Applied Surface Science 598 (2022) 153639

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Applied Surface Science

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

Full Length Article

Fabrication of superhydrophobic and lyophobic paper for self‑cleaning,

moisture-proof and antibacterial activity
Fan Zhang a, b, Chao Wang a, b, Xinyue Wang a, b, Jiarui Wang a, b, Hao Zhang a, Ying Liu a,
Xiaona Huang a, Kun Xu a, *, Yungang Bai a, *, Pixin Wang a, b
a
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
b
University of Science and Technology of China, Hefei 230026, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Paper-based materials have been used in every aspect of social life. However, the current paper-based materials
Paper face unprecedented challenges, such as limited lifespan and poor mechanical strength, owing to the deformation
Internal sizing technology after absorbing a large amount of water and bacterial erosion. Herein, superhydrophobic and lyophobic paper
Superhydrophobic and lyophobic
was fabricated using internal sizing technology. Hydrophobically modified starch and Ag@SiO2 particles were
Self-cleaning
Moisture-proof
added as two functional additives to paper pulp to promote a hierarchical structure formation with low surface
Antibacterial energy. Consequently, the water and linseed oil contact angles of the obtained paper reached 154.8◦ and 138.4◦ ,
respectively. The resistance to moisture and water vapor also improved under high-humidity condition, the
relative moisture content decreased from 511% to 278% and water vapor transmission rate also decreased from
97.44 to 21.23 g/m2⋅h. Furthermore, its mechanical properties could also be well maintained with a high fracture
stress of 4.91 MPa. Besides, some liquid food, such as honey, easily rolled off the surface without leaving behind
any residue, which demonstrated its self-cleaning ability. Furthermore, the modified paper exhibited notable
bacterial repellency and antibacterial activity. This study provides an innovative method for endowing con­
ventional paper with superhydrophobic and antibacterial properties, which can effectively expand their appli­
cation scope.

1. Introduction Superhydrophobic surfaces are common in nature. Lotus leaves, ci­

cada wings, and water strider legs are the most typical examples of
As a necessity in human social life, paper-based materials play an superhydrophobic surfaces [12]. Such superhydrophobic surfaces are
important role in many aspects of our daily life because of their low cost defined as surfaces with water contact angles (WCAs) greater than 150◦
and remarkable physical and chemical properties, including adequate [13]. In fact, with the discovery and ensuing studies on the hydrophobic
tensile strength, renewability, and degradability [1–6]. However, as is phenomenon, various physical and chemical approaches have been
well known, the main components of paper, namely cellulose and proposed to prepare hydrophobic and superhydrophobic surfaces. These
hemicellulose, contain a large number of hydrophilic hydroxyl groups, include chemical vapor deposition [14], plasma-based technologies
which lead to the super water absorption property of paper. After water [15], layer-by-layer self-assembly [16], and sol–gel techniques [17]. For
absorption, the tensile strength of paper deteriorates, resulting in a example, Wong et al. [18] fabricated a hydrophobic surface using
significant decrease in its operational life [7,8]. Moreover, the super­ several silanes, including PFOS, trichloro(3,3,3-trifluoropropyl)silane,
hydrophilicity of paper results in contaminant adhesion, bacterial n-dodecyltrichlorosilane, and octadecyltrichlorosilane, to treat SiO2
erosion, and even bacterial growth, which also limit its application in spheres, followed by Au deposition on the treated SiO2 spheres and
many fields [9,10]. To address these issues, increased attention has been subsequent heat treatment to form Au nanoparticles on their surfaces.
paid over the past decades to the development of paper-based materials The WCA of the obtained material increased from 120◦ to 157.2◦ , and
with good hydrophobicity as well as self-cleaning and antibacterial the material exhibited excellent superhydrophobicity and stability. Shen
properties in a simple manner [11]. et al. [19] successfully prepared superhydrophobic surfaces on three

* Corresponding authors.
E-mail addresses: [email protected] (K. Xu), [email protected] (Y. Bai).

https://doi.org/10.1016/j.apsusc.2022.153639
Received 18 April 2022; Received in revised form 6 May 2022; Accepted 9 May 2022
Available online 11 May 2022
0169-4332/© 2022 Elsevier B.V. All rights reserved.
F. Zhang et al. Applied Surface Science 598 (2022) 153639

polycrystalline metals, namely aluminum, copper, and zinc, by simple Kaiyin Chemical Co. Ltd. (Shanghai, China).
chemical etching followed by the reaction of the etched metallic surfaces
with fluoroalkylsilane. The modified metal surfaces exhibited super­ 2.2. Synthesis of a mixed ester derivative of starch (S-FAS-PC)
hydrophobic properties with WCAs greater than 150◦ as well as roll-off
angles less than 10◦ . Thus, the hydrophobic functionalization of certain S-FAS-PC was synthesized using a two-step esterification reaction.
materials, such as glass [20,21], metals [22,23], and polymeric mate­ First, 5 g of acidified corn starch was dispersed in a mixture of DMF
rials [24], is mature. However, the hydrophobic functionalization of (35 mL) and pyridine (15 mL) in a 100 mL three-necked flask under
cellulose-based materials, such as paper, is still challenging. magnetic stirring for 3 h at 80 ◦ C. Next, 19 g of PC diluted with 10 mL of
It is well known that a typical papermaking process involves the DMF was reacted with starch in the presence of 0.1 g of DMAP as a
treatment of fibers derived from wood, rice straw, or reeds with a strong catalyst for 2 h at 80 ◦ C. The so-obtained starch ester (S-PC) was
acid or base to obtain pulp, followed by the removal of excess liquid by precipitated, washed with water and ethanol three times each, and dried
vacuum filtration to finally obtain paper with a certain mechanical at 60 ◦ C for 24 h in an oven. Next, 1 g of S-PC was dispersed in a mixture
strength [25]. For obtaining functional paper, the most practical and of 20 mL of DMF and 10 mL of pyridine in a 50 mL three-necked flask
effective method is to add functional additives during the papermaking under magnetic stirring for 0.5 h at 80 ◦ C. Then, 3.4 g of FAS diluted
process [26–28]. For this, surface and internal sizing technologies have with 10 mL of isopropanol was reacted with S-PC in the presence of 0.1 g
been widely developed according to the desired position of the func­ of DMAP as a catalyst for 2 h at 80 ◦ C. Finally, the obtained mixed ester
tional additives in paper. For instance, Cao et al. [29] proposed an of starch (S-FAS-PC) was precipitated, washed with water and ethanol
approach for preparing eco-friendly, low-cost, and water-resistant paper three times each, and dried at 60 ◦ C for 24 h in an oven.
coatings using palm kernel oil as a hydrophobic coating material. The
hydrophobic paper with this coating had a WCA of ~ 120◦ , and it is a 2.3. Fabrication of Ag@SiO2 composite particles
potential candidate for oil/water separation, moisture-proof packaging,
and self-cleaning applications. According to previous studies, the surface First, 7.5 mL of 0.1 mol/L NH3⋅H2O was added dropwise to 2.5 mL of
sizing technology is still the most common method for preparing func­ 0.1 mol/L aqueous AgNO3 until a clear solution of silver ammonia was
tional paper. However, surface sizing papermaking still suffers from obtained. Next, 0.5 g of SiO2 was suspended in 50 g of DMAc in a 100 mL
many drawbacks, such as the requirement of expensive equipment and conical flask. The as-prepared silver ammonia solution and 0.25 g of PVP
complex preparation processes. Despite all this, less relevant research on as a reductant were added to the SiO2 suspension under magnetic stir­
functional amphiphobic paper fabricated by internal sizing technology ring, and the mixture was heated at 50 ◦ C for 5 h. Finally, the Ag@SiO2
has been reported because of the waste of functional additives. In fact, composite particles were separated, washed with ethanol and deionized
the internal sizing technology is a three-dimensional operation, it could water through centrifugation, and dried in an oven at 50 ◦ C for 24 h.
easily completely change the properties of the paper fibers over all three
dimensions with less dosage. The paper-based materials prepared by this 2.4. Fabrication of a Paper-Based material
method have stable performance and long service life.
In this study, a superhydrophobic and lyophobic paper-based mate­ A paper-based blend was prepared using a facile internal sizing
rial with excellent self-cleaning and moisture-proof properties, water method, as shown in Fig. 1. First, pristine paper was washed several
vapor permeation resistance, and antibacterial activity was prepared times with water and ethanol and then dried at 60 ◦ C for 24 h in an oven.
using the internal sizing technology. Starch particles modified with Then, 1 g of the clean pristine paper was cut into small pieces and mixed
(Heptadecafluoro-1,1,2,2-tetradecyl)trimethoxysilane (FAS) and pal­ with 50 g of DMAc in a 100 mL conical flask under magnetic stirring at
mitoyl chloride (PC) (denoted as S-FAS-PC) and Ag@SiO2 composite 25 ◦ C until a uniform paper pulp was formed. Subsequently, 0.5 g of S-
particles were added to the paper pulp during the papermaking process. FAS-PC and 0.3 g of Ag@SiO2 composite particles were dispersed in
S-FAS-PC tightly adhered to every cellulose fiber because of its good 50 mL of DMAC and mixed with the as-prepared paper pulp for 12 h.
compatibility with cellulose fibers and formed a dense coating with a Thereafter, 20 mL of a 10% GA solution (pH 1) was added to the mixture
low surface energy, endowing the paper with superhydrophobicity and for 4 h. Finally, the paper-based blend was collected by vacuum filtra­
lyophobicity. Ag@SiO2 composite particles included as antibacterial tion and dried in an oven at 50 ◦ C and named as P-2. Furthermore, a
additives not only enhanced the antibacterial activity of the paper but series of paper was prepared by adjusting the dosages of the S-FAS-PC
also promoted the formation of a hierarchical structure. The stable and Ag@SiO2 composite particles. For comparison, the pristine paper
superhydrophobicity of the obtained paper can protect it from wetting named as P-0 and the modified paper fabricated by adding 0.5 g of S-
with water and other liquids and contamination with dust in practical FAS-PC as functional additive was named as P-1. P-0, P-1 and P-2 was
applications. In addition, owing to its superior water repellency, the chosen as representatives in the next tests.
modified paper significantly reduced bacterial (Escherichia coli) adhe­
sion, abrogated the development of bacterial biofilms on the surface, 2.5. Self-Cleaning test
and inhibited the growth of bacteria for a considerable duration. These
advantages of the obtained functional paper-based material are ex­ For evaluating the self-cleaning property, P-0, P-1 and P-2 were cut
pected to pave a promising pathway for their widespread application. into 4 cm × 2 cm rectangles. The rectangular specimens were immobi­
lized on slightly inclined glass slides and contaminated with dirt
2. Experimental (methylene blue powder). The contaminated surfaces were then rinsed
with water droplets, and the washing process was recorded using a
2.1. Materials phone camera.

Acidified corn starch was prepared according to a previously re­ 2.6. Analysis of moisture resistance
ported method [30,31]. (Heptadecafluoro-1,1,2,2-tetradecyl)trime­
thoxysilane (FAS), palmitoyl chloride (PC), 4-dimethylaminopyridine Rectangular specimens (4 cm × 2 cm) of P-0, P-1 and P-2 were used
(DMAP), and glutaraldehyde (GA) were procured from Sigma-Aldrich. in this analysis. First, the weight of the dry paper sample (m0) was ob­
N,N’-dimethylformamide (DMF) and pyridine were procured from tained by drying it at 105 ◦ C until a constant weight was reached.
Xilong Scientific Co. Ltd. (Shantou, China). Silver nitrate (AgNO3), Subsequently, the paper sample was placed in a constant temperature
polyvinyl pyrrolidone (PVP), and dimethylacetamide (DMAC) were and humidity incubator for 24 h at 50 ◦ C under different relative hu­
procured from Sigma-Aldrich. The SiO2 particles were procured from midity, and its weight (m1) was obtained again. The moisture content

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F. Zhang et al. Applied Surface Science 598 (2022) 153639

Fig. 1. Schematic of the preparation of paper with superhydrophobic and lyophobic properties.

(M) of the sample and the relative moisture content (Rm) were calculated 2.9. Friction robustness tests
using Equations (1) and (2), respectively.
m1 − m0 A sandpaper friction test was performed using a piece of 800-grit SiC
M= (1) sandpaper as the friction surface. The modified paper with a loaded
m0
weight of 200 g was placed face-down on the sandpaper and then moved
where m0 and m1 are the weights of the dry and moisture-treated paper back and forth over 10 cm distance. This step is defined as one friction
samples, respectively. cycle. The change in the WCA of the paper after friction tests was used to
analyze the friction resistance.
M
Rm = × 100% (2)
M35%
2.10. Antimicrobial assay
where M and M35% (%) are the moisture contents of the paper samples at
a certain relative humidity and 35% relative humidity, respectively. The antibacterial properties of the obtained paper were investigated
using the standard plate count method. Escherichia coli (E. coli) and
Staphylococcus aureus (S. aureus) were used to evaluate the antimicrobial
2.7. Tensile strength analysis at different relative humidity activity of P-0, P-1 and P-2. The paper sample was cut into 3 cm × 3 cm
squares, immobilized at the bottom of 12-well plates, and covered with
The fracture stresses of P-0, P-1 and P-2 were measured after the 2 mL of the bacterial solution (108 CFU/mL). Then, the paper samples
paper samples were treated at 50 ◦ C under different relative humidity were co-cultured with bacteria for 1 h at 37 ◦ C. After incubation, the
for 24 h. The relative fracture stress was calculated using Equation (3). samples were washed with 2 mL of normal saline, and 500 µL of the
diluted bacterial solution was spread at the center of an agar plate and
T
RT = × 100% (3) incubated for 12 h at 37 ◦ C.
T35%

where T and T35% are the fracture stresses (in MPa) of the paper samples 2.11. Characterization
at a certain relative humidity and 35% relative humidity, respectively.
Fourier-transform infrared (FTIR) spectra of the acidic starch and S-
FAS-PC samples were recorded on a Perkin-Elmer Spectrum 100 spec­
2.8. Analysis of the water vapor permeation resistance trometer (USA) using the KBr pellet method. Before FTIR analysis, the
samples were mixed with dry KBr powder, and the mixture was pressed
According to GB/T 12704.2–2009, 100 g of deionized water was into pellets. The particles size and polydispersity of Ag@SiO2 composite
taken in a conical flask, and P-0, P-1 and P-2 was cut into circles with a were measured by dynamic light scattering (DLS) using a 90 Plus par­
radius of 1 cm and fixed at the mouth of the conical flask with a double ticle size analyzer (Brookhaven, USA) at 25 ◦ C. The attenuated total
breathable film. The temperature and humidity were controlled using a reflection (ATR) FTIR spectrum of the as-prepared paper was also
constant temperature and humidity incubator. The mass of the water recorded using the Perkin-Elmer Spectrum 100 spectrometer (USA). X-
vapor transmission cup was measured after 24 h. The water vapor ray photoelectron (XPS) spectroscopy was performed on an ESCALAB
transmission rate (WVTR) of the samples was calculated using Equation MKII instrument. The micro-appearance was characterized using scan­
(4). ning electron microscopy (SEM) with a Merlin FE-SEM (ZEISS). For SEM,
m0 − m1 the samples were cut into small pieces and covered with gold. The
WVTR = (4) contact angles (CAs) of the liquids on the as-prepared paper surface were
A×t
measured using a CA measuring instrument (KRÜSS, DSA100). The WCA
where m0 and m1 are the initial weight and the weight at time t (g) of the and the oil CA were measured directly on the sample table using a water
water vapor transmission cup, respectively; A is the area of the sample or oil syringe. The roughness of the as-prepared paper was measured by
(m2) sealed on the water vapor transmission cup; and t is the time of 3D measurement macroscope (KEYENCE VR-3200). The samples were
incubation (h) in the constant temperature and humidity incubator. cut it into small pieces and stuck on the glass sheet with double-sided

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F. Zhang et al. Applied Surface Science 598 (2022) 153639

adhesive before measured. Humidity was controlled using a constant 3.2. Morphology and chemical composition of the modified paper
temperature and humidity incubator (TEMI 1000). The samples were
then placed in an incubator at 50 ◦ C under different relative humidity The surface morphologies of different paper samples were examined
(35%, 45%, 55%, 65%, 75%, 85%, and 95%) for 24 h before measuring using SEM (Fig. 2a–d), and the loading density of the two functional
the moisture content. A WSN-10kN universal tension machine (Chang­ additives on the surface was calculated by weighing, as shown in
chun Intelligence) was employed to measure the tensile strength of the Table S1. As shown in Fig. 2a and b, pristine paper (P-0) consisted of
samples under different humidity conditions. For water vapor perme­ randomly stacked cellulose fibers with a porous structure and exhibited
ation resistance analysis, the water vapor transmission cup was placed in a coarse surface. After modification, the fiber surface showed different
an incubator at 50 ◦ C under different relative humidity (45%, 65%, and structures. The paper modified with S-FAS-PC (P-1) showed a smooth
85%) for 24 h before measuring the mass of water. morphology, which indicated that S-FAS-PC was uniformly distributed
and tightly adhered to every cellulose fiber because of its good
3. Results and discussion compatibility with cellulose fibers. The loading density of S-FAS-PC on
the surface was 5.73 mg/cm2. To further promote the formation of a
3.1. Chemical composition of esterified starch hierarchical structure, Ag@SiO2 composite particles were added into the
paper pulp to prepare P-2. The structure of Ag@SiO2 composite particles
Commercially available starch was successively esterified using FAS is shown in Figure S2a. The size of composite particles was approxi­
and PC. In this study, FAS (a low-surface-energy modifier) and PC with a mately 1 µm, and many silver nanoparticles (AgNPs) were scattered on
long carbon chain (a hydrophobic modifier) were used to tailor the the SiO2 particle surface. DLS analysis indicated that the obtained
hydrophilic/hydrophobic properties of starch. FAS is abundant in active composite particles had a size of ~ 1 µm and a size polydispersity index
Si-O groups, which can easily react with the hydroxyl groups of starch. of 0.743 (Figure S2b). As shown in Fig. 1c and d, evenly distributed
In addition, the hydroxyl groups of starch could undergo an esterifica­ nano-scale protruding structures were formed on the fiber surface when
tion reaction with the functional acyl chloride groups at the end of the the loading density of the two functional additives was increased to
long-chain PC molecules. Figure S1 shows the FTIR and XPS profiles of 8.41 mg/cm2. The surface roughness of P-2, which consisted of
acidic starch and S-FAS-PC. In the FTIR spectrum of acidic starch, the randomly stacked fibers with a low-surface-energy coating and hierar­
characteristic peak originating from the O–H stretching vibrations of chical micro- and nano-scale structures, increased by a large margin, as
starch appeared at 3413 cm− 1. After modification, the band width of this shown in Figure S3. The surface chemical compositions of P-0, P-1, and
peak (3413 cm− 1) became sharper and narrower, and a new strong peak P-2 were also investigated by energy-dispersive X-ray spectroscopy
emerged at 1737 cm− 1, corresponding to the stretching vibration of (EDS; Figure S4). P-0 typically contained carbon (50.61%) and oxygen
C = O, indicating that most hydroxyl groups were esterified. The char­ (44.75%). After the coating of S-FAS-PC, the atomic concentrations (%)
acteristic absorption peaks of the –CH and –CH2 bonds appeared at 2839 of carbon and oxygen increased to 55.6% and 46.73%, respectively, and
and 720 cm− 1, respectively, confirming that the long carbon chain of PC the atomic concentration of fluorine was 6.73% (indicated by green
was introduced into the starch structure. In addition, the apparent C–F spots) for P-1. In the case of P-2, the atomic concentrations of carbon,
and Si–O stretching vibration peaks at 1213 and 900 cm− 1, respectively, oxygen, fluorine, silicon (indicated by blue spots), and silver (purple
also indicated the successful modification of starch with FAS. The XPS spots) were 46.98%, 43.28%, 2.54%, 4.6%, and 1.12%, respectively.
profiles of starch and S-FAS-PC are shown in Figure S1b. The XPS profile EDS mapping confirmed the uniform distribution of F, Si, and Ag on the
of acidic starch exhibited two peaks corresponding to C 1 s and O 1 s. surface of P-2.
After modification, two new peaks attributed to Si 2p and F 1 s appeared To further confirm the elemental composition and the interaction
at 103 and 686 eV, respectively, in the spectrum of S-FAS-PC, suggesting between the cellulose fiber and the two functional additives, ATR-FTIR
the successful modification of starch with FAS. and XPS analyses were conducted. The ATR-FTIR spectra of P-0, P-1, and

Fig. 2. Surface structure characterization. SEM images of (a) P-0, (b) P-1, and (c) P-2. (d) Enlarged view of (c).

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F. Zhang et al. Applied Surface Science 598 (2022) 153639

P-2 exhibited significant differences, as shown in Fig. 3a. The spectrum 3.3. Contact Angles on Paper Surfaces
of P-0 showed the characteristic O–H stretching vibration peak of cel­
lulose at 3346 cm− 1. After modification, this peak became wider and Owing to the combined effect of the chemical composition and the
weaker, suggesting that most hydroxyl groups on cellulose were cross­ hierarchical structure, paper wettability completely changed. Fig. 4
linked with S-FAS-PC and Ag@SiO2 nanoparticles through GA. In shows the CAs of the paper samples. As shown in Fig. 4a and b, the
addition, the stronger peak at 1029 cm− 1, which corresponds to the surface of P-0 could be easily wetted by water and ethylene glycol (EG)
stretching vibration of C–O–C, also indicated a successful crosslinking droplets; in both these cases, the CAs were ~ 0◦ within 1 s, indicating an
reaction. The formation of stable chemical bonds plays a significant role amphiphilic surface. In contrast, a significantly improved hydrophobic
in the stability of the multifunctional property of the resultant paper. In and lyophobic property was observed after modification, as shown in
addition, the new strong peaks at 2919, 1727, and 1447 cm− 1 corre­ Fig. 4c and d. Because of the low-surface-energy coating of S-FAS-PC, the
sponding to the stretching vibrations of C–H, C = O, and C–F, respec­ hydrophobicity of P-1 was improved, and it exhibited a WCA of 143.7◦ .
tively, in the spectra of P-1 and P-2 confirmed the successful Meanwhile, after hierarchical structures combined micro cellulose fibers
introduction of S-FAS-PC. Furthermore, the strong new peak at and Ag@SiO2 nanoparticles constructing, a rougher surface formed
810 cm− 1 corresponding to the stretching vibration of Si–O in the (Figure S3) which decreased the contact area between water droplet and
spectrum of P-2 confirmed the successful introduction of the Ag@SiO2 paper surface resulting a superhydrophobic surface with a WCA of
particles. Fig. 3b shows the XPS profiles of P-0, P-1, and P-2. The spec­ 154.8◦ for P-2. Although the WCAs of P-1 and P-2 also decreased with
trum of P-0 indicated the presence of carbon (285 eV) and oxygen time, the WCA was 118.2◦ for P-1 and 135.2◦ for P-2 after 30 min, these
(532 eV) as the main constituent elements of cellulose fibers. The results still demonstrate their excellent hydrophobicity. Furthermore,
spectrum of P-1 showed additional peaks of fluorine (688 eV) and silicon the surfaces of P-1 and P-2 were also lyophobic, as verified using some
(101 and 150 eV) [32]. Meanwhile, fluorine, silicon, and silver (386 eV) liquids, such as EG, formamide (FA), glycerin (GC), propanediol (PA),
peaks appeared in the spectrum of P-2, suggesting the modification of soybean oil (SO), and linseed oil (LO), as shown in Figure S5. The CAs of
the cellulose fibers with both S-FAS-PC and Ag@SiO2 nanoparticles. all liquids were above 100◦ on these samples, indicating the lyopho­
Furthermore, Fig. 3c showed the high-resolution C 1 s spectrum of P-2. It bicity of their surfaces. Figure S6 shows the results of a dynamic water
found that the surface exhibited distinct peaks at 284.8, 286.4, 288.1 eV droplet adhesion test performed with P-0 and P-2. When a water droplet
and 292.1 eV which correspond to C-C/C-H, C-O-C, O-C = O and C − F, was fully pressed to come in contact with the surface of P-2 and then
respectively [33,34]. Fig. 3d showed the high-resolution Ag 3d spectrum released in air, there was almost no deformation of the droplet. The
of P-2. The Ag3d5/2 and Ag3d3/2 peaks of P-2 were located at 368.2 eV droplet maintained its spherical form upon leaving the surface, con­
and 374.2 eV, respectively. The slitting of the Ag 3d was 6.0 eV, which firming that the surface of P-2 had ultralow water adhesion. However, in
further verified the successful generation of metallic silver [35]. In the case of P-0, the water droplet adhered to the surface as soon as it
summary, the results of EDS, ATR-FTIR spectroscopy, and XPS contacted, indicating a highly adhesive hydrophilic surface, as shown in
confirmed that S-FAS-PC and Ag@SiO2 nanoparticles were successfully Figure S6ai–iii.
fixed on the paper fiber surface through crosslinking. Furthermore, different dosages of S-FAS-PC (0.2–1.0 g) and Ag@SiO2
composite particles (0–0.75 g) were used in this study as independent

Fig. 3. Chemical compositions of P-0, P-1, and P-2. (a) FTIR and (b) XPS profiles. The high-resolution XPS spectrum of P-2 of (c) C 1 s and (d) Ag 3d.

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F. Zhang et al. Applied Surface Science 598 (2022) 153639

Fig. 4. Surface wettability of the paper samples. Photographs illustrating (a) water–air and (b) ethylene glycol-air contact angles (CAs) of P-0. Photographs of the
water–air CAs of (c) P-1 and (d) P-2.

parameters to evaluate their effects on the wettability of the modified and water vapor permeation resistance, which could improve its
paper. Fig. 5a shows the measured WCAs of paper after processing in the applicability.
S-FAS-PC solutions of different concentrations. The WCA of paper √̅̅̅̅̅̅̅̅̅̅̅ √̅̅̅̅̅̅̅̅̅̅̅
gradually increased from 121.5◦ to 143.7◦ as the S-FAS-PC content was γ LV (1 + cosθ) = 2 γdS γdLV + 2 γpS γ pLV (5)
increased from 0.2 to 0.5 g in the solution. However, with further in­
crease in the dosage of S-FAS-PC, the WCA decreased to 123.9◦ , because
3.4. Moisture Resistance Analysis
an excess of S-FAS-PC could not be dispersed well in DMAc and it even
agglomerated. As a result, the distribution of hydrophobic domains was
Paper-based materials are typically developed for packaging in daily
non-uniform and the effect of S-FAS-PC was not fully manifested.
life. However, the moisture resistance of the paper is poor owing to its
Therefore, in the following experiments, the S-FAS-PC dosage was fixed
inherent superhydrophilicity. Superhydrophobic paper can improve the
at 0.5 g. An optimal composite particle dosage could further help form
moisture resistance of paper to some extent. Fig. 6a shows the relative
well-defined hierarchical structures and amplify the hydrophobicity of
moisture content as a function of the relative humidity (%) for P-0, P-1,
paper. To determine the optimal percentage of Ag@SiO2 composite
and P-2. When the relative humidity was between 35% and 65%, the
particles, four different dosages of composite particles (0.2, 0.3, 0.5, and
relative moisture content increased slightly but was below 150% for all
0.75 g) were used. As shown in Fig. 5b, the WCA increased from 143.7◦
samples. When the humidity was increased further, the relative moisture
to 146◦ when 0.2 g of composite particles was used. However, when the
content of P-0 increased significantly, with an increase of approximately
dosage of composite particles was increased further, there was no
350%. In comparison, the relative moisture contents of P-1 and P-2 were
noticeable influence on the WCA, and the WCA of paper was above 146◦
significantly lower, with an increase of approximately 118% and 105%,
at higher dosages. When the dosages of the S-FAS-PC and Ag@SiO2
respectively. The unique wettability and internal structures of P-1 and P-
composite particles were 0.5 and 0.3 g, respectively, the maximum WCA
2 played critical roles in improving their moisture resistance. The
of the as-prepared paper (154.8◦ ) was observed, indicating that these
superhydrophobic S-FAS-PC wrapped the entire fiber surface and the
could be the optimal dosages. In general, superhydrophobic and
composite particles filled the fiber voids, thereby significantly reducing
lyophobic surfaces have a low surface energy. On this basis, the surface
water absorption. Consequently, the moisture resistances of P-1 and P-2
energies of P-0, P-1, and P-2 were calculated using the Wendt geometric
improved significantly. In addition, the mechanical properties of paper-
mean equation (Equation (5)). As shown in Fig. 5c, the surface energy of
based materials are important for practical applications. As is well
P-2 was calculated to be 3.77 mN/m, which is 20 times lower than that
known, because of the absorption of a large amount of water under high
of the amphiphilic P-0 (57.06 mN/m). Theoretically, in the case of
relative humidity conditions, the mechanical properties of paper-based
paper, a superhydrophobic and lyophobic surface with a low surface
material deteriorate with time, considerably limiting its lifespan.
energy can exhibit excellent self-cleaning property, moisture resistance,
Fig. 6b shows the relative tensile strength as a function of the relative

Fig. 5. Water contact angles (WCAs) and surface energies of the paper samples. (a) Variation in the WCA of paper as a function of the S-FAS-PC dosage. (b) Variation
in the contact angle of paper as a function of the Ag@SiO2 composite particle dosage. (c) Surface energies of P-0, P-1, and P-2.

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F. Zhang et al. Applied Surface Science 598 (2022) 153639

Fig. 6. Moisture resistance tests. (a) Relative moisture content vs. relative humidity for P-0, P-1, and P-2. (b) Relative tensile strength vs. relative humidity for P-0, P-
1, and P-2. (c) Fracture stress of P-0, P-1, and P-2 at ambient temperature (20 ◦ C) and humidity (40%) and after high-temperature treatment (50 ◦ C) in a humid
environment (relative humidity, 85%) for 24 h.

humidity for P-0, P-1, and P-2. When the relative humidity was below concentration gradient of the water vapor on either side of the paper
55%, the relative tensile strength did not decrease significantly because decreased gradually as the humidity of the constant temperature and
of the similar moisture resistance capabilities of P-0, P-1, and P-2. When humidity incubator increased, but the humidity of the air in the cup was
the relative humidity was above 55%, a large amount of water was almost unchanged. Therefore, the resistance to water vapor permeation
absorbed by the hydrophilic P-0 sample, and its relative tensile strength increased and the WVTR decreased. In addition, the WVTRs of P-1 and P-
decreased sharply from 128% to 19%. However, samples P-1 and P-2 2 were much lower than that of P-0 at any relative humidity. For
still had higher tensile strengths than P-0; only a slight decrease of example, at the relative humidity of 45%, P-0, P-1, and P-2 exhibited
approximately 30% was observed as the relative humidity increased stable WVTRs of 413.12, 86.90, and 79.68 g/m2⋅h, respectively. The
from 35% to 95%. Thus, P-1 and P-2 could maintain their mechanical differences could be explained by the mechanism of water vapor
properties under high-humidity conditions because of their excellent transmission through hydrophilic and hydrophobic papers in a humid
moisture resistance. The fracture stresses of P-0, P-1, and P-2 are shown environment, as shown in Fig. 7b. The S-FAS-PC coating wrapped the
in Fig. 6c. After treatment in a high-temperature (50 ◦ C) and humidity fibers tightly and enhanced the water barrier properties of P-1, while the
(85%) environment for 24 h, the fracture stress of P-0 decreased sharply composite particles additionally filled the fiber voids in the case of P-2,
(from 4.09 to 1.30 MPa). In contrast, P-1 and P-2 still exhibited high thereby inhibiting the diffusion and absorption of water vapor by the
fracture stresses of 3.56 and 4.91 MPa, respectively, after treatment. The paper. Thus, the water vapor resistance ability of P-2 increased signifi­
high fracture stress of the composite paper suggests that the paper fiber cantly under the synergistic effect of the S-FAS-PC coating and com­
was well protected by the S-FAS-PC coating and composite particles, posite particles. However, P-0 absorbed a large amount of water because
which could prevent water absorption by the paper and help maintain its of its inherent superhydrophilicity and macropores, which led to a
mechanical properties. higher WVTR. In brief, the excellent moisture, water vapor resistance,
and superior mechanical properties of the modified paper (P-2) could
3.5. Water Vapor Permeation Resistance further expand its application in many fields and render it suitable for
use in highly humid environments.
Considering practical applications, paper-based materials should
also possess excellent water vapor permeation resistance. The setup of 3.6. Self-Cleaning Property
the water vapor permeation experiment is shown in Figure S7. The water
vapor transmission cup was placed in a constant temperature and hu­ As shown in Fig. 8, a self-cleaning test was performed using a thin
midity incubator for 24 h at 50 ◦ C at different relative humidity to obtain layer of methylene blue powder as a model contaminant. The samples of
a stable value of WVTR. As shown in Fig. 7a, the WVTRs of P-0, P-1, and P-0 and P-2 contaminated with methylene blue powder were slightly
P-2 decreased gradually with an increase in the relative humidity. The inclined on petri dishes and then washed with water droplets, as

Fig. 7. Antimoisture filtration performance of the modified paper. (a) Water vapor transmission rates of P-0, P-1, and P-2 at different relative humidity. (b)
Antimoisture filtration mechanism.

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F. Zhang et al. Applied Surface Science 598 (2022) 153639

Fig. 8. Self-cleaning performance of the modified paper. (a, b) Self-cleaning mechanism. (c) Self-cleaning properties of P-2 contaminated with methylene blue. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

illustrated in Fig. 8a and b. As shown in Fig. 8c, the dirt on P-0 was not surface of P-2 in a spherical form. In addition, all tested liquid foods
removed and the flowing water droplets with the powder adhered to the could easily roll off the superhydrophobic surface of P-2 without leaving
surface, resulting in a dirtier surface. In contrast, the water droplets behind any residue (Movie S1–6). These results indicate that the surface
rolled down rapidly along the surfaces of P-2, as shown in Fig. 8d, Hy­ of P-2 has an outstanding self-cleaning ability.
drophilic contaminants on hydrophobized paper can be easily picked up
by rolling water droplets and then carried away from the surface. Thus,
3.7. Antibacterial Activity Test
the contaminated surfaces of P-2 were cleaned swiftly and thoroughly.
In addition, the dynamic and static wetting behaviors of P-0 and P-2
Increasing the antibacterial activity is in fact another important goal
were also carried out. As shown in Figure S8, the P-0 was dyed blue by
for paper-based materials. Most previous studies on bactericidal surfaces
immersing into dirty water within a few times, whereas the P-2 was still
paid less attention to the long-term antibacterial performance of paper.
clean and showed a remarkable antifouling ability in dirty water. The
For achieving a long-term antibacterial effect, it is crucial for the pre­
static wetting behaviors of was tested as shown in Figure S9. The water
pared material to possess super-repellency to water for preventing
dyed by methylene blue was prepared for a 30-min water immersion
bacterial adhesion. In this regard, the antibacterial activities of samples
test. It was found that P-0 became dirtier after immersion shown in
were assessed based on the adhesion and survival rate of bacteria. E. coli
Figure S9a. Conversely, for P-2, the water droplets were remained
and S. aureus were selected as representative gram-negative and gram-
spherical on its surface after immersion and 141.3◦ of WCA was ob­
positive bacteria to investigate the antibacterial properties of P-2. P-
tained. The above dynamic and static wetting behaviors jointly
0 and P-1 were used as controls. As shown in Fig. 9a, the adhesion rate of
demonstrated the remarkable self-cleaning performance of P-2.
E. coli and S. aureus on the surface of P-1 were only 19.66% and 22.18%,
Furthermore, the static CAs of a variety of liquid foods on the surface of
respectively, while that of the amphiphilic surface of P-0 was nearly
P-2 are shown in Figure S10. Various liquid food droplets, such as honey,
100%. This result indicates that a hydrophobic surface (P-1), can
coffee, green tea, Mirinda, Coca Cola, and milk, could reside on the
significantly reduce the adhesion rate of bacteria. Further, Fig. 9b

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F. Zhang et al. Applied Surface Science 598 (2022) 153639

Fig. 9. Antibacterial activity test of P-0, P-1, and P-2. (a) Bacterial adhesion rate of P-0 and P-1. (b) Bacterial survival rate of P-1 and P-2.

clearly reveals that under the effect of Ag@SiO2 nanoparticles as active The WCA of P-2 decreased only slightly from 154.8◦ to 113.0◦ after 100
biocidal species, the survival rate of E. coli and S. aureus were extremely friction cycles, indicating that it still had good hydrophobicity. Despite
low, about 9.68% and 11.12%, indicating that the superhydrophobic progressive wearing with increasing friction cycles, the P-2 surface
paper can kill most of E. coli and S. aureus colonies below and around retained its hydrophobicity, and water droplets still maintained a
them. According to the results, the good antibacterial activity of spherical shape on it. This result indicates a relatively better durability
superhydrophobic paper (P-2) can be attributed to the excellent water of P-2 against mechanical friction. We speculate that this is due to the
repellency and Ag nanoparticles as active biocidal species on its surface unique advantages of the internal sizing papermaking technology. It
which could significantly abrogate the development of the E. coli and completely changed the properties of the paper fiber in all three di­
S. aureus biofilm on its surface and inhibit the growth of bacteria for a mensions and endowed the paper with persistent hydrophobicity.
long time. Figure S11 showed the cross-section SEM images of P-2. The existence of
the Ag@SiO2 composite particles proved the successful modification
3.8. Friction Tests from three-dimensional angles.
The persistent hydrophobicity of P-2 is the basis for its multiple
In general, a paper-based material is easily worn during its use functions. Thus, the effects of the repeated friction on mechanical
because of frequent contact with hard surfaces, and the hydrophobicity properties, WVTR, antibacterial activity, and self-cleaning performance
of paper surface tends to deteriorate with age. A friction test was con­ were investigated in detail (Fig. 10c–f and Movie S7). The fracture
ducted to assess the durability of the superhydrophobicity of P-2 stresses of P-0 and P-2 before and after friction under different condi­
(Fig. 10a). The sample loaded with a weight of 200 g was placed face- tions are shown in Fig. 10c and d. In an ambient environment (tem­
down on sandpaper and then moved back and forth over 10 cm dis­ perature: 20 ◦ C; humidity: 40%), the fracture stress of P-0 decreased
tance. WCAs measured after 100 friction cycles are shown in Fig. 10b. from 4.09 to 0.54 MPa after 100 cycles of friction and was far inferior to

Fig. 10. Friction tests. (a) Side view of the schematic setup used for friction tests. (b) WCAs of P-2 after each friction with a load of 200 g. Fracture stresses of P-0 and
P-2 after friction under (c) ambient temperature (20 ◦ C) and humidity (40%) and under (d) high-temperature (50 ◦ C) and humidity (85%) conditions for 24 h. (e)
Water vapor transmission rates of P-0 and P-2 at the relative humidity of 85% after friction. (f) Bacterial survival rate on the surface of P-2 after friction.

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F. Zhang et al. Applied Surface Science 598 (2022) 153639

that of P-2. After modification, the fiber of P-2 was well protected by the interests or personal relationships that could have appeared to influence
low-surface-energy coating; therefore, the paper exhibited excellent the work reported in this paper.
wear resistance with a small decrease in the fracture stress from 6.22 to
5.10 MPa. Similarly, after treatment in a high-temperature (50 ◦ C) and Acknowledgment
humidity (85%) environment for 24 h followed by friction, faster water
absorption occurred. Thus, a sharp decline in the fracture stress was Financial support was provided by the Jilin Province Science and
observed for P-0, and its fracture stress was only 0.29 MPa after the Technology Development Project Foundation (grant no.
friction test. Comparatively, there was only a slight decrease from 4.91 20200708061YY), Capital Care Foundation in Jilin Province Budget
to 4.34 MPa in the fracture stress of P-2, as shown in Fig. 10d. Due to its (grant no. 20210201124GX) and Special Funds of the Science and
persistent hydrophobicity, P-2 still prevented the diffusion of water and Technology Cooperation of the Chinese Academy of Sciences (grant no.
thus maintained its mechanical properties. Fig. 10e shows the WVTRs of 2021SYHZ0018).
P-0 and P-2 at a relative humidity of 85% after friction. Owing to the
inevitable mechanical damage during friction, the WVTR of P- Appendix A. Supplementary material
0 increased by a large margin from 97.44 to 123.7 g/m2⋅h. However, in
the case of P-2, although the fiber and the coating were destroyed after Supplementary data to this article can be found online at https://doi.
repeated friction, the hydrophobicity was not lost. Therefore, the WVTR org/10.1016/j.apsusc.2022.153639.
increased slightly from 21.23 to 34.22 g/m2⋅h but was still significantly
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