- Email: [email protected]
Facile construction of robust fluorine-free superhydrophobic TiO2@fabrics with excellent anti-fouling, water-oil separation and UV-protective properties
Accepted Manuscript Facile construction of robust fluorine-free superhydrophobic TiO2@fabrics with excellent anti-fouling, water-oil separation and UV-protective properties
Shouwei Gao, Jianying Huang, Shuhui Li, Hui Liu, Feiyang Li, Yuwei Li, Guoqiang Chen, Yuekun Lai PII: DOI: Reference:
S0264-1275(17)30448-3 doi: 10.1016/j.matdes.2017.04.091 JMADE 3013
To appear in:
Materials & Design
Received date: Revised date: Accepted date:
15 February 2017 20 April 2017 26 April 2017
Please cite this article as: Shouwei Gao, Jianying Huang, Shuhui Li, Hui Liu, Feiyang Li, Yuwei Li, Guoqiang Chen, Yuekun Lai , Facile construction of robust fluorine-free superhydrophobic TiO2@fabrics with excellent anti-fouling, water-oil separation and UVprotective properties, Materials & Design (2017), doi: 10.1016/j.matdes.2017.04.091
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
PT
ACCEPTED MANUSCRIPT
SC
RI
Facile Construction of Robust Fluorine-free Superhydrophobic TiO2@fabrics with Excellent Anti-fouling, Water-oil Separation and UVprotective Properties
NU
Shouwei Gao, Jianying Huang, Shuhui Li, Hui Liu, Feiyang Li, Yuwei Li, Guoqiang Chen, Yuekun Lai*
MA
National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou 215123, PR China Abstract
AC C
EP T
ED
The superhydrophobic TiO2 coating was fabricated on cotton fabric through a facile one step hotpressing process after being dipped in n-octyltriethoxysilane and Ti-containing precursor mixed solution. The as-prepared fabric exhibited robust superhydrophobic with a water contact angle higher than 150 ° and realized an optimized UV protective factor of 45. The as-constructed superhydrophobic fabric was able to withstand more than 800 cycles of abrasion. Moreover, there was not apparent decrease of superhydrophobicity after 10 cycles of accelerated machine wash and the as-constructed fabric also showed a strong ability to resist acidic and alkaline solutions. Finally, the protential applications of such value-added fabrics self-cleaning, anti- fouling, and water-oil separation were investigated as well. The results demonstrated that the combination of noctyltriethoxysilane and Ti-containing precursor coating endowed the pristine fabrics with excellent self-cleaning for dusts and anti- fouling for methylene blue dye, as well as excellent separation efficiency for the oil-water mixtures. This facile synthesis stragegy can also be extended to quickly construct multifunctional fabrics with speical wettability in a large scale and utilized in some promising fields. Keywords: TiO 2 @fabric; superhydrophobic; environmental- friendly; UV protection; self-cleaning; oil- water separation 1. Introduction Inspired by lotus effect, superhydrophobic surfaces with a water contact angle (CA) greater than 150° and sliding angle (SA) lower than 10°,[1-4] have attract tremendous interest for numerous applications, including self- cleaning property,[5-7] oil- water separation,[8-10] energy 1
PT
ACCEPTED MANUSCRIPT
ED
MA
NU
SC
RI
conversion,[11, 12] anti- fogging/icing,[13-15] and anti-drag/corrosion etc.[16-18] The keys to create superhydrophobic surfaces are building hierarchical micro/nano structures and introducing hydrophobic chemical groups.[19-22] Based on these two factors, many approaches have been used like chemical vapor deposition (CVD),[23, 24] hydrothermal technique,[25, 26] sol- gel method,[27-29] lithographically etch,[30, 31] grafting coating and electrospinning method etc.[3237] While most of these techniques suffer from disadvantages to some extent. Firstly, most of these methods depend on complex instruments and time-consuming processes, which are not suitable for industrial production. Secondly, the inherent merits of the foreign components have not been fully utilized. For instance, people introduced particles just for building micro/nano structures but ignored the nature of the particle itself. Moreover, the expensive and potential toxic fluorinecontaining reagents are applied for the construction of superhydrophobic surfaces, which is over the requirement of common utilization, in fact, alkane derivatives was enough. Last, the poor washing and abrasion durability strict their application. Therefore, there is an urgent requirement for preparing fluorine- free durable and multifunctional superhydrophobic coating.
AC C
EP T
Padder process is a common strategy in fabric finishing process.[38, 39] Liu et al. reported a stimuli-responsive, multifunctional superhydrophobic surface through dip-pad-dry-curing method, which is easy but multi-step.[39] In fact, to make it more efficient, all these process can be blended into one step. The hot pressing method (HoP), similar as calendaring in fabric finishing process, was used to fabricate MOFs (metal-organic frameworks) on all kinds of substrates by Chen et al. The MOF-decorated devices obtained through such method displayed excellent uniformity and robustness.[40] Inspired by this, we hold a view that the introduction of HoP process must shorten the time for fabrication superhydrophobic surfaces. TiO 2 semiconductor nanoparticles have strong UV-shielding ability, high stability and safety.[41-44] Ren et al. fabricated rattle-type TiO 2 /SiO 2 core/shell particles on polyurethane films which exhibited very good UV-shielding property.[45] So it is very suitable to employ TiO2 to construct UV-shielding fabrics. In this work, a facile fluorine-free machine durable and multifunctional superhydrophobic coating method combining HoP and the UV-shielding capacity of TiO 2 is reported. The as-prepared fabric exhibited robust superhydrophobic with a water CA higher than 150°, and it was able to withstand more than 800 cycles of abrasion without apparent decrease of CA. Meanwhile there was not obvious decrease of contact angle after 10 cycles of accelerated machine wash process and the asconstructed fabric also showed a strong ability to resist acidic and alkaline solutions. Finally, air permeability, water-oil separation ability and UV-shielding test were tested as well. It is noteworthy that as prepared cotton can get excellent UV-shielding property with the UPF value of 45+. As far as we known, there was rare report that machine durable multifunctional fabrics had been fabricated with the CA was more than 150° and the UPF value was 45+ in just 10 min via a 2
PT
ACCEPTED MANUSCRIPT
RI
simple HoP process. This facile synthesis strategy has a potential application in scalable fabrication of value-added multifunctional fabrics.
MA
NU
SC
2. Experimental Work 2.1. Materials: Cotton adjacent fabric was purchased from Shanghai Textile Industry of technical Supervision. Before dried for further process, the cotton adjacent fabrics were cleaned with deionized water, ethanol and acetone to remove any impurities. Tetrabutyl Titanate (TBOT) was obtained from Sinopharm Chemical Reagent Co., Ltd. N, N- Dimethylformamide (DMF), Acetic acid (HAc), Dichloromethane and Ammonium Solution (NH3 ) were purchased from Chinasun Speciality Products Co., Ltd. n-Octyl triethoxysilane (OTES) was purchased from Nanjing Capatue Chemical Co., Ltd.
ED
2.2. Preparation of dipping solution: The dipping solution was prepared according to previous work with some changes.[46] In brief, a certain amount of TBOT (0.5 ml, 1 ml and 2 ml) was added into an organic solvent containing 20 ml DMF and 0.04 ml HAc. Finally, 4 ml OTES was mixed. All the process was under the condition of magnetic stirring. Without special mention, the volume of TBOT added is 2.0 ml.
AC C
EP T
2.3. Preparation of TiO2 @fabrics: The cleaned cotton adjacent fabrics were immersed into the asprepared solution for 2 min and then taken out. Next the fabrics were packed with aluminium foil and heated in drying oven at 200 o C for 10 min with a heavy weight. After peeling off the aluminium foil, the fabrics were washed with ethanol and dried at 80 o C prior to use for characterizations. 2.4. Characterizations of TiO2 @fabrics: The morphology of the modified fabrics was performed by a field-emission scanning electron microscope (FESEM, Hitachi S-4800), and the chemical composition and disrtibution were investigated by an energy-dispersive X-ray spectrometer (EDS). A Kratos Axis-Ultra HSA X-ray photoelectron spectrometer (XPS) was also utilized to analyzed the chemical composition. Static contact angles were measured using an optical contact angle measuring system (Krüss DSA100, Germany). The volumes of droplets were 6 μL.The anti-UV property of the fabric was tested by a Labsphere UV-1000F ultraviolet transmittance analyser. In addition, the surface roughness was investigated using an atomic force microscope (AFM, Bruker Company). Besides, the mechanical durability was evaluated by a dry crocking method (Color Fastness to Rubbing Tester 680) basing on GB/T 3920-2008 standard. The washing durability was evaluated according to the 2A codition of the AATCC 61-2006 standard method. The air permeability was estimated by digital air permeability instrument (YG461E-11).
3
PT
ACCEPTED MANUSCRIPT
RI
3. Results and Discussion
AC C
EP T
ED
MA
NU
SC
Scheme 1 showed the preparation process of the superhydrophobic TiO 2 @fabrics. It was interesting that the Hop duration required to realize TiO 2 coating for super-antiwetting was within 10 min through such a simple strategy. Figure 1a-c showed the SEM imagine of fabric and modified fabric (2.0 ml TBOT/20 ml DMF). It could be seen that there existed natural grains on the cotton fibre (Figure 1a), but after treated through HoP method, the grains were filled with TiO 2 . It was noteworthy that the TiO 2 was not in a certain shape, meanwhile dispersed and embedded on the fibre surfaces randomly (Figure 1b-d). The CA of the modified fabrics was more than 150°, indicating the hydrophobic groups of CH3 and CH2 were effectively grafted on the fiber surface to resist the direct contact and invasion of droplet. Moreover, a large amount of air was trapped between water and fibers with the micro and nano dual-scale structures provided by the inherent fabric texture and TiO 2 particles decoration, to form the typical wetting state of Cassie-Baxter. All those factors made it impossible for water to permeate through the fabric. To detect the elements on the fabric the energy-dispersive X-ray spectrometer (EDS) was applied. Figure 1e,f showed that there appeared Ti and Si on the modified fabric compared with pristine cotton (Figure S1). In addition, the mapping images exhibited that all the elements distributed homogeneously, which was consistent with the result of SEM characterization.
Scheme 1. Schemat ic illustration of the processing to prepare durablefluorine-free and mu ltifunctional superhydrophobic fabric exh ibit ing effect ive oil-water separation property and UV-shield ing property.
4
ED
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
EP T
Figure 1. SEM images of the pristine (a) and modified (b -d) cotton fabric (1 ml/20 ml DMF) with d ifferent enlargement factor. Element mapping (e) and EDS spectrum (f) of mod ified fabric. Inset of (b) is the corresponding static behaviour of droplet on the modified fabric.
AC C
As shown in Figure 2a, the presence of the strong Ti 2p peak (456.0 eV), Si 2p peak (100.1 eV) and Si 2s peak (150.5 eV) indicated that TiO 2 particles and OTES had been successfully coated compared with the pristine cotton. Figure 2b showed Ti 2p XPS survey spectra, where two distinct peaks of Ti 2p3/2 and 2p1/2 appeared on their corresponding position at 458.9 and 464.6 eV, respectively. At the same time, the splitting energy between the Ti 2p 3/2 and 2p1/2 core levels was 5.7 eV (Figure 2c), which attibuted to the existence of Ti4+, according to the reported data for TiO 2 .[47]
Figure 2. W ide XPS (a) spectra of the pristine cotton and the modified cotton fabric. Corresponding high -resolution XPS spectra of Si 2p (b) and Ti 2p (c).
5
PT
ACCEPTED MANUSCRIPT
ED
MA
NU
SC
RI
To clarify the influence of TiO 2 on the morphology of the fabric, the atomic force microscopy (AFM) was ultilized to exhibit and calculate the surface roughness. As shown in Figure 3a, the roughness of pristine cotton was quite smooth with a root- mean-square (RMS) value of 14.6 nm.. While, after modified with the mixture solution, the RMS value increased to 48.2 nm (Figure 3b). The increase of the RMS value represented the increase of the surface roughness which was important for designing superhydrophobic surface. So this could clarify the hydrophobicity of the modified fabric to some extent.
EP T
Figure 3. A FM imagines of the surface of (a) pristine cotton fabric, (b) mod ified cotton fabric.
AC C
Figure 4 showed the morphology of the as-prepared TiO 2 modified cotton with various TBOT concentrations. From a low TBOT concentration (0.5 ml/20 ml DMF; Figure 4a) to middle TBOT concentration (1.0 ml/20 ml DMF; Figure 4b) and high TBOT concentration (2.0 ml/20 ml TBOT; Figure 4c), it was obvious that at a low concentration, the grains on pristine cotton were distinct, as the concentration increased, the grains were gradually filled with TiO 2 until the TiO 2 covered the fibres like a shell. Meanwhile energy-dispersive X-ray spectrometer (EDS) also clearly confirmed that the content of Ti increased (Figure S2).
Figure 4. SEM images showing the modified cotton fabric surface structure functionalized with various TBOT volu me in 20 ml DM F: 0.5 ml (a), 1.0 ml (b), 2.0 ml (c).
6
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
As we known, the cotton fabrics are widely used in garment industry, while UV radiation can easily transmit through the cotton fabrics without any finishing treatment.therefore, it is important to apply TiO 2 particles to enhance the absorption of UV radiation. Figure 5 showed the UV-shielding property of TiO 2 @fabrics fabricated with different TBOT concentration. As given in Table 1, the percentages of UV transmittance for UVB which represented the light wave band from 280 nm to 320 nm dramatically decreased after modified with TiO 2 . In addition, it was obvious that with the increasing of the concentration of TiO 2 , the ultraviolet protection factor (UPF) value of the fabric was improved sharply to about 45 within 10 min which was 10 times higher than pristine cotton.In addition to short duration requirement, it should be noticed that the practical consumption amount of TiO 2 on the whole fabric was very little even modified with high concentrate of TiO 2 sol- gel solution (Figure 1f) compared with our previous work.[48] We believe that the great UV-shielding ability may due to the crystal phase transition caused by the high temperature.[49] When the asprepared cotton fabric was irradiated by UV light for more than 24 h, the CA on the plane of illuminated side decreased lightly while there was no obvious CA decrease for the back side superhydrophobic surface. This may because of the photocatalytic decomposition of the OTES monolayer by TiO 2 structure surface.[50] More interestingly, the superhydrophobic ability could recover after being treated by hot for a little time, that’s may owe to the fast migration of the free OTES from the internal fiber driven by high temperature.[51] These results proved that as- modified cotton fabric not only exhibited a good UV-shielding property but also possessed self- healing ability, which have promising applications in wettability adjusting between superhydrophobicity and hydrophilicity.[52]
Figure 5. UV transmittance for d ifferent volume of TBOT d issolved in DMF before coated onto cotton fabric samp les.
7
PT
ACCEPTED MANUSCRIPT
UVA 28.69% 7.01% 7.02% 6.07%
SC
UPF 4.57 25.68 30.75 45.00
UVB 20.31% 3.41% 2.73% 1.81%
NU
Sample Pristine Cotton Cotton + TiO2 (0.5 ml) Cotton + TiO2 (1.0 ml) Cotton + TiO2 (2.0 ml)
RI
Table 1. UV-shield ing properties of the modified cotton fabric with different volu me of TBOT dissolved in DMF.
AC C
EP T
ED
MA
There was a drawback for many kinds of superhydrophobic surfaces, it was that their superhydrophobic property would easily disappear once agninst a high liquid pressure or under machine as well as extreme chemical environment damage. That’s why almost all superhydrophobic product couldn’t be put into mass industrial application. Figure 6a and b showed the image of the modified fabric (2.0 ml TBOT/20 ml DMF) and the pristine fabric subermerged in water viewed at a glancing angle, respectively. It was obvious that compared with the pristine cotton fabric, the trapped air covered the modified superhydrophobic surface and made it like a silver mirror. These air pockets could prevent the water from penetrating through the fabric and keep it away from wetting even though after being immersed for a long time. That meaned that asprepared superhydrophobic fabric possessed an outstanding property against liquid-pressure. Besides, highiy concentrated acidic solution (HCl, pH=1) and basic solution (NaOH, pH=13) were introduced to assess the stability of the superhydrophobic ability under extreme chemical environment. As shown in Figure 6c, after being immersed in corresponding solution for 24 h, there was no obvious reduction of CA despite of acidc or basic environment. That was of a great meaning in some special situation, which would undoubtedly broaden its application field.
Figure 6. Image of the modified fabric (2.0 ml TBOT/20 ml DM F) and pristine cotton submerged in water slide angle (a, b); the CA of the modified cotton fabric after immersed into HCl solution(pH=1) and NaOH solution (pH=13) for 24 h (b), Inset image is the corresponding droplet on the modified cotton fabric.
8
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
Mechanical stability was evaluated by the abrasion process. The modified fabric was under the pressure of 3.5 kPa with pristine cotton fabric served as an abrasion surface which was dragged at a speed of 3 cm s-1 for 11 cm and every round trip was defined as a cycle. There were two reasons to choose pristine cotton fabric as an abrasion surface. Firstly, compared with sandpaper, pristine cotton fabrics were smoother and more practical to simulate the destroy of micro/nano structure of the fabrics. Secondly, the abrasion between fabrics was more common in our daily life. The CA variation on the fabric (2.0 ml TBOT/20 ml DMF) with abrasion cycles was shown in Figure 7a. It’s interesting to know that the modified fabric surface (2.0 ml TBOT/20 ml DMF) remained superhydrophobic even the fabric was worn out after 800 cycles of abrasion. In addition, excellent water-fastness was also necessary for the modified superhydrophobic fabric. On the basis of the 2A condition of the AATCC 61-2006 standard method, the modified cotton fabric was performed to investigate the accelerated laundering durability. The CA variation on the modified cotton with laundering cycles was shown in Figure 7b. The modified cotton displayed no obvious CA decrease after 10 cycles indicating good laundering durability.[53] Figure 7c and d were the SEM images of the modified cotton abraded after 800 cycles and machine washed after 10 cycles, respectively. Compared with the modified cotton without abrasion or laundering washing, little part of the TiO 2 on the post-treated fabric started to be scratched off from the fibre, while there still a large amount of TiO 2 was left. This TiO 2 was not in a certain shape, meanwhile dispersed and embedded on the fiber surfaces randomly. These surface morphologies were similar as that before the test. In addition, as shown in Figure S3, the sol could easily permeat into the inner layer of the yarn so that the TiO 2 could be modified on every single fiber resulted in the improvement of the machine durability. Apart from these, HoP was a common method in cloth industry, which could realize firmly coating with high density through heating and pressing powder.[54] In fact, to confirm the impact of pressing, the cotton modified by sol- gel without pressing was also constructed for comparison. Figure S4 was the SEM image, the shape of TiO 2 structure was sphere and the shell was not as compact as the cotton modified under pressing. Therefore, it could be concluded that the remaining micro/nano structure and the high density of the TiO2 may account for the robust superhydrophobic property.
9
AC C
EP T
ED
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
Figure 7. The effect of (a) abrasion and (b) laundering times on CA and SA. Insets of (a, b) are the static and sliding droplet images on the corresponding modified cotton fabric. SEM images of the as -prepared cotton fabric surface (2.0 ml TBOT/ 20 ml DMF) after 800 cycles of abrasion (c) or 10 cycles of laundering (d).
By taking the pencil shavings as dust, self- cleaning property was demonstrated. As shown in Figure 8a-d, the pristine cottton fabric and modified fabric were placed on a tilting platform with the pencil shavings distributed uniformly on them. When water droplets were dropped, the dust was carried away by the spherial water droplet and rolled down from the surface quickly. This phenomenon confirmed that the surface energy of the modified fabric was lower than the water surface tension though contained the dust and that played an important role in self-cleaning property. In addition, the anti- fouling property was also tested by immersing the superhydrophobic fabric (2.0 ml TBOT/20 ml DMF) into solution dyed by methylene blue (1 M). After being immersed in the dyed solution for certain duration, the pristine cotton was completely dyed blue 10
PT
ACCEPTED MANUSCRIPT
EP T
ED
MA
NU
SC
RI
(Figure 8e and f), while there was no obvious dyed liquid pinned on the superhydrophobic fabric surface. Moreover, this ramdomly attached dyed droplets would be easily removed by rinsing to recover its origianl clean state (Figure 8g). These results indicate that the as-constructed superhydrophobic fabrics keep excellent self-clening and anti- fouling ability in an outdoor enviroment.
AC C
Figure 8. The self-cleaning process of the modified superhydrophobic fabric (a -d, the left was the modified fabric, the right was the pristine cotton); the anti-fouling property of different samples (e-g): images of modified cotton fabric (left) pristine cotton fabric (right) before (e) and after (f) immersed into methylene blue solution; (g) images of samples followed after being rinsed and dried.
Beside these, the excellent properties weren’t at the expense of sacrificing some wearability like air permeability. Though the digital air permeability measuring instrument showed that the air permeability decreased to some extent from 421.55 to 252.38 mm s-1 , it was larger than many other fabrics and still good enough for wearing. To make it more visual, herein, as presented in Figure 9, water droplets were used to represent the waterproofness, and the pH indicator droplets were utilized as indicators to confirm the air permeability through the fabric. The modified fabric (2.0 ml TBOT/20 ml DMF) was covered on a beaker filled with water (Figure 9b) and another with ammonium hydroxide (Figure 9c). It could be seen that the colour of the pH indicator droplets turned from green to purple immediately as soon as dropped. That proved as modified fabric possessed a great air permeability.
11
ED
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
EP T
Figure 9. The schematic illustration of the test for air permeability of the modified fabric (a). The modified fabric was covered on a beaker filled with water (b) or with ammoniu m hydro xide (c), where the liquid drop lets formed with logo of “S” and “U” are water droplets and pH indicator drop lets.
AC C
Moreover, the superhydrophobic modified fabrics demonstrate potential selective separation ability due to the immiscibility of oil and water. As a proof-of-concept study, the modified fabric was performed to investigate the oil-water separation ability, as shown in Figure 10a-c. The superhydrophobic fabric (2.0 ml TBOT/20 ml DMF) was mounted between two glass tubes and the mixtures of oil (dichloromethane) and water (50 vol%) were poured onto the modified fabric membrane, to made it more distinct, the water was dyed by methylene blue. The oil quickly permeated through the membrane under the gravity, while the water was retained above the porous fabric membrane because of its excellent superhydrophobic ability of the treated fabric (Figure 10c).[55] The water and the oil were collected to calculate the separation efficiency. As the Figure 10d and e showed, the volume of the oil was decrease because of the evaporation of the dichloromethane, while the volume of water was still remain about 100 ml indicating that the effective separation efficiency was approach to 100%. The same process was carried out for 5 times, the result exhibited that the fabric still prossessed excellent oil-water separation property even after 5 times continuous test and retained its superhydrophobic ability after cleaned with alcohol and water (Figure S5).
12
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
ED
Figure 10. Time sequence of the oil-water separation process with the superhydrophobic modified fabric (2 .0 ml/20 ml DMF) (a-c); the volu me of water and dichloro methane before (d) and after (e) separation.
EP T
4. Conclusions
AC C
In summary, we constructed a fluorine- free multifunctional superhydrophobic fabric through a rapid hot-pressing process within 10 min. The combination of hydrophobic groups derived from the cheap material silane material of OTES and the micro/nano dual-scale structure of the surface provided by the coating of TiO 2 particles endowed the compostie TiO 2 @fabrics with outstanding superhydrophobic property. Because of the irregular shape of the TiO 2 and the dense structure attributing to the interation of temperature and pressure, the as-modified fabric could withstand hundreds of abrasion cycles and at least ten laundering cycles. Moreover, the required TiO 2 amount for the effective construction of superhydrophobic cotton fabrics with superior UV-protective property was low. In addition, it was of remarkable durability against chemical interaction, fine air permeability, excellent self-cleaning and anti- foiling ability, as well as excellent separation efficiency for the oil- water mixtures. These findings provided a facile avenue for the rational design and effective construction of durable superhydrophobic fabrics, and the scale-up preparation of multifuntional textiles for personal daily life or sport protection, and oil- water separation. Acknowledgements The authors thank the Natural Science Foundation of Jiangsu Province of China (BK20140400), Natural Science Foundation of the Jiangsu Higher Education Institutions of People's Republic of China (15KJB430025), National Natural Science Foundation of China (21501127 and 51502185). We also acknowledge the funds from the Priority Academic 13
PT
ACCEPTED MANUSCRIPT
RI
Program Development of Jiangsu Higher Education Institutions (PAPD), and Project for Jiangsu Scientific and Technological Innovation Team (2013).
SC
References
AC C
EP T
ED
MA
NU
[1] A. Tuteja, W. Choi, M. Ma, J.M. Mabry, S.A. Mazzella, G.C. Rutledge, G.H. McKinley, R.E. Cohen, Designing superoleophobic surfaces, Science 318 (2007) 1618-1622. [2] J.V.I. Timonen, M. Latikka, L. Leibler, R.H.A. Ras, O. Ikkala, Switchable Static and Dynamic Self- Assembly of Magnetic Droplets on Superhydrophobic Surfaces, Science 341 (2013) 253-257. [3] H.Y. Erbil, A.L. Demirel, Y. Avci, O. Mert, Transformation of a simple plastic into a superhydrophobic surface, Science 299 (2003) 1377-1380. [4] X.F. Wang, J.Y. Yu, G. Sun, B. Ding, Electrospun nanofibrous materials: a versatile medium for effective oil/water separation, Mater. Today 18 (2006) 403-414. [5] S.T. Wang, K.S. Liu, X. Yao, L. Jiang, Bioinspired Surfaces with Superwettability: New Insight on Theory, Design, and Applications, Chem. Rev. 115 (2015) 8230-8293. [6] Y.K. Lai, J.Y. Huang, Z.Q. Cui, M.Z. Ge, K.Q. Zhang, Z. Chen, L.F. Chi, Recent Advances in TiO 2 Based Nanostructured Surfaces with Controllable Wettability and Adhesion, Small 12 (2016) 2203-2224. [7] I. Hejazi, G.M.M. Sadeghi, S.H. Jafari, H.A. Khonakdar, J. Seyfi, M. Holzschuh, F. Simon, Transforming an intrinsically hydrophilic polymer to a robust self-cleaning superhydrophobic coating via carbon nanotube surface embedding, Mater. Des. 86 (2015) 338-346. [8] H. Zhu, F. Yang, J. Li, Z. Guo, High-efficiency water collection on biomimetic material with superwettable patterns, Chem. Commun. 52 (2016) 12415-12417. [9] J. Ju, K. Xiao, X. Yao, H. Bai, L. Jiang, Bioinspired Conical Copper Wire with Gradient Wettability for Continuous and Efficient Fog Collection, Adv. Mater. 25 (2013) 5937-5942. [10] Q. Wang, B. Dai, J. Bai, Z. Yang, S. Guo, Y. Ding, L. Yang, P. Lei, J. Han, J. Zhu, Synthesis of vertically aligned composite microcone membrane filter for water/oil separation, Mater. Des. 111 (2016) 9-16. [11] N. Miljkovic, R. Enright, E.N. Wang, Effect of Droplet Morphology on Growth Dynamics and Heat Transfer during Condensation on Superhydrophobic Nanostructured Surfaces, ACS Nano 6 (2012) 1776-1785. [12] S.N. Zhang, J.Y. Huang, Z. Chen, Y.K. Lai, Bioinspired Special Wettability Surfaces: From Fundamental Research to Water Harvesting Applications, Small 13 (2017) 1602992. [13] N.-R. Chiou, C. Lui, J. Guan, L.J. Lee, A.J. Epstein, Growth and alignment of polyaniline nanofibres with superhydrophobic, superhydrophilic and other properties, Nat. Nanotechnol. 2 (2007) 354-357. [14] K.S. Liu, M.Y. Cao, A. Fujishima, L. Jiang, Bio-Inspired Titanium Dioxide Materials with Special Wettability and Their Applications, Chem. Rev. 114 (2014) 10044-10094. 14
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
[15] S. Zheng, C. Li, Q. Fu, W. Hu, T. Xiang, Q. Wang, M. Du, X. Liu, Z. Chen, Development of stable superhydrophobic coatings on aluminum surface for corrosion-resistant, self-cleaning, and anti- icing applications, Mater. Des. 93 (2016) 261-270. [16] K.M. Ahmmed, C. Patience, A.M. Kietzig, Internal and External Flow over Laser-Textured Superhydrophobic Polytetrafluoroethylene (PTFE), ACS Appl. Mater. Interfaces 8 (2016) 2741127419. [17] G. Wang, Z. Zeng, H. Wang, L. Zhang, X. Sun, Y. He, L. Li, X. Wu, T. Ren, Q. Xue, Low Drag Porous Ship with Superhydrophobic and Superoleophilic Surface for Oil Spills Cleanup, ACS Appl. Mater. Interfaces 7 (2015) 26184-26194. [18] Y.K. Lai, F. Pan, C. Xu, H. Fuchs, L.F. Chi, In Situ Surface- modification- induced superhydrophobic patterns with reversible wettability and adhesion, Adv. Mater. 25 (2013) 16821686. [19] S. Alexander, J. Eastoe, A.M. Lord, F. Guittard, A.R. Barron, Branched Hydrocarbon Low Surface Energy Materials for Superhydrophobic Nanoparticle Derived Surfaces, ACS Appl. Mater. Interfaces 8 (2016) 660-666. [20] T.L. Liu, C.J. Kim, Repellent surfaces. Turning a surface superrepellent even to completely wetting liquids, Science 346 (2014) 1096-100. [21] R. Nishimura, K. Hyodo, H. Sawaguchi, Y. Yamamoto, Y. Nonomura, H. Mayama, S. Yokojima, S. Nakamura, K. Uchida, Fractal Surfaces of Molecular Crystals Mimicking Lotus Leaf with Phototunable Double Roughness Structures, J. Am. Chem. Soc. 138 (2016) 10299-10303. [22] M. Gao, D.P. Wang, Y.F. Huang, S. Meng, W.H. Wang, Tunable hydrophobicity on fractal and micro-nanoscale hierarchical fracture surface of metallic glasses, Mater. Des. 95 (2016) 612617. [23] F. Li, M. Du, Q. Zheng, Dopamine/Silica Nanoparticle Assembled, Microscale Porous Structure for Versatile Superamphiphobic Coating, ACS Nano 10 (2016) 2910-2921. [24] Y.Y. Wu, M. Bekke, Y. Inoue, H. Sugimura, H. Kitaguchi, C.S. Liu, O. Takai, Mechanical durability of ultra-water-repellent thin film by microwave plasma-enhanced CVD, Thin Solid Films 457 (2004) 122-127. [25] H. Wang, Q. Yao, C. Wang, B. Fan, Q. Sun, C. Jin, Y. Xiong, Y. Chen, A simple, one-step hydrothermal approach to durable and robust superparamagnetic, superhydrophobic and electromagnetic wave-absorbing wood, Sci. Rep. 6 (2016) 35549. [26] X. Wang, M.Q. Zhang, R. Kou, L.L. Lu, Y. Zhao, X.W. Xu, G.M. Liu, Y.M. Zheng, S.H. Yu, Unique Necklace-Like Phenol Formaldehyde Resin Nanofibers: Scalable Templating Synthesis, Casting Films, and Their Superhydrophobic Property, Adv. Funct. Mater. 26 (2016) 5086-5092. [27] L. Feng, Z.Y. Zhang, Z.H. Mai, Y.M. Ma, B.Q. Liu, L. Jiang, D.B. Zhu, A super- hydrophobic and super-oleophilic coating mesh film for the separation of oil and water, Angew. Chem. Int. Edit. 43 (2004) 2012-2014.
15
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
[28] S.H. Li, J.Y. Huang, Z. Chen, G.Q. Chen, Y.K. Lai, A review on special wettability textiles: theoretical models, fabrication technologies and multifunctional applications, J. Mater. Chem. A 5 (2017) 31-55. [29] X. Wu, Q. Fu, D. Kumar, J.W.C. Ho, P. Kanhere, H. Zhou, Z. Chen, Mechanically robust superhydrophobic and superoleophobic coatings derived by sol- gel method, Mater. Des. 89 (2016) 1302-1309. [30] A.Y. Vorobyev, C. Guo, Direct femtosecond laser surface nano/microstructuring and its applications, Laser Photonics Rev. 7 (2013) 385-407. [31] D. Gong, J. Long, D. Jiang, P. Fan, H. Zhang, L. Li, M. Zhong, Robust and Stable Transparent Superhydrophobic Polydimethylsiloxane Films by Duplicating via a Femtosecond Laser Ablated Template, ACS Appl. Mater. Interfaces 8 (2016) 17511-17518. [32] J. New, I.S. Zope, S.N.A. Rahman, X.L.W. Yap, A. Dasari, Physiological comfort and flame retardancy of fabrics with electrostatic self-assembled coatings, Mater. Des. 89 (2015) 413-420. [33] H. Wang, H. Zhou, H. Niu, J. Zhang, Y. Du, T. Lin, Dual- Layer Superamphiphobic/Superhydrophobic-Oleophilic Nanofibrous Membranes with Unidirectional OilTransport Ability and Strengthened Oil-Water Separation Performance, Adv. Mater. Interfaces 2 (2015) 1400506. [34] H. Bellanger, T. Darmanin, E.T. de Givenchy, F. Guittard, Chemical and Physical Pathways for the Preparation of Superoleophobic Surfaces and Related Wetting Theories, Chem. Rev. 114 (2014) 2694-2716. [35] S.N. Zhang, J.Y. Huang, Y.X. Tang, S.H. Li, M.Z. Ge, Z. Chen, K.Q. Zhang, Y.K. Lai, Understanding the Role of Dynamic Wettability for Condensate Microdrop Self-Propelling Based on Designed Superhydrophobic TiO 2 Nanostructures, Small 13 (2017) 1600687. [36] S.H. Li, J.Y. Huang, M.Z. Ge, C.Y. Cao, S. Deng, S.N. Zhang, G.Q. Chen, K.Q. Zhang, S.S. Al-Deyab, Y.K. Lai, Robust Flower-Like TiO 2 @Cotton Fabrics with Special Wettability for Effective Self-Cleaning and Versatile Oil/Water Separation, Adv. Mater. Interfaces 2 (2015) 1500220. [37] S.H. Li, J.Y. Huang, M.Z. Ge, S.W. Li, T.L. Xing, G.Q. Chen, Y.Q. Liu, K.Q. Zhang, S.S. AlDeyab, Y.K. Lai, Controlled grafting superhydrophobic cellulose surface with environmentally friendly short fluoroalkyl chains by ATRP, Mater. Des. 89 (2015) 815-822. [38] C.H. Xue, L. Zhang, P. Wei, S.T. Jia, Fabrication of superhydrophobic cotton textiles with flame retardancy, Cellulose 23 (2016) 1471-1480. [39] Y. Liu, X. Wang, B. Fei, H. Hu, C. Lai, J.H. Xin, Bioinspired, Stimuli-Responsive, Multifunctional Superhydrophobic Surface with Directional Wetting, Adhesion, and Transport of Water, Adv. Funct. Mater. 25 (2015) 5047-5056. [40] Y. Chen, S. Li, X. Pei, J. Zhou, X. Feng, S. Zhang, Y. Cheng, H. Li, R. Han, B. Wang, A Solvent-Free Hot-Pressing Method for Preparing Metal-Organic-Framework Coatings, Angew. Chem. Int. Edit. 55 (2016) 3419-3423. 16
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
[41] Z.-Y. Deng, W. Wang, L.-H. Mao, C.-F. Wang, S. Chen, Versatile superhydrophobic and photocatalytic films generated from TiO 2 -SiO2 @PDMS and their applications on fabrics, J. Mater. Chem. A 2 (2014) 4178-4184. [42] M. Wang, J. Ioccozia, L. Sun, C. Lin, Z. Lin, Inorganic- modified semiconductor TiO 2 nanotube arrays for photocatalysis, Energy Environ. Sci. 7 (2014) 2182-2202. [43] M. Yu, Z. Wang, H. Liu, S. Xie, J. Wu, H. Jiang, J. Zhang, L. Li, J. Li, Laundering Durability of Photocatalyzed Self-Cleaning Cotton Fabric with TiO 2 Nanoparticles Covalently Immobilized, ACS Appl. Mater. Interfaces 5 (2013) 3697-3703. [44] M.Z. Ge, Q.S. Li, C.Y. Cao, J.Y. Huang, S.H. Li, S.N. Zhang, Z. Chen, K.Q. Zhang, S.S. AlDeyab, Y.K. Lai, One-dimensional TiO 2 Nanotube Photocatalysts for Solar Water Splitting, Adv. Sci. 4 (2017) 1600152. [45] Y. Ren, M. Chen, Y. Zhang, L. Wu, Fabrication of rattle-type TiO 2 /SiO 2 core/shell particles with both high photoactivity and UV-shielding property, Langmuir 26 (2010) 11391-11396. [46] H.B. Wu, H.H. Hng, X.W. Lou, Direct Synthesis of Anatase TiO 2 Nanowires with Enhanced Photocatalytic Activity, Adv. Mater. 24 (2012) 2567-2571. [47] Y. Lai, Y. Tang, J. Gong, D. Gong, L. Chi, C. Lin, Z. Chen, Transparent superhydrophobic/superhydrophilic TiO 2 -based coatings for self-cleaning and anti- fogging, J. Mater. Chem. 22 (2012) 7420-7426. [48] J.Y. Huang, S.H. Li, M.Z. Ge, L.N. Wang, T.L. Xing, G.Q. Chen, X.F. Liu, S.S. A l-Deyab, K.Q. Zhang, T. Chen, Y.K. Lai, Robust superhydrophobic TiO 2 @fabrics for UV shielding, selfcleaning and oil–water separation, J. Mater. Chem. A 3 (2015) 2825-2832. [49] M. Jarosz, K. Syrek, J. Kapusta-Kolodziej, J. Mech, K. Malek, K. Hnida, T. Lojewski, M. Jaskula, G.D. Sulka, Heat Treatment Effect on Crystalline Structure and Photoelectrochemical Properties of Anodic TiO 2 Nanotube Arrays Formed in Ethylene Glycol and Glycerol Based Electrolytes, J. Phys. Chem. C 119 (2015) 24182-24191. [50] X. Zhang, H. Kono, Z. Liu, S. Nishimoto, D.A. Tryk, T. Murakami, H. Sakai, M. Abe, A. Fujishima, A transparent and photo-patternable superhydrophobic film, Chem. Commun. 46 (2007) 4949-4951. [51] A. Oláh, H. Hillborg, G.J. Vancso, Hydrophobic recovery of UV/ozone treated poly(dimethylsiloxane): adhesion studies by contact mechanics and mechanism of surface modification, Appl. Surf. Sci. 239 (2005) 410-423. [52] H. Bai, L. Wang, J. Ju, R. Sun, Y. Zheng, L. Jiang, Efficient Water Collection on Integrative Bioinspired Surfaces with Star-Shaped Wettability Patterns, Adv. Mater. 26 (2014) 5025-5030. [53] C. Cao, M. Ge, J. Huang, S. Li, S. Deng, S. Zhang, Z. Chen, K. Zhang, S.S. Al- Deyab, Y. Lai, Robust fluorine- free superhydrophobic PDMS–ormosil@fabrics for highly effective self-cleaning and efficient oil–water separation, J. Mater. Chem. A 4 (2016) 12179-12187. [54] B. Poudel, Q. Hao, Y. Ma, Y. Lan, A. Minnich, B. Yu, X. Yan, D. Wang, A. Muto, D. Vashaee, X. Chen, J. Liu, M.S. Dresselhaus, G. Chen, Z. Ren, High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys, Science 320 (2008) 634-638. 17
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
[55] Y. Shang, Y. Si, A. Raza, L. Yang, X. Mao, B. Ding, J. Yu, An in situ polymerization approach for the synthesis of superhydrophobic and superoleophilic nanofibrous membranes for oil- water separation, Nanoscale 4 (2012) 7847-7854.
18
AC C
Graphical abstract
EP T
ED
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
19
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
Highlights Multifunctional fabrics were constructed via a facile one-step hot-pressing process. Environmentally- friendly fluorine- free silane was grafted to realize superhydrophobic. Excellent anti-wetting property with superior abrasion and laundering stability. UV-protection and oil-water separation ability of TiO 2 @fabrics were demonstrated.
20
Shouwei Gao, Jianying Huang, Shuhui Li, Hui Liu, Feiyang Li, Yuwei Li, Guoqiang Chen, Yuekun Lai PII: DOI: Reference:
S0264-1275(17)30448-3 doi: 10.1016/j.matdes.2017.04.091 JMADE 3013
To appear in:
Materials & Design
Received date: Revised date: Accepted date:
15 February 2017 20 April 2017 26 April 2017
Please cite this article as: Shouwei Gao, Jianying Huang, Shuhui Li, Hui Liu, Feiyang Li, Yuwei Li, Guoqiang Chen, Yuekun Lai , Facile construction of robust fluorine-free superhydrophobic TiO2@fabrics with excellent anti-fouling, water-oil separation and UVprotective properties, Materials & Design (2017), doi: 10.1016/j.matdes.2017.04.091
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
PT
ACCEPTED MANUSCRIPT
SC
RI
Facile Construction of Robust Fluorine-free Superhydrophobic TiO2@fabrics with Excellent Anti-fouling, Water-oil Separation and UVprotective Properties
NU
Shouwei Gao, Jianying Huang, Shuhui Li, Hui Liu, Feiyang Li, Yuwei Li, Guoqiang Chen, Yuekun Lai*
MA
National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou 215123, PR China Abstract
AC C
EP T
ED
The superhydrophobic TiO2 coating was fabricated on cotton fabric through a facile one step hotpressing process after being dipped in n-octyltriethoxysilane and Ti-containing precursor mixed solution. The as-prepared fabric exhibited robust superhydrophobic with a water contact angle higher than 150 ° and realized an optimized UV protective factor of 45. The as-constructed superhydrophobic fabric was able to withstand more than 800 cycles of abrasion. Moreover, there was not apparent decrease of superhydrophobicity after 10 cycles of accelerated machine wash and the as-constructed fabric also showed a strong ability to resist acidic and alkaline solutions. Finally, the protential applications of such value-added fabrics self-cleaning, anti- fouling, and water-oil separation were investigated as well. The results demonstrated that the combination of noctyltriethoxysilane and Ti-containing precursor coating endowed the pristine fabrics with excellent self-cleaning for dusts and anti- fouling for methylene blue dye, as well as excellent separation efficiency for the oil-water mixtures. This facile synthesis stragegy can also be extended to quickly construct multifunctional fabrics with speical wettability in a large scale and utilized in some promising fields. Keywords: TiO 2 @fabric; superhydrophobic; environmental- friendly; UV protection; self-cleaning; oil- water separation 1. Introduction Inspired by lotus effect, superhydrophobic surfaces with a water contact angle (CA) greater than 150° and sliding angle (SA) lower than 10°,[1-4] have attract tremendous interest for numerous applications, including self- cleaning property,[5-7] oil- water separation,[8-10] energy 1
PT
ACCEPTED MANUSCRIPT
ED
MA
NU
SC
RI
conversion,[11, 12] anti- fogging/icing,[13-15] and anti-drag/corrosion etc.[16-18] The keys to create superhydrophobic surfaces are building hierarchical micro/nano structures and introducing hydrophobic chemical groups.[19-22] Based on these two factors, many approaches have been used like chemical vapor deposition (CVD),[23, 24] hydrothermal technique,[25, 26] sol- gel method,[27-29] lithographically etch,[30, 31] grafting coating and electrospinning method etc.[3237] While most of these techniques suffer from disadvantages to some extent. Firstly, most of these methods depend on complex instruments and time-consuming processes, which are not suitable for industrial production. Secondly, the inherent merits of the foreign components have not been fully utilized. For instance, people introduced particles just for building micro/nano structures but ignored the nature of the particle itself. Moreover, the expensive and potential toxic fluorinecontaining reagents are applied for the construction of superhydrophobic surfaces, which is over the requirement of common utilization, in fact, alkane derivatives was enough. Last, the poor washing and abrasion durability strict their application. Therefore, there is an urgent requirement for preparing fluorine- free durable and multifunctional superhydrophobic coating.
AC C
EP T
Padder process is a common strategy in fabric finishing process.[38, 39] Liu et al. reported a stimuli-responsive, multifunctional superhydrophobic surface through dip-pad-dry-curing method, which is easy but multi-step.[39] In fact, to make it more efficient, all these process can be blended into one step. The hot pressing method (HoP), similar as calendaring in fabric finishing process, was used to fabricate MOFs (metal-organic frameworks) on all kinds of substrates by Chen et al. The MOF-decorated devices obtained through such method displayed excellent uniformity and robustness.[40] Inspired by this, we hold a view that the introduction of HoP process must shorten the time for fabrication superhydrophobic surfaces. TiO 2 semiconductor nanoparticles have strong UV-shielding ability, high stability and safety.[41-44] Ren et al. fabricated rattle-type TiO 2 /SiO 2 core/shell particles on polyurethane films which exhibited very good UV-shielding property.[45] So it is very suitable to employ TiO2 to construct UV-shielding fabrics. In this work, a facile fluorine-free machine durable and multifunctional superhydrophobic coating method combining HoP and the UV-shielding capacity of TiO 2 is reported. The as-prepared fabric exhibited robust superhydrophobic with a water CA higher than 150°, and it was able to withstand more than 800 cycles of abrasion without apparent decrease of CA. Meanwhile there was not obvious decrease of contact angle after 10 cycles of accelerated machine wash process and the asconstructed fabric also showed a strong ability to resist acidic and alkaline solutions. Finally, air permeability, water-oil separation ability and UV-shielding test were tested as well. It is noteworthy that as prepared cotton can get excellent UV-shielding property with the UPF value of 45+. As far as we known, there was rare report that machine durable multifunctional fabrics had been fabricated with the CA was more than 150° and the UPF value was 45+ in just 10 min via a 2
PT
ACCEPTED MANUSCRIPT
RI
simple HoP process. This facile synthesis strategy has a potential application in scalable fabrication of value-added multifunctional fabrics.
MA
NU
SC
2. Experimental Work 2.1. Materials: Cotton adjacent fabric was purchased from Shanghai Textile Industry of technical Supervision. Before dried for further process, the cotton adjacent fabrics were cleaned with deionized water, ethanol and acetone to remove any impurities. Tetrabutyl Titanate (TBOT) was obtained from Sinopharm Chemical Reagent Co., Ltd. N, N- Dimethylformamide (DMF), Acetic acid (HAc), Dichloromethane and Ammonium Solution (NH3 ) were purchased from Chinasun Speciality Products Co., Ltd. n-Octyl triethoxysilane (OTES) was purchased from Nanjing Capatue Chemical Co., Ltd.
ED
2.2. Preparation of dipping solution: The dipping solution was prepared according to previous work with some changes.[46] In brief, a certain amount of TBOT (0.5 ml, 1 ml and 2 ml) was added into an organic solvent containing 20 ml DMF and 0.04 ml HAc. Finally, 4 ml OTES was mixed. All the process was under the condition of magnetic stirring. Without special mention, the volume of TBOT added is 2.0 ml.
AC C
EP T
2.3. Preparation of TiO2 @fabrics: The cleaned cotton adjacent fabrics were immersed into the asprepared solution for 2 min and then taken out. Next the fabrics were packed with aluminium foil and heated in drying oven at 200 o C for 10 min with a heavy weight. After peeling off the aluminium foil, the fabrics were washed with ethanol and dried at 80 o C prior to use for characterizations. 2.4. Characterizations of TiO2 @fabrics: The morphology of the modified fabrics was performed by a field-emission scanning electron microscope (FESEM, Hitachi S-4800), and the chemical composition and disrtibution were investigated by an energy-dispersive X-ray spectrometer (EDS). A Kratos Axis-Ultra HSA X-ray photoelectron spectrometer (XPS) was also utilized to analyzed the chemical composition. Static contact angles were measured using an optical contact angle measuring system (Krüss DSA100, Germany). The volumes of droplets were 6 μL.The anti-UV property of the fabric was tested by a Labsphere UV-1000F ultraviolet transmittance analyser. In addition, the surface roughness was investigated using an atomic force microscope (AFM, Bruker Company). Besides, the mechanical durability was evaluated by a dry crocking method (Color Fastness to Rubbing Tester 680) basing on GB/T 3920-2008 standard. The washing durability was evaluated according to the 2A codition of the AATCC 61-2006 standard method. The air permeability was estimated by digital air permeability instrument (YG461E-11).
3
PT
ACCEPTED MANUSCRIPT
RI
3. Results and Discussion
AC C
EP T
ED
MA
NU
SC
Scheme 1 showed the preparation process of the superhydrophobic TiO 2 @fabrics. It was interesting that the Hop duration required to realize TiO 2 coating for super-antiwetting was within 10 min through such a simple strategy. Figure 1a-c showed the SEM imagine of fabric and modified fabric (2.0 ml TBOT/20 ml DMF). It could be seen that there existed natural grains on the cotton fibre (Figure 1a), but after treated through HoP method, the grains were filled with TiO 2 . It was noteworthy that the TiO 2 was not in a certain shape, meanwhile dispersed and embedded on the fibre surfaces randomly (Figure 1b-d). The CA of the modified fabrics was more than 150°, indicating the hydrophobic groups of CH3 and CH2 were effectively grafted on the fiber surface to resist the direct contact and invasion of droplet. Moreover, a large amount of air was trapped between water and fibers with the micro and nano dual-scale structures provided by the inherent fabric texture and TiO 2 particles decoration, to form the typical wetting state of Cassie-Baxter. All those factors made it impossible for water to permeate through the fabric. To detect the elements on the fabric the energy-dispersive X-ray spectrometer (EDS) was applied. Figure 1e,f showed that there appeared Ti and Si on the modified fabric compared with pristine cotton (Figure S1). In addition, the mapping images exhibited that all the elements distributed homogeneously, which was consistent with the result of SEM characterization.
Scheme 1. Schemat ic illustration of the processing to prepare durablefluorine-free and mu ltifunctional superhydrophobic fabric exh ibit ing effect ive oil-water separation property and UV-shield ing property.
4
ED
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
EP T
Figure 1. SEM images of the pristine (a) and modified (b -d) cotton fabric (1 ml/20 ml DMF) with d ifferent enlargement factor. Element mapping (e) and EDS spectrum (f) of mod ified fabric. Inset of (b) is the corresponding static behaviour of droplet on the modified fabric.
AC C
As shown in Figure 2a, the presence of the strong Ti 2p peak (456.0 eV), Si 2p peak (100.1 eV) and Si 2s peak (150.5 eV) indicated that TiO 2 particles and OTES had been successfully coated compared with the pristine cotton. Figure 2b showed Ti 2p XPS survey spectra, where two distinct peaks of Ti 2p3/2 and 2p1/2 appeared on their corresponding position at 458.9 and 464.6 eV, respectively. At the same time, the splitting energy between the Ti 2p 3/2 and 2p1/2 core levels was 5.7 eV (Figure 2c), which attibuted to the existence of Ti4+, according to the reported data for TiO 2 .[47]
Figure 2. W ide XPS (a) spectra of the pristine cotton and the modified cotton fabric. Corresponding high -resolution XPS spectra of Si 2p (b) and Ti 2p (c).
5
PT
ACCEPTED MANUSCRIPT
ED
MA
NU
SC
RI
To clarify the influence of TiO 2 on the morphology of the fabric, the atomic force microscopy (AFM) was ultilized to exhibit and calculate the surface roughness. As shown in Figure 3a, the roughness of pristine cotton was quite smooth with a root- mean-square (RMS) value of 14.6 nm.. While, after modified with the mixture solution, the RMS value increased to 48.2 nm (Figure 3b). The increase of the RMS value represented the increase of the surface roughness which was important for designing superhydrophobic surface. So this could clarify the hydrophobicity of the modified fabric to some extent.
EP T
Figure 3. A FM imagines of the surface of (a) pristine cotton fabric, (b) mod ified cotton fabric.
AC C
Figure 4 showed the morphology of the as-prepared TiO 2 modified cotton with various TBOT concentrations. From a low TBOT concentration (0.5 ml/20 ml DMF; Figure 4a) to middle TBOT concentration (1.0 ml/20 ml DMF; Figure 4b) and high TBOT concentration (2.0 ml/20 ml TBOT; Figure 4c), it was obvious that at a low concentration, the grains on pristine cotton were distinct, as the concentration increased, the grains were gradually filled with TiO 2 until the TiO 2 covered the fibres like a shell. Meanwhile energy-dispersive X-ray spectrometer (EDS) also clearly confirmed that the content of Ti increased (Figure S2).
Figure 4. SEM images showing the modified cotton fabric surface structure functionalized with various TBOT volu me in 20 ml DM F: 0.5 ml (a), 1.0 ml (b), 2.0 ml (c).
6
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
As we known, the cotton fabrics are widely used in garment industry, while UV radiation can easily transmit through the cotton fabrics without any finishing treatment.therefore, it is important to apply TiO 2 particles to enhance the absorption of UV radiation. Figure 5 showed the UV-shielding property of TiO 2 @fabrics fabricated with different TBOT concentration. As given in Table 1, the percentages of UV transmittance for UVB which represented the light wave band from 280 nm to 320 nm dramatically decreased after modified with TiO 2 . In addition, it was obvious that with the increasing of the concentration of TiO 2 , the ultraviolet protection factor (UPF) value of the fabric was improved sharply to about 45 within 10 min which was 10 times higher than pristine cotton.In addition to short duration requirement, it should be noticed that the practical consumption amount of TiO 2 on the whole fabric was very little even modified with high concentrate of TiO 2 sol- gel solution (Figure 1f) compared with our previous work.[48] We believe that the great UV-shielding ability may due to the crystal phase transition caused by the high temperature.[49] When the asprepared cotton fabric was irradiated by UV light for more than 24 h, the CA on the plane of illuminated side decreased lightly while there was no obvious CA decrease for the back side superhydrophobic surface. This may because of the photocatalytic decomposition of the OTES monolayer by TiO 2 structure surface.[50] More interestingly, the superhydrophobic ability could recover after being treated by hot for a little time, that’s may owe to the fast migration of the free OTES from the internal fiber driven by high temperature.[51] These results proved that as- modified cotton fabric not only exhibited a good UV-shielding property but also possessed self- healing ability, which have promising applications in wettability adjusting between superhydrophobicity and hydrophilicity.[52]
Figure 5. UV transmittance for d ifferent volume of TBOT d issolved in DMF before coated onto cotton fabric samp les.
7
PT
ACCEPTED MANUSCRIPT
UVA 28.69% 7.01% 7.02% 6.07%
SC
UPF 4.57 25.68 30.75 45.00
UVB 20.31% 3.41% 2.73% 1.81%
NU
Sample Pristine Cotton Cotton + TiO2 (0.5 ml) Cotton + TiO2 (1.0 ml) Cotton + TiO2 (2.0 ml)
RI
Table 1. UV-shield ing properties of the modified cotton fabric with different volu me of TBOT dissolved in DMF.
AC C
EP T
ED
MA
There was a drawback for many kinds of superhydrophobic surfaces, it was that their superhydrophobic property would easily disappear once agninst a high liquid pressure or under machine as well as extreme chemical environment damage. That’s why almost all superhydrophobic product couldn’t be put into mass industrial application. Figure 6a and b showed the image of the modified fabric (2.0 ml TBOT/20 ml DMF) and the pristine fabric subermerged in water viewed at a glancing angle, respectively. It was obvious that compared with the pristine cotton fabric, the trapped air covered the modified superhydrophobic surface and made it like a silver mirror. These air pockets could prevent the water from penetrating through the fabric and keep it away from wetting even though after being immersed for a long time. That meaned that asprepared superhydrophobic fabric possessed an outstanding property against liquid-pressure. Besides, highiy concentrated acidic solution (HCl, pH=1) and basic solution (NaOH, pH=13) were introduced to assess the stability of the superhydrophobic ability under extreme chemical environment. As shown in Figure 6c, after being immersed in corresponding solution for 24 h, there was no obvious reduction of CA despite of acidc or basic environment. That was of a great meaning in some special situation, which would undoubtedly broaden its application field.
Figure 6. Image of the modified fabric (2.0 ml TBOT/20 ml DM F) and pristine cotton submerged in water slide angle (a, b); the CA of the modified cotton fabric after immersed into HCl solution(pH=1) and NaOH solution (pH=13) for 24 h (b), Inset image is the corresponding droplet on the modified cotton fabric.
8
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
Mechanical stability was evaluated by the abrasion process. The modified fabric was under the pressure of 3.5 kPa with pristine cotton fabric served as an abrasion surface which was dragged at a speed of 3 cm s-1 for 11 cm and every round trip was defined as a cycle. There were two reasons to choose pristine cotton fabric as an abrasion surface. Firstly, compared with sandpaper, pristine cotton fabrics were smoother and more practical to simulate the destroy of micro/nano structure of the fabrics. Secondly, the abrasion between fabrics was more common in our daily life. The CA variation on the fabric (2.0 ml TBOT/20 ml DMF) with abrasion cycles was shown in Figure 7a. It’s interesting to know that the modified fabric surface (2.0 ml TBOT/20 ml DMF) remained superhydrophobic even the fabric was worn out after 800 cycles of abrasion. In addition, excellent water-fastness was also necessary for the modified superhydrophobic fabric. On the basis of the 2A condition of the AATCC 61-2006 standard method, the modified cotton fabric was performed to investigate the accelerated laundering durability. The CA variation on the modified cotton with laundering cycles was shown in Figure 7b. The modified cotton displayed no obvious CA decrease after 10 cycles indicating good laundering durability.[53] Figure 7c and d were the SEM images of the modified cotton abraded after 800 cycles and machine washed after 10 cycles, respectively. Compared with the modified cotton without abrasion or laundering washing, little part of the TiO 2 on the post-treated fabric started to be scratched off from the fibre, while there still a large amount of TiO 2 was left. This TiO 2 was not in a certain shape, meanwhile dispersed and embedded on the fiber surfaces randomly. These surface morphologies were similar as that before the test. In addition, as shown in Figure S3, the sol could easily permeat into the inner layer of the yarn so that the TiO 2 could be modified on every single fiber resulted in the improvement of the machine durability. Apart from these, HoP was a common method in cloth industry, which could realize firmly coating with high density through heating and pressing powder.[54] In fact, to confirm the impact of pressing, the cotton modified by sol- gel without pressing was also constructed for comparison. Figure S4 was the SEM image, the shape of TiO 2 structure was sphere and the shell was not as compact as the cotton modified under pressing. Therefore, it could be concluded that the remaining micro/nano structure and the high density of the TiO2 may account for the robust superhydrophobic property.
9
AC C
EP T
ED
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
Figure 7. The effect of (a) abrasion and (b) laundering times on CA and SA. Insets of (a, b) are the static and sliding droplet images on the corresponding modified cotton fabric. SEM images of the as -prepared cotton fabric surface (2.0 ml TBOT/ 20 ml DMF) after 800 cycles of abrasion (c) or 10 cycles of laundering (d).
By taking the pencil shavings as dust, self- cleaning property was demonstrated. As shown in Figure 8a-d, the pristine cottton fabric and modified fabric were placed on a tilting platform with the pencil shavings distributed uniformly on them. When water droplets were dropped, the dust was carried away by the spherial water droplet and rolled down from the surface quickly. This phenomenon confirmed that the surface energy of the modified fabric was lower than the water surface tension though contained the dust and that played an important role in self-cleaning property. In addition, the anti- fouling property was also tested by immersing the superhydrophobic fabric (2.0 ml TBOT/20 ml DMF) into solution dyed by methylene blue (1 M). After being immersed in the dyed solution for certain duration, the pristine cotton was completely dyed blue 10
PT
ACCEPTED MANUSCRIPT
EP T
ED
MA
NU
SC
RI
(Figure 8e and f), while there was no obvious dyed liquid pinned on the superhydrophobic fabric surface. Moreover, this ramdomly attached dyed droplets would be easily removed by rinsing to recover its origianl clean state (Figure 8g). These results indicate that the as-constructed superhydrophobic fabrics keep excellent self-clening and anti- fouling ability in an outdoor enviroment.
AC C
Figure 8. The self-cleaning process of the modified superhydrophobic fabric (a -d, the left was the modified fabric, the right was the pristine cotton); the anti-fouling property of different samples (e-g): images of modified cotton fabric (left) pristine cotton fabric (right) before (e) and after (f) immersed into methylene blue solution; (g) images of samples followed after being rinsed and dried.
Beside these, the excellent properties weren’t at the expense of sacrificing some wearability like air permeability. Though the digital air permeability measuring instrument showed that the air permeability decreased to some extent from 421.55 to 252.38 mm s-1 , it was larger than many other fabrics and still good enough for wearing. To make it more visual, herein, as presented in Figure 9, water droplets were used to represent the waterproofness, and the pH indicator droplets were utilized as indicators to confirm the air permeability through the fabric. The modified fabric (2.0 ml TBOT/20 ml DMF) was covered on a beaker filled with water (Figure 9b) and another with ammonium hydroxide (Figure 9c). It could be seen that the colour of the pH indicator droplets turned from green to purple immediately as soon as dropped. That proved as modified fabric possessed a great air permeability.
11
ED
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
EP T
Figure 9. The schematic illustration of the test for air permeability of the modified fabric (a). The modified fabric was covered on a beaker filled with water (b) or with ammoniu m hydro xide (c), where the liquid drop lets formed with logo of “S” and “U” are water droplets and pH indicator drop lets.
AC C
Moreover, the superhydrophobic modified fabrics demonstrate potential selective separation ability due to the immiscibility of oil and water. As a proof-of-concept study, the modified fabric was performed to investigate the oil-water separation ability, as shown in Figure 10a-c. The superhydrophobic fabric (2.0 ml TBOT/20 ml DMF) was mounted between two glass tubes and the mixtures of oil (dichloromethane) and water (50 vol%) were poured onto the modified fabric membrane, to made it more distinct, the water was dyed by methylene blue. The oil quickly permeated through the membrane under the gravity, while the water was retained above the porous fabric membrane because of its excellent superhydrophobic ability of the treated fabric (Figure 10c).[55] The water and the oil were collected to calculate the separation efficiency. As the Figure 10d and e showed, the volume of the oil was decrease because of the evaporation of the dichloromethane, while the volume of water was still remain about 100 ml indicating that the effective separation efficiency was approach to 100%. The same process was carried out for 5 times, the result exhibited that the fabric still prossessed excellent oil-water separation property even after 5 times continuous test and retained its superhydrophobic ability after cleaned with alcohol and water (Figure S5).
12
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
ED
Figure 10. Time sequence of the oil-water separation process with the superhydrophobic modified fabric (2 .0 ml/20 ml DMF) (a-c); the volu me of water and dichloro methane before (d) and after (e) separation.
EP T
4. Conclusions
AC C
In summary, we constructed a fluorine- free multifunctional superhydrophobic fabric through a rapid hot-pressing process within 10 min. The combination of hydrophobic groups derived from the cheap material silane material of OTES and the micro/nano dual-scale structure of the surface provided by the coating of TiO 2 particles endowed the compostie TiO 2 @fabrics with outstanding superhydrophobic property. Because of the irregular shape of the TiO 2 and the dense structure attributing to the interation of temperature and pressure, the as-modified fabric could withstand hundreds of abrasion cycles and at least ten laundering cycles. Moreover, the required TiO 2 amount for the effective construction of superhydrophobic cotton fabrics with superior UV-protective property was low. In addition, it was of remarkable durability against chemical interaction, fine air permeability, excellent self-cleaning and anti- foiling ability, as well as excellent separation efficiency for the oil- water mixtures. These findings provided a facile avenue for the rational design and effective construction of durable superhydrophobic fabrics, and the scale-up preparation of multifuntional textiles for personal daily life or sport protection, and oil- water separation. Acknowledgements The authors thank the Natural Science Foundation of Jiangsu Province of China (BK20140400), Natural Science Foundation of the Jiangsu Higher Education Institutions of People's Republic of China (15KJB430025), National Natural Science Foundation of China (21501127 and 51502185). We also acknowledge the funds from the Priority Academic 13
PT
ACCEPTED MANUSCRIPT
RI
Program Development of Jiangsu Higher Education Institutions (PAPD), and Project for Jiangsu Scientific and Technological Innovation Team (2013).
SC
References
AC C
EP T
ED
MA
NU
[1] A. Tuteja, W. Choi, M. Ma, J.M. Mabry, S.A. Mazzella, G.C. Rutledge, G.H. McKinley, R.E. Cohen, Designing superoleophobic surfaces, Science 318 (2007) 1618-1622. [2] J.V.I. Timonen, M. Latikka, L. Leibler, R.H.A. Ras, O. Ikkala, Switchable Static and Dynamic Self- Assembly of Magnetic Droplets on Superhydrophobic Surfaces, Science 341 (2013) 253-257. [3] H.Y. Erbil, A.L. Demirel, Y. Avci, O. Mert, Transformation of a simple plastic into a superhydrophobic surface, Science 299 (2003) 1377-1380. [4] X.F. Wang, J.Y. Yu, G. Sun, B. Ding, Electrospun nanofibrous materials: a versatile medium for effective oil/water separation, Mater. Today 18 (2006) 403-414. [5] S.T. Wang, K.S. Liu, X. Yao, L. Jiang, Bioinspired Surfaces with Superwettability: New Insight on Theory, Design, and Applications, Chem. Rev. 115 (2015) 8230-8293. [6] Y.K. Lai, J.Y. Huang, Z.Q. Cui, M.Z. Ge, K.Q. Zhang, Z. Chen, L.F. Chi, Recent Advances in TiO 2 Based Nanostructured Surfaces with Controllable Wettability and Adhesion, Small 12 (2016) 2203-2224. [7] I. Hejazi, G.M.M. Sadeghi, S.H. Jafari, H.A. Khonakdar, J. Seyfi, M. Holzschuh, F. Simon, Transforming an intrinsically hydrophilic polymer to a robust self-cleaning superhydrophobic coating via carbon nanotube surface embedding, Mater. Des. 86 (2015) 338-346. [8] H. Zhu, F. Yang, J. Li, Z. Guo, High-efficiency water collection on biomimetic material with superwettable patterns, Chem. Commun. 52 (2016) 12415-12417. [9] J. Ju, K. Xiao, X. Yao, H. Bai, L. Jiang, Bioinspired Conical Copper Wire with Gradient Wettability for Continuous and Efficient Fog Collection, Adv. Mater. 25 (2013) 5937-5942. [10] Q. Wang, B. Dai, J. Bai, Z. Yang, S. Guo, Y. Ding, L. Yang, P. Lei, J. Han, J. Zhu, Synthesis of vertically aligned composite microcone membrane filter for water/oil separation, Mater. Des. 111 (2016) 9-16. [11] N. Miljkovic, R. Enright, E.N. Wang, Effect of Droplet Morphology on Growth Dynamics and Heat Transfer during Condensation on Superhydrophobic Nanostructured Surfaces, ACS Nano 6 (2012) 1776-1785. [12] S.N. Zhang, J.Y. Huang, Z. Chen, Y.K. Lai, Bioinspired Special Wettability Surfaces: From Fundamental Research to Water Harvesting Applications, Small 13 (2017) 1602992. [13] N.-R. Chiou, C. Lui, J. Guan, L.J. Lee, A.J. Epstein, Growth and alignment of polyaniline nanofibres with superhydrophobic, superhydrophilic and other properties, Nat. Nanotechnol. 2 (2007) 354-357. [14] K.S. Liu, M.Y. Cao, A. Fujishima, L. Jiang, Bio-Inspired Titanium Dioxide Materials with Special Wettability and Their Applications, Chem. Rev. 114 (2014) 10044-10094. 14
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
[15] S. Zheng, C. Li, Q. Fu, W. Hu, T. Xiang, Q. Wang, M. Du, X. Liu, Z. Chen, Development of stable superhydrophobic coatings on aluminum surface for corrosion-resistant, self-cleaning, and anti- icing applications, Mater. Des. 93 (2016) 261-270. [16] K.M. Ahmmed, C. Patience, A.M. Kietzig, Internal and External Flow over Laser-Textured Superhydrophobic Polytetrafluoroethylene (PTFE), ACS Appl. Mater. Interfaces 8 (2016) 2741127419. [17] G. Wang, Z. Zeng, H. Wang, L. Zhang, X. Sun, Y. He, L. Li, X. Wu, T. Ren, Q. Xue, Low Drag Porous Ship with Superhydrophobic and Superoleophilic Surface for Oil Spills Cleanup, ACS Appl. Mater. Interfaces 7 (2015) 26184-26194. [18] Y.K. Lai, F. Pan, C. Xu, H. Fuchs, L.F. Chi, In Situ Surface- modification- induced superhydrophobic patterns with reversible wettability and adhesion, Adv. Mater. 25 (2013) 16821686. [19] S. Alexander, J. Eastoe, A.M. Lord, F. Guittard, A.R. Barron, Branched Hydrocarbon Low Surface Energy Materials for Superhydrophobic Nanoparticle Derived Surfaces, ACS Appl. Mater. Interfaces 8 (2016) 660-666. [20] T.L. Liu, C.J. Kim, Repellent surfaces. Turning a surface superrepellent even to completely wetting liquids, Science 346 (2014) 1096-100. [21] R. Nishimura, K. Hyodo, H. Sawaguchi, Y. Yamamoto, Y. Nonomura, H. Mayama, S. Yokojima, S. Nakamura, K. Uchida, Fractal Surfaces of Molecular Crystals Mimicking Lotus Leaf with Phototunable Double Roughness Structures, J. Am. Chem. Soc. 138 (2016) 10299-10303. [22] M. Gao, D.P. Wang, Y.F. Huang, S. Meng, W.H. Wang, Tunable hydrophobicity on fractal and micro-nanoscale hierarchical fracture surface of metallic glasses, Mater. Des. 95 (2016) 612617. [23] F. Li, M. Du, Q. Zheng, Dopamine/Silica Nanoparticle Assembled, Microscale Porous Structure for Versatile Superamphiphobic Coating, ACS Nano 10 (2016) 2910-2921. [24] Y.Y. Wu, M. Bekke, Y. Inoue, H. Sugimura, H. Kitaguchi, C.S. Liu, O. Takai, Mechanical durability of ultra-water-repellent thin film by microwave plasma-enhanced CVD, Thin Solid Films 457 (2004) 122-127. [25] H. Wang, Q. Yao, C. Wang, B. Fan, Q. Sun, C. Jin, Y. Xiong, Y. Chen, A simple, one-step hydrothermal approach to durable and robust superparamagnetic, superhydrophobic and electromagnetic wave-absorbing wood, Sci. Rep. 6 (2016) 35549. [26] X. Wang, M.Q. Zhang, R. Kou, L.L. Lu, Y. Zhao, X.W. Xu, G.M. Liu, Y.M. Zheng, S.H. Yu, Unique Necklace-Like Phenol Formaldehyde Resin Nanofibers: Scalable Templating Synthesis, Casting Films, and Their Superhydrophobic Property, Adv. Funct. Mater. 26 (2016) 5086-5092. [27] L. Feng, Z.Y. Zhang, Z.H. Mai, Y.M. Ma, B.Q. Liu, L. Jiang, D.B. Zhu, A super- hydrophobic and super-oleophilic coating mesh film for the separation of oil and water, Angew. Chem. Int. Edit. 43 (2004) 2012-2014.
15
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
[28] S.H. Li, J.Y. Huang, Z. Chen, G.Q. Chen, Y.K. Lai, A review on special wettability textiles: theoretical models, fabrication technologies and multifunctional applications, J. Mater. Chem. A 5 (2017) 31-55. [29] X. Wu, Q. Fu, D. Kumar, J.W.C. Ho, P. Kanhere, H. Zhou, Z. Chen, Mechanically robust superhydrophobic and superoleophobic coatings derived by sol- gel method, Mater. Des. 89 (2016) 1302-1309. [30] A.Y. Vorobyev, C. Guo, Direct femtosecond laser surface nano/microstructuring and its applications, Laser Photonics Rev. 7 (2013) 385-407. [31] D. Gong, J. Long, D. Jiang, P. Fan, H. Zhang, L. Li, M. Zhong, Robust and Stable Transparent Superhydrophobic Polydimethylsiloxane Films by Duplicating via a Femtosecond Laser Ablated Template, ACS Appl. Mater. Interfaces 8 (2016) 17511-17518. [32] J. New, I.S. Zope, S.N.A. Rahman, X.L.W. Yap, A. Dasari, Physiological comfort and flame retardancy of fabrics with electrostatic self-assembled coatings, Mater. Des. 89 (2015) 413-420. [33] H. Wang, H. Zhou, H. Niu, J. Zhang, Y. Du, T. Lin, Dual- Layer Superamphiphobic/Superhydrophobic-Oleophilic Nanofibrous Membranes with Unidirectional OilTransport Ability and Strengthened Oil-Water Separation Performance, Adv. Mater. Interfaces 2 (2015) 1400506. [34] H. Bellanger, T. Darmanin, E.T. de Givenchy, F. Guittard, Chemical and Physical Pathways for the Preparation of Superoleophobic Surfaces and Related Wetting Theories, Chem. Rev. 114 (2014) 2694-2716. [35] S.N. Zhang, J.Y. Huang, Y.X. Tang, S.H. Li, M.Z. Ge, Z. Chen, K.Q. Zhang, Y.K. Lai, Understanding the Role of Dynamic Wettability for Condensate Microdrop Self-Propelling Based on Designed Superhydrophobic TiO 2 Nanostructures, Small 13 (2017) 1600687. [36] S.H. Li, J.Y. Huang, M.Z. Ge, C.Y. Cao, S. Deng, S.N. Zhang, G.Q. Chen, K.Q. Zhang, S.S. Al-Deyab, Y.K. Lai, Robust Flower-Like TiO 2 @Cotton Fabrics with Special Wettability for Effective Self-Cleaning and Versatile Oil/Water Separation, Adv. Mater. Interfaces 2 (2015) 1500220. [37] S.H. Li, J.Y. Huang, M.Z. Ge, S.W. Li, T.L. Xing, G.Q. Chen, Y.Q. Liu, K.Q. Zhang, S.S. AlDeyab, Y.K. Lai, Controlled grafting superhydrophobic cellulose surface with environmentally friendly short fluoroalkyl chains by ATRP, Mater. Des. 89 (2015) 815-822. [38] C.H. Xue, L. Zhang, P. Wei, S.T. Jia, Fabrication of superhydrophobic cotton textiles with flame retardancy, Cellulose 23 (2016) 1471-1480. [39] Y. Liu, X. Wang, B. Fei, H. Hu, C. Lai, J.H. Xin, Bioinspired, Stimuli-Responsive, Multifunctional Superhydrophobic Surface with Directional Wetting, Adhesion, and Transport of Water, Adv. Funct. Mater. 25 (2015) 5047-5056. [40] Y. Chen, S. Li, X. Pei, J. Zhou, X. Feng, S. Zhang, Y. Cheng, H. Li, R. Han, B. Wang, A Solvent-Free Hot-Pressing Method for Preparing Metal-Organic-Framework Coatings, Angew. Chem. Int. Edit. 55 (2016) 3419-3423. 16
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
[41] Z.-Y. Deng, W. Wang, L.-H. Mao, C.-F. Wang, S. Chen, Versatile superhydrophobic and photocatalytic films generated from TiO 2 -SiO2 @PDMS and their applications on fabrics, J. Mater. Chem. A 2 (2014) 4178-4184. [42] M. Wang, J. Ioccozia, L. Sun, C. Lin, Z. Lin, Inorganic- modified semiconductor TiO 2 nanotube arrays for photocatalysis, Energy Environ. Sci. 7 (2014) 2182-2202. [43] M. Yu, Z. Wang, H. Liu, S. Xie, J. Wu, H. Jiang, J. Zhang, L. Li, J. Li, Laundering Durability of Photocatalyzed Self-Cleaning Cotton Fabric with TiO 2 Nanoparticles Covalently Immobilized, ACS Appl. Mater. Interfaces 5 (2013) 3697-3703. [44] M.Z. Ge, Q.S. Li, C.Y. Cao, J.Y. Huang, S.H. Li, S.N. Zhang, Z. Chen, K.Q. Zhang, S.S. AlDeyab, Y.K. Lai, One-dimensional TiO 2 Nanotube Photocatalysts for Solar Water Splitting, Adv. Sci. 4 (2017) 1600152. [45] Y. Ren, M. Chen, Y. Zhang, L. Wu, Fabrication of rattle-type TiO 2 /SiO 2 core/shell particles with both high photoactivity and UV-shielding property, Langmuir 26 (2010) 11391-11396. [46] H.B. Wu, H.H. Hng, X.W. Lou, Direct Synthesis of Anatase TiO 2 Nanowires with Enhanced Photocatalytic Activity, Adv. Mater. 24 (2012) 2567-2571. [47] Y. Lai, Y. Tang, J. Gong, D. Gong, L. Chi, C. Lin, Z. Chen, Transparent superhydrophobic/superhydrophilic TiO 2 -based coatings for self-cleaning and anti- fogging, J. Mater. Chem. 22 (2012) 7420-7426. [48] J.Y. Huang, S.H. Li, M.Z. Ge, L.N. Wang, T.L. Xing, G.Q. Chen, X.F. Liu, S.S. A l-Deyab, K.Q. Zhang, T. Chen, Y.K. Lai, Robust superhydrophobic TiO 2 @fabrics for UV shielding, selfcleaning and oil–water separation, J. Mater. Chem. A 3 (2015) 2825-2832. [49] M. Jarosz, K. Syrek, J. Kapusta-Kolodziej, J. Mech, K. Malek, K. Hnida, T. Lojewski, M. Jaskula, G.D. Sulka, Heat Treatment Effect on Crystalline Structure and Photoelectrochemical Properties of Anodic TiO 2 Nanotube Arrays Formed in Ethylene Glycol and Glycerol Based Electrolytes, J. Phys. Chem. C 119 (2015) 24182-24191. [50] X. Zhang, H. Kono, Z. Liu, S. Nishimoto, D.A. Tryk, T. Murakami, H. Sakai, M. Abe, A. Fujishima, A transparent and photo-patternable superhydrophobic film, Chem. Commun. 46 (2007) 4949-4951. [51] A. Oláh, H. Hillborg, G.J. Vancso, Hydrophobic recovery of UV/ozone treated poly(dimethylsiloxane): adhesion studies by contact mechanics and mechanism of surface modification, Appl. Surf. Sci. 239 (2005) 410-423. [52] H. Bai, L. Wang, J. Ju, R. Sun, Y. Zheng, L. Jiang, Efficient Water Collection on Integrative Bioinspired Surfaces with Star-Shaped Wettability Patterns, Adv. Mater. 26 (2014) 5025-5030. [53] C. Cao, M. Ge, J. Huang, S. Li, S. Deng, S. Zhang, Z. Chen, K. Zhang, S.S. Al- Deyab, Y. Lai, Robust fluorine- free superhydrophobic PDMS–ormosil@fabrics for highly effective self-cleaning and efficient oil–water separation, J. Mater. Chem. A 4 (2016) 12179-12187. [54] B. Poudel, Q. Hao, Y. Ma, Y. Lan, A. Minnich, B. Yu, X. Yan, D. Wang, A. Muto, D. Vashaee, X. Chen, J. Liu, M.S. Dresselhaus, G. Chen, Z. Ren, High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys, Science 320 (2008) 634-638. 17
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
[55] Y. Shang, Y. Si, A. Raza, L. Yang, X. Mao, B. Ding, J. Yu, An in situ polymerization approach for the synthesis of superhydrophobic and superoleophilic nanofibrous membranes for oil- water separation, Nanoscale 4 (2012) 7847-7854.
18
AC C
Graphical abstract
EP T
ED
MA
NU
SC
RI
PT
ACCEPTED MANUSCRIPT
19
PT
ACCEPTED MANUSCRIPT
AC C
EP T
ED
MA
NU
SC
RI
Highlights Multifunctional fabrics were constructed via a facile one-step hot-pressing process. Environmentally- friendly fluorine- free silane was grafted to realize superhydrophobic. Excellent anti-wetting property with superior abrasion and laundering stability. UV-protection and oil-water separation ability of TiO 2 @fabrics were demonstrated.
20