Next Article in Journal
Novel Alumina Dispersion-Strengthened 316L Steel Produced by Attrition Milling and Spark Plasma Sintering
Previous Article in Journal
A Simple and Effective Method to Adjust the Structure and Performance of DLC Films on Polymethyl Methacrylate(PMMA) Substrate
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Coatings
Volume 13
Issue 2
10.3390/coatings13020323
coatings-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Fluorine-Free Dual Superamphiphobic Cellulose Paper Coated with Mushroom-like Pillar Microstructure

by
Xun Ke
1,†,
Kaipeng Wang
1,†,
Lihong Zhao
1,2,*,
Zhiwei Wang
2 and
Min Wu
2
1
Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China
2
Guangxi Key Laboratory of Clean Pulp & Papermaking and Pollution Control, Guangxi University, Nanning 530004, China
*
Author to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Coatings 2023, 13(2), 323; https://doi.org/10.3390/coatings13020323
Submission received: 30 December 2022 / Revised: 22 January 2023 / Accepted: 26 January 2023 / Published: 1 February 2023
Browse Figures
Versions Notes

Abstract

:
In this work, we report a unique and facile approach to the manufacture of fluorine-free superamphiphobic paper. Based on the principle that Fe3O4 nanoparticles (NPs) arranged along the direction of a magnetic field, the mixture of Fe3O4 NPs and polydimethylsiloxane (PDMS) was coated on kraft paper through self-assembly and thermal-curing at a high temperature in a magnetic field, fabricating a mushroom-like microstructure on the paper. At an Fe3O4 NPs content of 75%, the radius of the mushroom-like pillar caps (RCAP) and center-to-center spacing between two pillars (S) obtained the optimal size of 37 ± 18 μm and 237 ± 38 μm, respectively. The oil-contact angle and water-contact angle of the fabricated paper were up to 156° and 160.4°, respectively. It also showed excellent oleophobic stability; the oil-contact angle was still maintained at 141.9° after 1 h. In addition, the contact angles of milk, ethylene glycol and castor oil were all above 150°, and the contact angle of diiodomethane was 134.2°. Moreover, the sample showed great oil resistance with a kit rating value of 12/12 and permeability of 1800+ s.

1. Introduction

Superhydrophobic and superoleophobic surfaces show excellent non-wetting properties due to a contact angle (CA) greater than 150° and sliding angle (SA) less than 10° [1]. Superamphiphobic paper is one of superamphiphobic materials, covering a wide range of applications such as packaging [2,3,4], antifouling biomedical devices [5], microfluidic devices [6,7,8], and medical testing strips [9,10]. However, it is difficult for paper surfaces to reach over 90° of the oil-contact angle (OCA) and water-contact angle (WCA), due to the abundant hydrophilic hydrogen-bonding hydroxyl group of cellulose and porous structure of the paper substrate [11]. In recent years, fluorinated chemicals and nanoparticles [12,13] were commonly used to impart satisfactory amphiphobicity to surfaces [14,15,16] (Table 1). However, the use of fluorinated chemicals is a serious threat to human health and environmental safety [17,18]. Therefore, it is necessary to find a greener way to improve the performance of paper. At present, there are only a few studies on the preparation of superamphiphobic paper with fluorine-free chemicals (Table 1), while most of them are commonly used to impart paper with excellent hydrophobicity but unsatisfactory lipophobicity [19,20,21,22,23].
The re-entrant microstructure significantly influences surface wettability [26]. Various methods have been utilized to construct re-entrant structures, such as 3D printing [27,28,29], photoetching [30,31], self-assembly [32], electrospinning [33] and solvothermal [34]. Although these methods have significant effectiveness, feasible methods are mainly applicable to rigid materials, for example silicon wafers, stainless steel mesh and quartz wafers. Paper is composed of interlaced fibers at micron and nanometer levels [35], which is a flexible material with a large specific surface area and an irregular coarse surface, so it is difficult to construct a regular rough structure on the surface similar to rigid materials.
PDMS is a polymer binder commonly used to construct environmentally friendly amphiphobic coatings, owing its degradation [36,37,38], low surface energy, chemical stability and high adhesion to the substrate [39]. Furthermore, Fe3O4 nanoparticles (NPs) have good magnetic responsiveness, high specific surface area and good biocompatibility [40,41]. Although the utilization of Fe3O4 NPs to construct re-entrant microstructures has been reported [42,43], the difference from previous work is the combination of mushroom-like microstructure with paper. The key to this design not only solves the difficulties in constructing re-entrant structures for flexible materials, but also provides an ideal scheme for the preparation of green fluorine-free double superamphiphobic paper.
Cellulosic paper is an extremely hydrophilic and lipophilic flexible fiber material, and it is challenging to render it resistant to liquids without using a fluoride that is harmful to the human body and environment. Herein, we report on an innovative method for making fluorine-free superamphiphobic cellulose paper. PDMS and Fe3O4 NPs were used to construct mushroom-like pillar arrays (MLPAs) on the surface of paper under a high-temperature magnetic field, resulting in oil- and water-repellent performance. The effects of the mushroom-like caps radius (RCAP), center-to-center spacing between two pillars (S) and pillar height for MLPAs on the amphiphobicity of the prepared papers were investigated, and the oil resistance behavior of the modified paper was also examined. In addition, the fluorine-free superamphiphobic paper was further characterized in terms of morphological structure, durability and mechanical properties. Consequently, this method could provide a good alternative to existing fluorinated paper.

2. Materials and Methods

2.1. Materials

Slide, rubidium magnet, kraft paper, cover glass, polyfluortetraethylene (PTFE) plate, and milk were purchased from retail stores. The PDMS and curing agent (Sylgard 184) were obtained from Dow Corning (Midland, MI, USA). Peanut oil was purchased from Beijing Golden Arowana Co., Ltd. (Shenzhen, China). Ethylene glycol, diiodomethane, castor oil, methylbenzene, n-heptane, turpentine, Fe3O4 NPs (radius: 200 nm, refractive index: 3.0) and quartz sand were obtained from Macklin Co., Ltd. (Shanghai, China).

2.2. Fabrication of Superamphiphobic Paper

The fluorine-free superamphiphobic paper was constructed by an effective self-assembly process assisted by magnetic Fe3O4 NPs. The Fe3O4 NPs were thoroughly mixed with PDMS at the mass contents of 70%, 72.5%, 75%, 80%, 85% and 90% (w/w). After vacuum degassing for 30 min, the mixture was coated on kraft paper adhered to the slide. Then, coverslips with a thickness of 400 μm were fixed to the ends of the substrate. The glass slides were fixed to a PTFE plate and placed above the slides with the PTFE plate side facing down [43]. A magnet was placed under the substrate and the self-assembly generated MLPAs along the direction of the magnetic field. The magnet was placed in an oven with samples after curing at 65°C for 2h. The curing and the magnetic field time provided by the magnet were the same for each sample. A mushroom-like microstructured surface with a kraft paper substrate was obtained.
The Fe3O4 NPs content was fixed at 75%, and coverslips with thicknesses of approximately 250, 300, 400, 500 and 600 μm were fixed at each end of the substrate, while other conditions were kept consistent to obtain MLPAs with different heights.

2.3. Characterization

2.3.1. Scanning Electron Microscopy (SEM)

The surface morphologies of the various samples were observed using a JEOL 6400 SEM (energy beam: 20 keV; working distance: 7.5 mm, Jeol Ltd., Tokyo, Japan). Samples were prepared for SEM characterization by mounting them onto aluminum stubs using a carbon double-sided tape and spraying with Au.

2.3.2. Contact Angles (CAs) and Sliding Angles (SAs)

The CAs of different liquids were measured with a contact angle surface analyzer (Model OCA20, from Dataphysics Instruments GmbH, Filderstadt, Germany). Testing liquid droplets with a volume of approximately 5 μL were placed onto the specimen and the values were recorded after 30 s or a certain period of time. Five replications were recorded for each sample.
SAs were determined by adding a 100 µL droplet of the test liquid onto the surface of each specimen, which was affixed onto a steel plate. The angle of this steel plate with respect to the horizontal plane was then increased at a constant rate (2°/s) until the droplets began to slide. The angle of the steel plate at this point was recorded as the sliding angle of the specimen.

2.3.3. Grease Resistance and Grease Permeability Properties

A grease-resistance test followed the TAPPI standard T559 pm-96 protocol. Kit rating solutions were prepared by mixing castor oil, heptane, and toluene in various contents. The solutions were numbered from 1 to 12, representing oil repellency from poor to excellent. During each test, one kit rating solution was added dropwise onto the paper substrate for 15 s and then wiped away. If no oil mark was left on the paper surface after 15 s, that kit rating number was considered to be passed, and a higher number solution was then tested at the same position until the surface failed the test. The value reported herein for each sample corresponds to the average of three records.
Grease permeability of samples were tested using TAPPI standard T454om-10. Briefly, each specimen was placed on a white sheet of paper. Five grams of dry sand were placed into a 25 mm tube and then the tube was put onto the test specimen to obtain a heap and 1.1 mL of red-dyed turpentine was added dropwise to the heap of sand. The time in seconds was measured and indicated as the result, after which the first turpentine red penetration appeared on the white sheet of paper present underneath the test specimen. A length of 1800 s corresponds to a high penetration resistance to fats and oils, and the higher grease resistant paper was the specimen with a longer time (1800s+).

2.3.4. Caps Radius (RCAP) and Spacing between Two Pillars (S)

The morphology of the sample was observed by scanning electron microscope, then PS was used to process the picture so that the mushroom cap became black and the rest became white; then Nano Measure software (version 1.2) was used to analyze and calculate the image.

3. Result and Discussion

In order to prepare superamphiphobic paper with MLPAs, Fe3O4 NPs contents were fully mixed at 70, 72.5, 75, 80, 85 and 90 wt% of the PDMS weight. Then the kraft paper with MLPAs was manufactured through coating, self-assembly and thermal curing (Figure 1a). The parameters of the microstructure were adjusted by the content of Fe3O4 NPs, and it was found that the geometrical dimensions of the MLPAs on paper substrate could be tuned by the weight fraction of Fe3O4 NPs to PDMS. In addition, MLPAs with different heights were manufactured at a Fe3O4 NPs content of 75 wt%.
It could be observed by SEM that the MLPAs were effectively created by the self-assembly process (Figure 1b,c). Moreover, the geometrical dimensions of the MLPAs could be tuned by the concentration fraction of Fe3O4 NPs. As shown in Figure S1, some of the micropillars did not form mushroom-like caps and the spacing of the MLPAs was larger when the Fe3O4 NPs content was 70%. We used the softwares Photoshop (version CC 2018), Image-Pro Plus (version 7.0) and Nano Measurer to calculate the R and S in the SEM. The results are shown in Table 2 and Figure S2.
Untread paper has poor liquid resistance due to the porous structure of the paper (Figure S3). The OCA and WCA of the paper surface are 17.9° and 56.8°. Figure 1d depicts the OCAs and WCAs of samples with various RCAP and S. When the content of Fe3O4 NPs was increased from 70% to 75%, the surface oil wettability behavior dramatically transformed from an oleophilic state (an OCA of 39.4°) into a superoleophobic state (a maximum OCA of 156°). Then, the OCAs declined gradually after Fe3O4 NPs content continued to increase but remained significantly above 140°. The trend of WCAs was quite similar to that of OCAs. As the Fe3O4 NPs content increased from 70% to 90%, the WCA rose first (from 143.7° to 160.4°) and then declined (from 160.4° to 140.2°). However, the WCA basically remained around 150°, showing excellent hydrophobic performance.
The sliding angles of oil and water are shown in Figure 1e, which is an important manifestation of the surface wettability. A smaller sliding angle leads to better liquid repellency. With the gradual ascent of Fe3O4 NPs content, the oil and water slide angles of the samples initially decreased and then increased. With the increase in Fe3O4 NPs content from 72.5% to 75%, the oil sliding angle was reduced from 16.9° to a minimum of 8.1°. Afterwards, with the continuous increment of Fe3O4 NPs, the oil slide angle also climbed gradually, but all were below 15°. Trends in WCA were broadly consistent with those in OCA; with the increase of Fe3O4 NPs content from 70% to 75%, the oil sliding angle was reduced from a maximum of 23.3° to a minimum of 12.6°, and then gradually rose after Fe3O4 NPs content continued to increase.
Fixing the Fe3O4 NPs content at 75% and maintaining the parameters RCAP and S nearly constant, an analysis of the variation of OCAs and WCAs induced by the micropillar heights ranging from 50 μm to 400 μm was conducted. Figure 1f shows that the OCAs and WCAs were less influenced by the micropillar height and were largely maintained around 155° and 159°.
A 3D model was constructed for analyzing the surface liquid wettability of MLPAs, as shown in Figure 2. The liquid level that had no contact with the MLPAs depressurized downward due to gravity. Meanwhile, an additional upward pressure was generated on the concave surface of the sunken liquid level with the influence of surface tension. According to the Laplace equation:
∆P = 2γ/RCUR
∆P is additional pressure; γ is surface tension of the liquid; and RCUR is the radius of the curvature of the lower concave surface. The wetting process of the test liquid contacting the MLPAs is shown in Figure 2a–d. According to Equation (1) and Figure 2b, when the gap length (D = S − 2RCAP) is just equal to the curvature diameter of the concave surface of the liquid level, the radius of curvature is contracted to its minimum size and has an additional maximum upward pressure. However, when the D is larger, the additional maximum pressure generated by the concave liquid level cannot offset the pressure generated by liquid gravity. Therefore, the test liquid added to the surface of MLPAs will change in the range of Figure 2a–d, and the test liquid finally falls into the gap of MLPAs, so the solid-liquid contact conforms to the Wenzel model. When D is gradually reduced to a certain value, the maximum additional pressure is greater than or equal to the pressure generated by gravity. At this time, the liquid does not fall into the gap of the MLPAs, but remains in the state of Figure 2a,b; thus, the solid-liquid contact conforms to the Cassie model.
Therefore, for the sample with 70 wt% Fe3O4 NPs, the Wenzel model (see Figure S4) is applicable only when the D is larger. According to the Wenzel model formula:
cosθA = r cosθY
θA is apparent contact angle; (r > 1) is the surface roughness; and θY is the Young’s contact angle on the smooth surface. A further deduction demonstrates that, when θY < 90°, θA < θY is obtained through mathematical reasoning. In a similar way, θA > θY when the intrinsic surface is hygrophobic, which leads to an enhanced contact angle. In addition, it is concluded that the roughness can intensify the intrinsic wetting tendency to more hygrophilic (θY < 90°) or hygrophobic (θY > 90°). The OCA and WCA of the PDMS membrane were 66° and 120°, respectively. Thus, the OCA and WCA of the fabricated sample with a rough surface at 70 wt% Fe3O4 NPs were 39.4° and 143.7°, respectively. Moreover, the sliding resistance increased due to the test liquid being 25trapped in the gap of the MLPAs, so the oil slide angle and water slide angle of samples were larger.
The samples containing 75% to 90% Fe3O4 NPs supported the state of liquid droplets in the Cassie model due to the smaller D value. According to the Cassie model:
cosθA = f1 cosθY − f2 ≈ f1 (cosθY + 1) − 1 ≈ πRCAP2/S2 (cosθY + 1) − 1
where f1 and f2 are the solid-liquid and vapor-liquid area fractions, θA is the apparent contact angle, θY is the Young’s contact angle, RCAP is the radius of the mushroom-like caps, and S is the center-to-center spacing between two pillars. With the increase in Fe3O4 NPs content from 70% to 90%, the mushroom cap radius RCAP ascended from 32 ± 17 to 54 ± 24 μm, the microinterpillar spacing S descended from 318 ± 78 to 175 ± 39 μm, and the fraction RCAP/S increased from 0.1 to 0.31. It could be calculated from Equation (2) that higher RCAP/S fractions correspond to a higher solid-liquid area fraction f1, leading to a lower apparent contact angle θA. Therefore, while the content of Fe3O4 NPs continued to increase, the R rise, the S drop, and the RCAP/S fraction gradually ascend (see Table 2), and accordingly the CAs gradually decline. Furthermore, since the samples supported the status of liquid droplets in the Cassie model, its slide angles were smaller than the samples with 70% and 72.5% Fe3O4 NPs. However, as the RCAP/S fraction continued to increase, the contact area between the test liquid and the mushroom-like pillar gradually climbed, so the slide angles gradually mounted. Therefore, when the content of Fe3O4 NPs was 75%, an optimal RCAP and S was constituted, the OCA and WCA reached a maximum and the slide angle reached a minimum. According to Figure 2, while keeping the RCAP and S constant, the alterations of the pillar height had no effect on the solid-liquid contact, as was the case on the CA (Figure 1f).
The oleophobic stability of samples with various contents are shown in Figure 3. The OCA of the sample with 70 wt% Fe3O4 NPs was 30° in 30 s and dropped to 0° after 5 min, which showed oleophobic instability. However, the OCA of sample with 75 wt% Fe3O4 NPs was 154.3° in 30s and was maintained at 141.9° in the following 1 h, showing excellent oleophobic stability. For the samples with higher Fe3O4 NPs content, the OCAs were kept above 130° after 1 h.
In addition, we also conducted experiments on the oleophobic stability of samples with various pillar heights, as shown in Figure 3b. The OCA of each sample was maintained around 145° after 1 h, reflecting perfect oleophobic stability. Hence, a lower influence of pillar height on the oleophobicity could be demonstrated.
To further demonstrate the superamphiphobic property of the prepared paper, we systematically characterized the wettability of the sample containing 75% Fe3O4 NPs. Figure S5 shows photos of the as-prepared samples before and after being immersed in water dyed with methylene blue and peanut oil dyed red with Sudan III. The samples removed from the liquids retained their original color without a trace of pollution, illustrating an excellent water and oil repellency. Furthermore, the superamphiphobicity of the samples that repelled various liquids with different surface tensions was evaluated by measuring CAs and sliding angles. The CAs of milk, ethylene glycol and castor oil were all above 150°, and the CA of diiodomethane was 134.2°. The sliding angles of all liquids were maintained at about 10°, which confirmed the superamphiphobicity of the as-prepared samples with MLPAs. Compared with some previous studies on fluorine-free double amphiphobic paper (Table 2), both excellent waterproofing and oil-resistance are significant strengths of this study.
Durability is also a crucial criterion for coated paper. The superamphiphobic surfaces remained superhydrophobic after 1 h. The OCA of the sample containing 75% Fe3O4 NPs was 154.3° after 30 s and remained at 141.9° at 1 h (Figure 3d), indicating that the coated paper with mushroom-like microstructure has amphiphobic durability. The excellent durability and abrasion properties provide a wide range of applications for fluorine-free superamphiphobic paper. Moreover, the abrasion of the superamphiphobic surface was tested using sandpaper-abrasion experiment. As shown in Figure 3e, after 20 abrasion cycle tests, the paper exhibited exceedingly high durability (OCA and WCA > 150°).
In addition, we evaluated the grease resistance and grease permeability for the sample with the 75 wt% Fe3O4 NPs. The kit rating value of all the samples was 12/12, and all demonstrated low oil permeability at 1800+ s, owing to the dense membrane formed by PDMS after curing.

4. Conclusions

In summary, we have developed fluorine-free coatings that can enhance the liquid resistance for kraft paper. Based on the arrangement of Fe3O4 NPs along the magnetic field direction, a mushroom-like microstructure was constructed on the surface. The superamphiphobic paper-based material has a large contact angle for peanut oil, deionized water, milk, ethylene glycol, castor oil and diiodomethane. The sample also has outstanding oil resistance and repellent stability. Furthermore, we have used mathematical models to elucidate the paper-surface wetting mechanism. In summary, the paper with superamphiphobicity was developed without using fluorinated chemicals, which could contribute to the field of green chemistry and bring benefits to industries as well as the environment.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/coatings13020323/s1, Figure S1: SEM images of the top view of the as-prepared MLPAs (a–f); Figure S2: The histograms of diameter of (a–f) pillar caps (R) and (g–l) interpillar distance (S); Figure S3: SEM images of the untread paper; Figure S4: Three wetting models (a–c); Figure S5: (a) After immersing in rapeseed oil dyed red with Sudan III, the surface remains its original color, exhibiting water-repellent properties; (b) After immersing in methylene blue-dyed water, the surface is not contaminated by the oil, demonstrating the oil repellency.

Author Contributions

Conceptualization X.K.; methodology, K.W.; writing—original draft preparation, X.K.; writing—review and editing, L.Z.; formal analysis, L.Z.; software, M.W.; supervision, Z.W. All authors have read and agreed to the published version of the manuscript.

Funding

The project was supported by the Foundation (No. 2021KF24) of Guangxi Key Laboratory of Clean Pulp and Papermaking and Pollution Control, College of Light Industry and Food Engineering, Guangxi University.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Yong, J.; Chen, F.; Yang, Q.; Huo, J.; Hou, X. Superoleophobic surfaces. Chem. Soc. Rev. 2017, 46, 4168–4217. [Google Scholar] [CrossRef] [PubMed]
  2. Hamdani, S.S.; Li, Z.; Sirinakbumrung, N.; Rabnawaz, M. Zein and PVOH-based bilayer approach for plastic-free, repulpable and biodegradable oil-and water-resistant paper as a replacement for single-use plastics. Ind. Eng. Chem. Res. 2020, 59, 17856–17866. [Google Scholar] [CrossRef]
  3. Zhang, Y.; Kan, L.; Feng, H.; Ling, H.; Wang, X. All-biomass-based eco-friendly waterproof coating for paper-based green packaging. Green Chem. 2022, 24, 7039–7048. [Google Scholar]
  4. Kansal, D.; Hamdani, S.S.; Ping, R.; Sirinakbumrung, N.; Rabnawaz, M. Food-safe Chitosan−Zein dual-layer coating for water- and oil-repellent paper substrates. ACS Sustain. Chem. Eng. 2020, 8, 6887–6897. [Google Scholar] [CrossRef]
  5. Ying, B.; Park, S.; Chen, L.; Dong, X.; Young, E.W.K.; Liu, X. NanoPADs and nanoFACEs: An optically transparent nanopaper-based device for biomedical applications. Lab. Chip. 2020, 20, 3322–3333. [Google Scholar] [CrossRef]
  6. Jalal, U.M.; Jin, G.J.; Shim, J.S. Paper-plastic hybrid microfluidic device for smartphone-based colorimetric analysis of urine. Anal. Chem. 2017, 89, 13160–13166. [Google Scholar] [CrossRef]
  7. Gao, B.; Li, X.; Yang, Y.; Chu, J.; He, B. Emerging paper microfluidic devices. Analyst 2019, 144, 6497–6511. [Google Scholar] [CrossRef]
  8. Zhang, Z.; Ma, X.; Jia, M.; Li, B.; Rong, J.; Yang, X. Deposition of CdTe quantum dots on microfluidic paper chips for rapid fluorescence detection of pesticide 2,4-D. Analyst 2019, 144, 1282–1291. [Google Scholar] [CrossRef]
  9. Antosik, A.K.; Piątek, A.; Wilpiszewska, K. Carboxymethylated starch and cellulose derivatives-based film as human skin equivalent for adhesive properties testing. Carbohydr. Polym. 2019, 222, 115014–115020. [Google Scholar] [CrossRef]
  10. Liu, D.; Ju, C.; Han, C.; Shi, R.; Chen, X.; Duan, D.; Yan, J.; Yan, X. Nanozyme chemiluminescence paper test for rapid and sensitive detection of SARS-CoV-2 antigen. Biosens. Bioelectron. 2021, 173, 112817–112825. [Google Scholar] [CrossRef]
  11. Rhim, J.-W.; Lee, J.-H.; Hong, S.-I. Water resistance and mechanical properties of biopolymer (alginate and soy protein) coated paperboards. LWT Food Sci. Technol. 2006, 39, 806–813. [Google Scholar] [CrossRef]
  12. Dinh, T.D.; Phan, M.N.; Nguyen, D.T.; Le, T.M.D.; Nadda, A.K.; Srivastav, A.L.; Pham, T.N.M.; Pham, T.D. Removal of beta-lactam antibiotic in water environment by adsorption technique using cationic surfactant functionalized nanosilica rice husk. Environ. Res. 2022, 210, 112943. [Google Scholar] [CrossRef]
  13. Vu, T.N.; Le, P.H.P.; Pham, D.N.P.; Hoang, T.H.; Nadda, A.K.; Le, T.S.; Pham, T.D. Highly adsorptive protein inorganic nanohybrid of Moringa seeds protein and rice husk nanosilica for effective adsorption of pharmaceutical contaminants. Chemosphere 2022, 307, 135856. [Google Scholar] [CrossRef]
  14. Zhang, F.; Wang, C.; Wang, X.; Wang, J.; Zhang, H.; Liu, Y.; Huang, X.; Xu, K.; Bai, Y.; Wang, P. Fabrication of superhydrophobic and lyophobic paper for self-cleaning, moisture-proof and antibacterial activity. Appl. Surf. Sci. 2022, 598, 153639–153650. [Google Scholar] [CrossRef]
  15. Jiang, L.; Tang, Z.; Clinton, R.M.; Breedveld, V.; Hess, D.W. Two-step process to create “roll-off” superamphiphobic paper surfaces. ACS Appl. Mater. Interfaces 2017, 9, 9195–9203. [Google Scholar] [CrossRef]
  16. Tudu, B.K.; Kumar, A.; Bhushan, B. Fabrication of superoleophobic cotton fabric for multi-purpose applications. Philos. Trans. R. Soc. A 2019, 377, 20190129. [Google Scholar] [CrossRef]
  17. Huan, Z.; Huan, C.; Huan, K.; Qiu, L.; Lv, P.; Wu, P.; Yang, Y. Toxic effects of fluoride on organisms. Life Sci. Res. Rep. 2018, 198, 18–24. [Google Scholar]
  18. Araya, D.; Podgorski, J.; Kumi, M.; Mainoo, P.A.; Berg, M. Fluoride contamination of groundwater resources in Ghana: Country-wide hazard modeling and estimated population at risk. Water Res. 2022, 212, 118083–118092. [Google Scholar] [CrossRef]
  19. Kansal, D.; Hamdani, S.S.; Ping, R.; Rabnawaz, M. Starch and zein biopolymers as a sustainable replacement for PFAS, silicone oil, and plastic-coated paper. Ind. Eng. Chem. Res. 2020, 59, 12075–12084. [Google Scholar] [CrossRef]
  20. Wang, K.; Zhao, L.; He, B. Chitosan/montmorillonite coatings for the fabrication of food-safe greaseproof paper. Polymers 2021, 13, 1607. [Google Scholar] [CrossRef]
  21. Cheng, Q.-Y.; An, X.-P.; Li, Y.-D.; Huang, C.-L.; Zeng, J.-B. Sustainable and biodegradable superhydrophobic coating from epoxidized soybean oil and ZnO nanoparticles on cellulosic substrates for efficient oil/water separation. ACS Sustain. Chem. Eng. 2017, 5, 11440–11450. [Google Scholar] [CrossRef]
  22. Hamdani, S.S.; Li, Z.; Rabnawaz, M.; Kamdem, D.P.; Khan, B.A. Chitosan-graft-poly(dimethylsiloxane)/zein coatings for the fabrication of environmentally friendly oil- and water-resistant paper. ACS Sustain. Chem. Eng. 2020, 8, 5147–5155. [Google Scholar] [CrossRef]
  23. Zhang, F.; Tao, H.; Li, Y.; Wang, Y.; Zhou, Y.; Xu, Q.; Ma, J. Enhanced pickering emulsion stabilization of cellulose nanocrystals and application for reinforced and hydrophobic coatings. Coatings 2022, 12, 1594. [Google Scholar] [CrossRef]
  24. Gu, F.; Yang, W.; Song, J.; Xiao, H.; Wang, W.; Cai, Z. Crosslinked PVA/nanoclay hydrogel coating for improving water vapor barrier of cellulose-based packaging at high temperature and humidity. Coatings 2022, 12, 1562. [Google Scholar] [CrossRef]
  25. Tuteja, A.; Choi, W.; Ma, M.; Mabry, J.M.; Mazzella, S.A.; Rutledge, G.C.; McKinley, G.H.; Cohen, R.E. Designing superoleophobic surfaces. Science 2007, 318, 1618–1622. [Google Scholar] [CrossRef]
  26. Cao, P.; Tao, L.; Gong, J.; Wang, T.; Wang, Q.; Ju, J.; Zhang, Y. 4D printing of a sodium alginate hydrogel with step-wise shape deformation based on variation of crosslinking density. ACS Appl. Polym. Mater. 2021, 3, 6167–6175. [Google Scholar] [CrossRef]
  27. Zhang, Y.; Yin, M.-J.; Ouyang, X.; Zhang, A.P.; Tam, H.-Y. 3D μ-printing of polytetrafluoroethylene microstructures: A route to superhydrophobic surfaces and devices. Appl. Mater. Today 2020, 19, 110580–110589. [Google Scholar] [CrossRef]
  28. Shams, H.; Basit, K.; Khan, M.A.; Saleem, S.; Mansoor, A. Realizing surface amphiphobicity using 3D printing techniques: A critical move towards manufacturing low-cost reentrant geometries. Addit. Manuf. 2021, 38, 101777–101814. [Google Scholar] [CrossRef]
  29. Sun, Y.; Guo, Z. Recent advances of bioinspired functional materials with specific wettability: From nature and beyond nature. Nanoscale Horiz. 2019, 4, 52–76. [Google Scholar] [CrossRef]
  30. Kim, J.H.; Shim, T.S.; Kim, S.-H. Lithographic design of overhanging microdisk arrays toward omniphobic surfaces. Adv. Mater. 2016, 28, 291–298. [Google Scholar] [CrossRef]
  31. Jiao, L.; Tong, J.; Wu, Y.; Hu, Y.; Wu, H.; Li, D.; Chen, R. Self-assembly of supraparticles on a lubricated-superamphiphobic patterned surface. Appl. Surf. Sci. 2022, 576, 151684–151698. [Google Scholar] [CrossRef]
  32. Ganesh, V.A.; Dinachali, S.S.; Nair, A.S.; Ramakrishna, S. Robust superamphiphobic film from electrospun TiO2 nanostructures. ACS Appl. Mater. Interfaces 2013, 5, 1527–1532. [Google Scholar] [CrossRef]
  33. Yu, J.; Wang, H.; Yin, N.; Xu, X. HF-assisted one-step synthesis of pompon-like/chip-like FeSe2 particles and their superamphiphobic/antireflective property. RSC Adv. 2014, 4, 24163–24169. [Google Scholar] [CrossRef]
  34. Hyväluoma, J.; Raiskinmäki, P.; Jäsberg, A.; Koponen, A.; Kataja, M.; Timonen, J. Simulation of liquid penetration in paper. Phys. Rev. E 2006, 73, 36705–36713. [Google Scholar] [CrossRef]
  35. Masimukku, S.; Hu, Y.-C.; Lin, Z.-H.; Chan, S.-W.; Chou, T.-M.; Wu, J.M. High efficient degradation of dye molecules by PDMS embedded abundant single-layer tungsten disulfide and their antibacterial performance. Nano Energy 2018, 46, 338–346. [Google Scholar] [CrossRef]
  36. Lv, C.; Wang, J.; Li, Z.; Zhao, K.; Zheng, J. Degradable, reprocessable, self-healing PDMS/CNTs nanocomposite elastomers with high stretchability and toughness based on novel dual-dynamic covalent sacrificial system. Compos. Part B Eng. 2019, 177, 107270. [Google Scholar] [CrossRef]
  37. Beltran, F.O.; Houk, C.J.; Grunlan, M.A. Bioactive siloxane-containing shape-memory polymer (SMP) scaffolds with tunable degradation rates. ACS Biomater. Sci. Eng. 2021, 7, 1631–1639. [Google Scholar] [CrossRef] [PubMed]
  38. Liu, X.; Li, H.; Zhang, J.; Zhu, L.; Zhu, X.; Yu, S.; Xue, J.; Wang, R.; Gan, S.; Wei, B.; et al. Durable superhydrophobic engineered mesh with self-healing and anti-corrosive capabilities for efficient oil/water separation. J. Environ. Chem. Eng. 2022, 10, 108823–108832. [Google Scholar] [CrossRef]
  39. Lu, A.-H.; Salabas, E.L.; Schüth, F. Magnetic nanoparticles: Synthesis, protection, functionalization, and application. Angew. Chem. Int. Ed. 2007, 46, 1222–1244. [Google Scholar] [CrossRef]
  40. Anik, M.I.; Hossain, M.K.; Hossain, I.; Mahfuz, A.M.U.B.; Rahman, M.T.; Ahmed, I. Recent progress of magnetic nanoparticles in biomedical applications: A review. Nano Sel. 2021, 2, 1146–1186. [Google Scholar] [CrossRef]
  41. Huang, Y.; Stogin, B.B.; Sun, N.; Wang, J.; Yang, S.; Wong, T.S. A switchable cross-species liquid repellent surface. Adv. Mater. 2017, 29, 1604641. [Google Scholar] [CrossRef] [PubMed]
  42. Lu, H.; Zhang, M.; Yang, Y.; Huang, Q.; Fukuda, T.; Wang, Z.; Shen, Y. A bioinspired multilegged soft millirobot that functions in both dry and wet conditions. Nat. Commun. 2018, 9, 3944. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  43. Wang, H.; Zhang, Z.; Wang, Z.; Liang, Y.; Cui, Z.; Zhao, J.; Li, X.; Ren, L. Multistimuli-responsive microstructured superamphiphobic surfaces with large-range, reversible switchable wettability for oil. ACS Appl. Mater. Interfaces 2019, 11, 28478–28486. [Google Scholar] [CrossRef] [PubMed]
Coatings 13 00323 g001 550
Figure 1. (a) Schematic illustration of the fabrication of a MLPA with mushroom-like microstructures (b,c) SEM images of the top view and side view of the as-prepared MLPAs. (d) OCAs and WCAs on the surfaces with different Fe3O4 NPs content. (e) The slide angles of water and oil on the surfaces with different Fe3O4 NPs content. (f) Relationships between the CAs (oil, water) and pillar heights.
Figure 1. (a) Schematic illustration of the fabrication of a MLPA with mushroom-like microstructures (b,c) SEM images of the top view and side view of the as-prepared MLPAs. (d) OCAs and WCAs on the surfaces with different Fe3O4 NPs content. (e) The slide angles of water and oil on the surfaces with different Fe3O4 NPs content. (f) Relationships between the CAs (oil, water) and pillar heights.
Coatings 13 00323 g001
Coatings 13 00323 g002 550
Figure 2. (a–d) the different states of mushroom-like pillars support the liquid. (e) Schematic of as-prepared mushroom-like pillars. (S is center-to-center spacing between two pillars, RCUR is the radius of the curvature of the lower concave surface, RCAP is the radius of the mushroom-like pillar caps, ΔP is additional pressure, and ΔPmax is the additional maximum pressure).
Figure 2. (a–d) the different states of mushroom-like pillars support the liquid. (e) Schematic of as-prepared mushroom-like pillars. (S is center-to-center spacing between two pillars, RCUR is the radius of the curvature of the lower concave surface, RCAP is the radius of the mushroom-like pillar caps, ΔP is additional pressure, and ΔPmax is the additional maximum pressure).
Coatings 13 00323 g002
Coatings 13 00323 g003 550
Figure 3. (a) The OCAs of the papers with different Fe3O4 NPs concentrations in 1 h. (b) The OCAs of the papers with pillar heights in 1 h. (c) Apparent contact angle and sliding angle measurements of different liquids on the surfaces. (d) The OCAs and WCAs of papers at different times. (e) The OCAs of the papers with different abrasion cycles.
Figure 3. (a) The OCAs of the papers with different Fe3O4 NPs concentrations in 1 h. (b) The OCAs of the papers with pillar heights in 1 h. (c) Apparent contact angle and sliding angle measurements of different liquids on the surfaces. (d) The OCAs and WCAs of papers at different times. (e) The OCAs of the papers with different abrasion cycles.
Coatings 13 00323 g003
Table
Table 1. Summary of previously related fluorinated and fluorine-free amphiphobic papers.
Table 1. Summary of previously related fluorinated and fluorine-free amphiphobic papers.
CategoryChemical AgentWCA/°OCA/°Ref.
fluorinated(heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane154138Zhang et al. (2022) [14]
(heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane 163>150Jiang et al. (2017) [15]
Perfluorodecyltriethoxysilane171152Balraj et al. (2019) [16]
fluorine-freechitosan-graft-PDMS, zein12062.7Hamdani et al. (2020) [19]
chitosan, montmorillonite92.537.8Wang et al. (2021) [21]
soybean oil, stearic acid, and ZnO 145-Cheng et al. (2017) [22]
butyl acrylate grafted cellulose nanocrystal97.8-Zhang et al. (2022) [24]
crosslinked polyvinylalcohol, nanoclay108-Gu et al. (2022) [25]
Table
Table 2. Relationships between the geometrical parameters of the mushroom-like pillars and Fe3O4 NPs content.
Table 2. Relationships between the geometrical parameters of the mushroom-like pillars and Fe3O4 NPs content.
Fe3O4 NPs Content70%72.5%75%80%85%90%
RCAP (μm)32 ± 1735 ± 1337 ± 1848 ± 2351 ± 2054 ± 24
S (μm)318 ± 78283 ± 73237 ± 38231 ± 45217 ± 36175 ± 39
RCAP/S0.100.120.160.210.230.31
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Ke, X.; Wang, K.; Zhao, L.; Wang, Z.; Wu, M. Fluorine-Free Dual Superamphiphobic Cellulose Paper Coated with Mushroom-like Pillar Microstructure. Coatings 2023, 13, 323. https://doi.org/10.3390/coatings13020323

AMA Style

Ke X, Wang K, Zhao L, Wang Z, Wu M. Fluorine-Free Dual Superamphiphobic Cellulose Paper Coated with Mushroom-like Pillar Microstructure. Coatings. 2023; 13(2):323. https://doi.org/10.3390/coatings13020323

Chicago/Turabian Style

Ke, Xun, Kaipeng Wang, Lihong Zhao, Zhiwei Wang, and Min Wu. 2023. "Fluorine-Free Dual Superamphiphobic Cellulose Paper Coated with Mushroom-like Pillar Microstructure" Coatings 13, no. 2: 323. https://doi.org/10.3390/coatings13020323

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop