature for a specified duration and padded (with a wet pick-up of 80%) to micro-dissolve the superficial zone of the CFs (referred to as E-CFs). Next, the E-CFs were immersed in a coagulating bath containing 5 wt% H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e and 5 wt% Na\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e for 5 minutes to remove residual sodium hydroxide and coagulate the cellulose molecules on the surface of the E-CFs. The treated E-CFs were then washed with deionized water and dried at 80 ℃. Subsequently, the E-CFs were immersed in a mixed solution (with a bath ratio of 1:20) of HDTMS, BTCA, and SHP for 20 minutes and padded (with a wet pick-up of 80%). This dip-padding process was repeated several times. Finally, the treated samples were dried at 100 ℃ and cured at a high temperature for 3 minutes to obtain the superhydrophobic CFs.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eCharacterization\u003c/h2\u003e \u003cp\u003eThe surface morphologies were examined using scanning electron microscopy (SEM, Quanta250, FEI) and atomic force microscopy (AFM, SPM9700, Shimadzu). The chemical structures of the samples were analyzed using X-ray photoelectron spectrometry (XPS, Escalab 250Xi, Thermo Fisher Scientific) and attenuated total internal reflectance Fourier transform infrared spectrometry (ATR-FTIR, Nicolet iS10, Thermo Scientific, America).\u003c/p\u003e \u003cp\u003eWater contact angles (CAs) were measured using a contact angle meter (CAM, JC2000D2, Shanghai Zhongchen Digital Technology Equipment Co., Ltd, China) with 5 ml of deionized water at room temperature. Average CAs from five different positions on the fabric surface were reported for each sample.\u003c/p\u003e \u003cp\u003eThe washing durability of the coated cotton samples was evaluated according to AATCC Test Method 61-2006 under condition 2A. Abrasion durability was assessed following AATCC 165\u0026ndash;2007 standard. Breaking tenacity was measured using the raveled strip method as per IS-1969-1985 specification with a universal material testing machine (Instron 3365, USA). Bending length was determined following GB/T 3923.1.1\u0026ndash;2013 standard using an electronic fabric stiffness tester (Ningbo Textile Instrument Co., Ltd., China).\u003c/p\u003e \u003cp\u003eThe whiteness index of the samples was directly evaluated using the Hunter LabScale formula with an X-Rite COLOR i7 computer color matching instrument (USA). Moisture permeability was investigated using a digital moisture permeability measuring instrument (YG501D-II) following GB/T 14704.2\u0026ndash;2009 standard: textile fabric moisture permeability test, using the positive cup method.\u003c/p\u003e \u003c/div\u003e"},{"header":"Results and discussion","content":"\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003ePreparation and surface morphology of superhydrophobic fabrics\u003c/h2\u003e \u003cp\u003eThe sustainable superhydrophobic CFs were fabricated through a mild and eco-friendly two-step process, outlined in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Initially, a NaOH/urea solution was employed to dissolve the surface of cotton fibers in an aqueous solution at -10 ℃, without the introduction of any non-fiber bulk materials. This process facilitated the creation of a stable micro-nano rough structure on the cotton fiber surface, referred to as E-CFs. Subsequently, the E-CFs were immersed and heat-cured using HDTMS, BTCA, and SHP aqueous solutions. HDTMS, a silane compound, served as the hydrophobic agent, while BTCA functioned as a crosslinking medium. BTCA's carboxyl group underwent conversion into an unstable intermediate with the aid of sodium hypophosphite (SHP) acting as a catalyst. This intermediate then reacted with the hydroxyl group of HDTMS and the cotton fibers to form ester bonds, resulting in the formation of durable superhydrophobic fibers. To simplify, the modified E-CFs treated with HDTMS/BTCA were denoted as HDTMS/BTCA/E-CFs.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe surface roughness of CFs was induced through NaOH/urea etching at -10℃ for 1 hour, as depicted in Fig.\u0026nbsp;2. Initially, the surface morphologies and roughness of CFs after etching with different NaOH concentrations were assessed using SEM and AFM. Initially, the pristine CF surface appeared smooth, with corresponding root mean square (RMS) and arithmetic average roughness (Ra) values of 3.4 nm (Fig.\u0026nbsp;2a,e). Upon treatment with a 6 wt% NaOH solution, numerous grooves formed on the fiber surfaces, resulting in an increased Ra value of the E-CF to 6.5 nm (Fig.\u0026nbsp;2b,f), indicating successful integration of nanoscale and microscale roughness on the fiber surfaces. With higher NaOH concentrations, both the depth and number of gaps on the fiber surfaces increased, leading to further elevation in surface Ra values.\u003c/p\u003e \u003cp\u003eInterestingly, the Ra value of CF treatment with a 6 wt% NaOH solution was 12.7 nm. Notably, upon further increasing the NaOH concentration to 14 wt%, the Ra value decreased to 12.1 nm, accompanied by the formation of a new morphology resembling insect phagocytosis (Fig.\u0026nbsp;2d,h). This phenomenon can be attributed to the ineffective encapsulation of a large number of dissolved flocculent chain segments by urea, resulting in their adsorption onto the fabric surface and subsequent formation of a cluster-like \"insect phagocytosis\" structure (Cuissinat et al., 2008; Zhang et al., \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;2 SEM images and AFM topography images of CF (a, e) and E-CFs obtained after treatment with NaOH and urea solution for 6% NaOH/9% urea solution (b, f), 10% NaOH/13.5% urea solution (c, g) and14% NaOH/21% urea solution (d, h), respectively\u003c/p\u003e \u003cp\u003eTo further refine the experimental conditions for developing hydrophobic surfaces, the impact of NaOH concentration on the surface wettability of HDTMS/BTCA/E-CFs was investigated. In this study, the concentration of HDTMS was maintained at 4 wt%, while the concentrations of BTCA and SHF were fixed at 3%. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, when utilizing a 4% NaOH solution, HDTMS/BTCA/E-CFs exhibited only modest hydrophobicity with a contact angle (CA) value of 144\u0026deg;. Elevating the NaOH concentration from 6\u0026ndash;10% resulted in an increase in CA from 151\u0026deg; to 155\u0026deg;. However, further escalation of the NaOH concentration to 14% did not enhance the hydrophobicity of HDTMS/BTCA/E-CFs.\u003c/p\u003e \u003cp\u003eThis phenomenon can be attributed to the deposition of flocculent cellulose, which covered the surface of the initially deep and dense gap structure, thus creating a rough surface resembling \"insect phagocytosis.\" This surface topology was relatively flat and exhibited lower roughness (Cuissinat et al., 2008; Zhang et al., \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2016\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eEtching processes can introduce inherent roughness to fabric surfaces, but traditional chemical etching methods often compromise the mechanical properties of fabrics. Hence, the mechanical properties of various E-CFs were investigated. In Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003eb, the relationship between the breaking strength of the samples and NaOH concentration is illustrated. Unlike conventional chemical etching methods for fabrics, the breaking strength of fabrics increased from 354 to 416 N with an increase in NaOH concentration from 2 to 14 wt%. This enhancement in breaking strength can be primarily attributed to the contraction and tightening of fabrics induced by fiber swelling. Simultaneously, some fibers underwent reduced twisting and further splitting, contributing to the overall increase in fabric breaking strength (Zhong et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2016\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eSurface Composition\u003c/h2\u003e \u003cp\u003eThe chemical structures of the original and treated CFs were analyzed using XPS. In Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003ea, the pristine fabric surface exhibited characteristic peaks of O1s (531 eV) and C1s (284.7 eV) (Xu et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Kang et al., \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Conversely, the modified fabric displayed new characteristic peaks of Si 2s (153 eV) and Si 2p (101 eV) (Rahman et al., \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), indicating successful incorporation of HDTMS onto the fabric surfaces.\u003c/p\u003e \u003cp\u003eFTIR spectroscopy was employed to further examine the chemical composition of the coated CF, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003eb. Relative to the pristine fabric, a shoulder peak emerged around 1722 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, attributed to the characteristic C\u0026thinsp;=\u0026thinsp;O stretching of BTCA (Schramm et al., \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e1997\u003c/span\u003e; Rilda et al., \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). It's worth noting that the distinction between the binding of BTCA and HDTMS was challenging due to the overlap of ester peaks (Hern\u0026aacute;ndez-Padr\u0026oacute;n et al., \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2004\u003c/span\u003e). The absorption peak at 2840 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e corresponded to the stretching vibration peak of CH in the long chain of the hydrophobic compound HDTMS (Xu et al., \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Rahman et al., \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). Simultaneously, the vibration absorption peaks representing the Si-O bond appeared at 894 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 463 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Xu et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2016\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), further confirming the grafting of HDTMS onto the fibers.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003eMechanical durability and chemical stability\u003c/h2\u003e \u003cp\u003eIn practical applications, the durability of superhydrophobic materials is paramount. To assess the mechanical robustness and environmental durability of superhydrophobic CFs, their wettability after exposure to various harsh conditions was investigated. In this study, the effective strategy of constructing inherently rough structures through surface micro-dissolve treatment of CFs and forming covalent bonds between CFs and HDTMS using BTCA was employed to enhance the durability and robustness of the superhydrophobic surface. Here, the mechanical damage and chemical stability of the superhydrophobic CFs were evaluated by measuring water contact angles (CAs), as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003e.\u003c/p\u003e \u003cp\u003eThe resistance against mechanical damage of superhydrophobic CFs was assessed, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ea. The CAs of the superhydrophobic CFs experienced a slight decline after 800 abrasion cycles, with further decreases as the number of abrasion cycles increased. Nevertheless, even after 4000 cycles, the CAs remained as high as 148\u0026deg;, indicating remarkable resistance against abrasion. Furthermore, the laundering durability of HDTMS/BTCA/E-CF was evaluated using a standard laundering method (AATCC 61-2006, condition 2A). Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003eb illustrates the change in CAs of the modified fabrics after repeated washing. After 30 washing cycles, the CAs of the superhydrophobic CFs gradually decreased from an initial 154\u0026deg; to 149\u0026deg;, suggesting that BTCA effectively facilitated firm binding between HDTMS and the fabrics, rendering the coating difficult to peel off. It is noteworthy that the CA of HDTMS/BTCA/E-CFs slightly increased after five washes. This could be attributed to the dissolution of SHP crystals embedded in the fiber surfaces during the washing cycles, resulting in increased surface roughness (Isobe et al., \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2005\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIn addition to physical abrasion, the chemical stability of HDTMS/BTCA/E-CFs was evaluated by immersing modified fabrics into water solutions with pH values ranging from 1 to 14 for 48 hours. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ec demonstrates that superhydrophobic fabrics exhibited satisfactory durability across the pH range, with contact angles exceeding 150\u0026deg;. Furthermore, the CAs of HDTMS/BTCA/E-CFs were tested at different droplet temperatures. It was observed that the CAs changed only slightly when the droplet temperature was below 70\u0026deg;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ed). Unfortunately, beyond 70\u0026deg;C, the CAs decreased from 150\u0026deg;C to 121\u0026deg;C. This can be attributed to the decrease in water surface tension with increasing temperature, leading to enhanced wetting ability of droplets on fiber surfaces and consequently, decreased CAs (Liu et al., \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Zhang et al., \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e2023\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cdiv id=\"Sec10\" class=\"Section3\"\u003e \u003ch2\u003eWater-proofing, anti-fouling and oil/water separation\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe stain resistance and self-cleaning properties of the prepared superhydrophobic carbon fibers (CFs) were evaluated, with results presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003e(a-f). When the superhydrophobic fabric was exposed to a flowing faucet, the water droplets were completely repelled from the fabric's surface, leaving no trace or moisture behind (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003ea). Additionally, common liquids such as milk, coffee, and dyed water were applied to the treated white fabric, as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003eb. The droplets on the superhydrophobic surface maintained a spherical shape and did not soak into the fabric, indicating the material's excellent stain resistance.\u003c/p\u003e \u003cp\u003eTo further demonstrate the stain resistance abilities of HDTMS/BTCA/E-CFs, methylene blue dye was applied to an inclined superhydrophobic fabric, which was then rinsed with water. As the water droplets rolled down the inclined surface, they carried the dye away, leaving the fabric unstained (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003ed-f). These results confirm that the transparent superhydrophobic coating provides effective self-cleaning and stain-resistant protection for fabrics.\u003c/p\u003e \u003cp\u003eThough the HDTMS/BTCA/E-CFs exhibited excellent water repellency, they had extremely poor oil repellency, a property that proved beneficial for oil-water separation applications. The oil-water separation capacity of HDTMS/BTCA/E-CFs was tested, using the superhydrophobic fibers as a filter in an oil-water mixture containing 10 mL of dichloromethane (dyed red) and 10 mL of water (dyed blue). As the mixture was poured through a funnel, the oil droplets quickly penetrated the superhydrophobic surface and passed into the bottom container, while the water droplets remained on top (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003ea). Further investigations examined the separation efficiency and flux of various oil-water mixtures, including n-hexane-water (H-W), toluene-water (T-W), petroleum ether-water (P-W), and crude oil-water (C-W). Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003eb shows that the separation efficiencies for all mixtures exceeded 98%. As for flux, low-viscosity organics like dichloromethane, n-hexane, toluene, and petroleum ether had high fluxes ranging from 60 to 70 kLm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003eh\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, whereas the flux for high-viscosity crude oil was only 5.8 kLm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003eh\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e due to its high adhesion.\u003c/p\u003e \u003cp\u003eTo assess the reusability of the prepared fibers, their separation efficiencies and contact angles were measured after 20 consecutive uses with dichloromethane-water and crude oil-water mixtures. Figures\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003ec and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003ed demonstrate that the separation efficiencies remained above 98% and the contact angles above 150\u0026deg;, indicating remarkable reusability. The experimental results confirm that the superhydrophobic HDTMS/BTCA/E-CFs exhibit high oil-water separation efficiency, good flux, and sustainable reusability, attributes that stem from their robust mechanical durability and chemical stability.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003ephysical properties\u003c/h2\u003e \u003cp\u003eOther physical properties of the pristine and treated cotton fabrics were tested, the results are shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003ePhysical properties of raw and modified fabrics\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTreatments\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003ebreak strength(N)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMoisture permeability\u003c/p\u003e \u003cp\u003e(mg/(cm\u003csup\u003e2\u003c/sup\u003e\u0026middot;h))\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ewhiteness index (hunter)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCFs\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e357\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.139\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e86.1\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eE-CFs\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e423\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.993\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e85.3\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eHDTMS/BTCA/E-CFs\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e326\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.914\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e85.7\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e As depicted in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, chemical corrosion led to a notable enhancement in fabric strength, reaching approximately 118%. Subsequent treatment with HDTMS and BTCA resulted in a relatively significant loss of fiber strength. This can be attributed primarily to the cross-linking effect of BTCA, which restricts the relative sliding of cellulose macromolecular chains, particularly under high temperature and acidic conditions (Huang et al., \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). However, when compared to conventional CFs, HDTMS/BTCA/E-CFs exhibited lesser damage. Although the moisture permeability of the superhydrophobic fabrics experienced a slight decrease, the whiteness remained largely unchanged. This can be attributed to the formation of a network structure on the fiber surface due to the coating, which partially closed the gaps between fibers. Additionally, the low film density of the small HDTMS molecule layer resulted in a minor reduction in moisture permeability. However, the decrease in strength was more pronounced.\u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eWe have successfully developed fully sustainable, nanoparticle-free, and fluorine-free superhydrophobic cotton fabrics (CFs) through a process involving NaOH/urea pretreatment, which had no detrimental effect on the mechanical properties of the fabrics. This was followed by surface modification using the low-energy substrate HDTMS, crosslinked with BTCA. The resulting cotton fabric exhibited outstanding superhydrophobic properties, with a water contact angle reaching up to 155\u0026deg;. Moreover, these superhydrophobic CFs demonstrated remarkable durability, maintaining their surface superhydrophobicity even after exposure to mechanical abrasion, laundering, chemical agents, and high temperatures.\u003c/p\u003e \u003cp\u003eFurthermore, the superhydrophobic CFs exhibited excellent self-cleaning properties when subjected to liquid pollutants. Most notably, they demonstrated exceptional oil/water separation performance, achieving high separation efficiency. Additionally, these CFs displayed impressive reusability, with the surface contact angles remaining unchanged even after 20 cycles of reuse. Overall, the nanoparticle-free, fluorine-free, and robust nature of these superhydrophobic CFs presents them as promising candidates for eco-friendly and efficient oil/water separation applications.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research was supported by the Basic Public Welfare Research Program,\u0026nbsp;funded by\u0026nbsp;Department of Science and Technology of\u0026nbsp;Zhejiang Province, China, under\u0026nbsp;award\u0026nbsp;No.\u0026nbsp;LGG20E030001. Key Investment Plan for High-level Talents is supported by Zhejiang Industrial Polytechnic College\u0026nbsp;under\u0026nbsp;award\u0026nbsp;No. 112709010921621119. Functional Textile Dyeing and Finishing Technology Innovation Team\u0026nbsp;is\u0026nbsp;funded by Shaoxing City government, Zhejiang, China\u0026nbsp;under\u0026nbsp;award\u0026nbsp;No. 222709010921621502.\u0026nbsp;The authors acknowledge\u0026nbsp;the support in part through services provided by Analysis Test Management Platform of Zhejiang University, China, and\u0026nbsp;College of Bioresources Chemical \u0026amp; Materials Engineering,\u0026nbsp;Shaanxi University of Science and Technology, China.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe Basic Public Welfare Research Program is supported\u0026nbsp;by\u0026nbsp;Zhejiang Provincial Natural Science Foundation, China under\u0026nbsp;award\u0026nbsp;No.\u0026nbsp;LGG20E030001. The research \u0026nbsp;was supported by Key Investment Plan for High-level Talents of Zhejiang Industrial Polytechnic College\u0026nbsp;under\u0026nbsp;award\u0026nbsp;No. 112709010921621119. Functional Textile Dyeing and Finishing Technology Innovation Team\u0026nbsp;is\u0026nbsp;supported\u0026nbsp;by Shaoxing City government, Zhejiang, China\u0026nbsp;under\u0026nbsp;award\u0026nbsp;No. 222709010921621502.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics declarations\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthical approval\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable, no animal or human studies.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eYan XJ, Zhu XW, Ruan YT, Xing TL, Chen GQ, Zhou CX (2020) Biomimetic, dopamine-modified\u0026ensp;superhydrophobic\u0026ensp;cotton\u0026ensp;fabric\u0026ensp;for oil-water separation. \u003cem\u003eCellulose\u003c/em\u003e 27(13):7873-7885. https://doi.org/10.1007/s10570-020-03336-x\u003c/li\u003e\n\u003cli\u003eXue QW, Wu JQ, Lv ZS, Lei Y, Liu XG, Huang YF (2023) Photothermal \u0026ensp;Superhydrophobic\u0026ensp;Chitosan- Based\u0026ensp;Cotton\u0026ensp;Fabric\u0026ensp;for Rapid Deicing and Oil/Water Separation. 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Appl Surf Sci 257(9): 4443-4448. https://doi.org/10.1016/j.apsusc.2010.12.087\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"superhydrophobic cotton fabrics, nanoparticle-free, NaOH/urea etching, durability, self-cleaning, Oil/water separation","lastPublishedDoi":"10.21203/rs.3.rs-4356473/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4356473/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe preparation of durable super-hydrophobic cotton fabrics (CFs) poses a significant challenge for oil-water separation, primarily due to nanoparticle loss and the utilization of toxic auxiliaries. This study proposes a sustainable method for creating superhydrophobic CFs. Initially, CFs are treated with a mixture of NaOH and urea at low temperatures to enhance surface roughness while preserving mechanical integrity. Subsequently, hexadecyl trimethoxysilane (HDTMS) and butane tetracarboxylic acid (BTCA) are applied to reduce fiber surface energy. This combined approach results in CFs with outstanding superhydrophobic properties, boasting a water contact angle of up to 155\u0026deg;, surpassing nanoparticle-based surfaces. Furthermore, these fabrics exhibit remarkable mechanical and chemical stability, along with enduring washing durability. Notably, they demonstrate effective self-cleaning abilities in the presence of liquid contaminants and excellent oil/water separation performance with a high separation efficiency. The developed CFs hold promise for diverse applications in both household and industrial settings.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e","manuscriptTitle":"Fabrication of robust and sustainable superhydrophobic cotton fabrics via surface micro-dissolve methode for oil/water separation","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-05-09 17:43:09","doi":"10.21203/rs.3.rs-4356473/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-05-05T14:34:58+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-05-04T03:47:40+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-05-04T03:47:40+00:00","index":"","fulltext":""},{"type":"submitted","content":"Cellulose","date":"2024-05-02T02:36:38+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"27a32dc1-a5bf-4d07-a5ab-23dc0fd3b10b","owner":[],"postedDate":"May 9th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-12-23T15:59:06+00:00","versionOfRecord":{"articleIdentity":"rs-4356473","link":"https://doi.org/10.1007/s10570-024-06336-3","journal":{"identity":"cellulose","isVorOnly":false,"title":"Cellulose"},"publishedOn":"2024-12-18 15:56:57","publishedOnDateReadable":"December 18th, 2024"},"versionCreatedAt":"2024-05-09 17:43:09","video":"","vorDoi":"10.1007/s10570-024-06336-3","vorDoiUrl":"https://doi.org/10.1007/s10570-024-06336-3","workflowStages":[]},"version":"v1","identity":"rs-4356473","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4356473","identity":"rs-4356473","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}