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A Journal of
Accepted Article
Title: Low-Cost and Scaled-up Production of Fluorine-Free, SubstrateIndependent, Large-Area Superhydrophobic Coatings Based on
Hydroxyapatite Nanowires Bundles
Authors: Fei-Fei Chen, Zi-Yue Yang, Ying-Jie Zhu, Zhi-Chao Xiong, LiYing Dong, Bing-Qiang Lu, Jin Wu, and Ri-Long Yang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201703894
Link to VoR: http://dx.doi.org/10.1002/chem.201703894
Supported by
10.1002/chem.201703894
Chemistry - A European Journal
DOI: 10.1002/ ((please add manuscript number))
Article type: Full Paper
Low-Cost and Scaled-up Production of Fluorine-Free, Substrate-Independent, LargeArea Superhydrophobic Coatings Based on Hydroxyapatite Nanowire Bundles
Bing-Qiang Lu,[a] Jin Wu,[a] Ri-Long Yang[a, b]
[a] F. F. Chen, Prof. Dr. Y. J. Zhu, Dr. Z. C. Xiong, Dr. L. Y. Dong, Dr. B. Q. Lu, Dr. J. Wu,
R. L. Yang
State Key Laboratory of High Performance Ceramics and Superfine Microstructure
Shanghai Institute of Ceramics, Chinese Academy of Sciences
Shanghai, 200050, P. R. China
E-mail: y.j.zhu@mail.sic.ac.cn (Y.-J. Zhu); zcxiong@mail.sic.ac.cn (Z.-C. Xiong)
[b] F. F. Chen, Prof. Dr. Y. J. Zhu, R. L. Yang
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China
[c] Z. Y. Yang
Sino-German College of Technology
East China University of Science and Technology
Shanghai, 200237, P. R. China
Supporting Information is available from the Wiley Online Library.
1
This article is protected by copyright. All rights reserved.
Accepted Manuscript
Fei-Fei Chen,[a, b] Zi-Yue Yang,[c] Ying-Jie Zhu,*[a, b] Zhi-Chao Xiong,*[a] Li-Ying Dong,[a]
10.1002/chem.201703894
Chemistry - A European Journal
Abstract: Up to date, the scaled-up production and large-area applications of the
superhydrophobic coatings are limited because the complicated procedures, environmentally
harmful fluorinated compounds, restrictive substrates, expensive equipments and raw
materials are usually involved in the fabrication process. Herein, we report the facile, low-cost
and green production of the superhydrophobic coatings based on hydroxyapatite nanowire
oleic acid as the structure-directing and hydrophobic agent. During the reaction process,
highly hydrophobic C–H groups of oleic acid molecules can be in-situ attached to the surface
of HNBs by the chelate interaction between Ca2+ ions and carboxylic groups. This facile
synthesis method allows the scaled-up production of HNBs up to ~8 litres, which is the
largest production scale of the superhydrophobic paint based on HNBs ever reported. In
addition, we also show the design of the 100-litre reaction system. The HNBs can be coated
on any substrate with an arbitrary shape by the spray coating technique. The self-cleaning
ability in air and oil, high-temperature stability, and excellent mechanical durability of the asprepared superhydrophobic coatings are demonstrated. More importantly, The HNBs are
coated on the large-sized practical objects to form large-area superhydrophobic coatings.
Introduction
Coatings on the substrates provides special functions such as wear resistance, corrosion
resistance, insulation, and decoration. An attractive hot research topic on coatings aims at
developing highly stable superhydrophobic surfaces since the lotus effect was investigated.[1, 2]
Superhydrophobic surfaces are very promising for applications such as self-cleaning
coatings,[3] corrosion-resistant metals,[4, 5] oil/water separation,[6, 7] ice prevention system,[8, 9]
antibacterials,[10, 11] anti-fogging,[12] and microfluidic devices.[13] After learning from nature
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Accepted Manuscript
bundles (HNBs). Hydrophobic HNBs are synthesized by one-step solvothermal method using
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Chemistry - A European Journal
for decades,[14] the fundamental strategy has been developed to construct the
superhydrophobic surfaces by fabricating the hierarchical rough structure together with the
surface modification with low surface energy compounds. Based on this strategy, many
superhydrophobic materials have been prepared successfully. However, the scaled-up
production and large-area applications of superhydrophobic coatings are still limited by the
exposure,[18, 19] and polymerization[10] are complicated, or dependent on the specific substrates;
(2) the fabrication and modification are usually separate,[12,
20, 21]
which increases the
operational steps and consumes the time; (3) the fluorinated compounds frequently used to
lower the surface energy are not only expensive but also cause environmental concerns and
biological impact;[22] (4) since the hierarchical rough structure is necessary for stable
superhydrophobicity, the mechanical stability of superhydrophobic coatings against physical
damages is not satisfying.[23, 24]
To solve these problems, efforts have been made to find robust materials and inexpensive
low surface energy compounds, simplify the fabrication process, and build environmentally
friendly and low-cost methods. For example, Lu et al.[3] and Chen et al.[25] coated the
modified nanoparticles on the substrates by simple spraying to form robust superhydrophobic
coatings, however, the expensive fluorinated compounds were used. Xie et al.[26] prepared the
fluorine-free and mechanically robust superhydrophobic coating on the glass using charcoal
particles. Metal-organic frameworks (MOFs), a class of coordination compounds assembled
by inorganic metal-containing nodes and organic linkers,[27] are another ideal alternatives for
fluorine-free superhydrophobic coatings.[28, 29] Recently, silane and polymers were used to
achieve high hydrophobicity. For instance, Vüllers et al.[30] constructed nanohairs on the
polycarbonate film by hot pulling. Mates et al.[31] developed a water-based and fluorine-free
superhydrophobic formulation by using environmentally safe constituents, TiO2 nanoparticles
and polyolefin copolymers. The hydrolysis of silane and polymer together with spray coating
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Accepted Manuscript
following reasons: (1) the fabrication methods such as multiple procedures,[15-17] flame
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Chemistry - A European Journal
also provide a fluorine-free, substrate-independent, and mechanically durable strategy for
superhydrophobic coatings.[32,
33]
In addition, there are some innovative superhydrophobic
coatings emerging continuously such as silica aerogel particles on biotic surfaces,[34] edible
materials-based liquid repellent coating,[35] and onionlike carbon microspheres converted
from waste polyethylene terephthalate.[36] Although many reports can solve some major
are usually limited at laboratory scale (usually ≤ 100 mL), and scaled-up production and
large-area applications are little explored.
Hydroxyapatite, the main inorganic constituent in bone and tooth,[37, 38] is biocompatible
and shows good mechanical properties against physical damages. Hydroxyapatite
biomaterials have been investigated for various applications such as drug delivery,[39]
regenerative medicine,[40] and strong and tough structural materials.[41] In addition, high
biocompatibility and mechanical stability/durability are ideal for the construction of
environmentally friendly and robust superhydrophobic coatings. However, previous methods
such as direct transformation from monetite,[42] template directed method,[43] and solid-state
conversion[44] are not satisfactory to produce superhydrophobic nanostructured hydroxyapatite
by one step. Molecular manipulation offers an effective solution to the problem.[45] This
technique is a very powerful tool to alter the microstructure and impart new functional
properties simultaneously. Fortunately, during the evolution of hydroxyapatite-related tissues,
molecular manipulation is frequently involved. For example, it is believed that amelogenin as
an organic manipulator plays a critical role in the formation of the tooth enamel.[38] The
organic manipulators in the biological systems show somewhat similarities. They have
carboxylic groups that exhibit a high affinity to metal ions and thus can graft functional
groups to the solid surface. This feature inspires us to look for the ideal organic manipulator
that is capable of synthesizing hydrophobic hydroxyapatite nanowires.
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Accepted Manuscript
problems and show respective advantages, however, the studies on superhydrophobic coatings
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Chemistry - A European Journal
Fatty acid with the hydrophobic C-H chain end and hydrophilic carboxylic head is an
appropriate choice due to the following reasons: (1) some fatty acids such as oleic acid,
linoleic acid, and linolenic acid exist in traditional edible fats and oils, which provide human
beings with necessary nutrition,[46] so they are a class of biocompatible and green materials; (2)
carboxylic acids with C-H chains can efficiently transform the hydrophilic surface into
with a long C-H chain has been utilized in the one-step fabrication of hydrophobic alkyl-silica
nanowires, and in constructing the superhydrophobic materials.[48]
Herein, we report the facile, low-cost and environmentally friendly scaled-up production
of the superhydrophobic coatings based on hydroxyapatite nanowire bundles (HNBs).
Hydrophobic HNBs are synthesized by one-step solvothermal method using oleic acid as the
structure-directing and hydrophobic agent. This facile method allows the scaled-up production
of HNBs using an autoclave with a volume of 10 litres, which is the largest production scale
of the superhydrophobic paint based on HNBs ever reported. To further scale up the
production of HNBs, a 100-litre reaction system is designed. The superhydrophobic paint
based on HNBs can be coated on any substrate with an arbitrary shape and on large-sized
practical objects by the spray coating technique. The as-prepared superhydrophobic coatings
have many advantages such as self-cleaning ability both in air and oil, high-temperature
stability, and excellent mechanical durability. To the best of our knowledge, this is the first
report simultaneously demonstrating the scaled-up production and large-area applications of
superhydrophobic coatings based on HNBs with fluorine-free and substrate-independent
features.
Results and Discussion
Synthesis and Characterization of Hydrophobic HNBs.
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Accepted Manuscript
superhydrophobic one;[47] (3) trimethoxy(octadecyl)silane with a similar structure to fatty acid
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Chemistry - A European Journal
We select one of fatty acids, oleic acid, as an organic manipulator for one-step synthesis
of hydrophobic hydroxyapatite nanowire bundles (HNBs). Oleic acid, calcium source,
phosphorus source and NaOH are mixed homogeneously in water and ethanol (Figure 1a),
and the resulting mixture is transferred into an autoclave, sealed, and solvothermally treated.
The as-prepared product consists of bundles assembled with parallel aligned hydroxyapatite
from 2~5 μm in length direction and 0.4~1.5 μm in diameter direction. The morphology
evolution of the product over time is shown in Figure S1 (Supporting Information). The
chemical reactions involved in the synthesis process of HNBs are as follows:
RCOOH + NaOH → RCOONa + H2O
(1)
2RCOONa + CaCl2 → (RCOO)2Ca + 2NaCl
(2)
NaH2PO4 + 2OH− → PO43− + 2H2O + Na+
(3)
10(RCOO)2Ca + 6PO43− + 2OH− → Ca10(OH)2(PO4)6 + 20RCOO−
(4)
R = CH3(CH2)7CH=CH(CH2)7−
In this work, the liquid-solid-solution (LSS) strategy is involved in the formation of
calcium oleate as the precursor (Figure S2, Supporting Information).[49,
50]
Briefly, after
introducing an aqueous solution containing Ca2+ ions to the mixture of oleic acid and ethanol
in a basic environment, Ca2+ ions transfer from the solution phase (water + ethanol) to the
liquid phase (oleic acid + ethanol). The complexation between Ca2+ ions and oleic acid
molecules results in the formation of calcium oleate as the precursor (solid precursor phase),
which further reacts with PO43- ions to form the amorphous product (Figure S3, Supporting
Information).
The high temperature and high pressure in the autoclave drive the amorphous product to
grow and crystallize under solvothermal conditions. Oleic acid is considered as a structuredirecting agent to efficiently inhibit the growth rate along some crystallographic directions.[51,
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nanowires (Figure 1b and 1c). The sizes of hydroxyapatite nanowire bundles (HNBs) vary
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Chemistry - A European Journal
52]
As a result, the elongated growth of hydroxyapatite nanocrystals into one-dimensional
nanowires is observed (Figure 1b, and Figure S1 in Supporting Information). The detailed
morphology evolution during the solvothermal process is shown in Figure S1 (Supporting
Information). At the early stage, the product is in the form of aggregated nanosheets and
nanowires, it is possible that the oriented attachment of hydroxyapatite nanocrystals is
interface create the controlled ordered space for the crystal growth. Then, the nuclei form and
grow in this space, and subsequently nanosheets form, and then nanosheets transform to
nanowires with increasing solvothermal time. The nanowires are self-assembled through
oriented attachment to form bundle-like structures.
The weight ratio of oleic acid to ethanol dramatically affects the length of hydroxyapatite
nanowires. At the high weight ratio (1:1), ultralong hydroxyapatite nanowires are obtained.[54]
Figure S4 (Supporting Information) shows the scanning electron microscopy (SEM)
micrograph of the as-prepared ultralong hydroxyapatite nanowires. It should be mentioned
that the bundles assembled with ultralong hydroxyapatite nanowires are observed as well
(Figure S4, Supporting Information). Ultralong hydroxyapatite nanowires can interweave with
each other to form the three-dimensional porous network. This feature is suitable for the
fabrication of highly flexible fire-resistant paper.[54, 55] However, in the spray coating process,
we find that ultralong hydroxyapatite nanowires frequently clog the spray nozzle, hindering
their application for the superhydrophobic coating. In this work, we decrease the weight ratio
of oleic acid to ethanol to 1:2, and as a result, the length of the as-prepared hydroxyapatite
nanowires is reduced sharply. As shown in Figure 1e1, the lengths of hydroxyapatite
nanowires vary in the range of 360~1100 nm, which is suitable for the application in spray
coating.
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Accepted Manuscript
involved at this stage.[53] Briefly, oleic acid molecules distributed in the water-surfactant
Figure 1. (a) Schematic illustration of the fabrication process of the superhydrophobic
coating based on HNBs. (b) TEM micrograph of HNBs. (c) SEM micrograph of HNBs.
(d1, e1) High magnification TEM micrographs of ultralong hydroxyapatite nanowires
and short hydroxyapatite nanowires. (d2, e2) Schematic illustration of the formation of
hydroxyapatite nanowires with different lengths.
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10.1002/chem.201703894
Chemistry - A European Journal
10.1002/chem.201703894
Chemistry - A European Journal
We propose the possible formation mechanism of hydroxyapatite nanowires with
different lengths. The viscosity of the reaction system plays a key role in regulating the length
of nanowires. At the high weight ratio (oleic acid/ethanol = 1:1), the reaction system is highly
viscous (484.00 ± 38.16 cP, Figure S5 in the Supporting Information), and the movement of
ions is jammed. During the LSS process, the reactions between Ca2+ ions with oleic acid
slow, which causes significant amounts of Ca2+ and PO43- ions remaining in the solution phase
(Figure 1d2). Under solvothermal conditions, there are enough free ions for nuclei to grow
into ultralong hydroxyapatite nanowires. In contrast, at the low weight ratio (oleic
acid/ethanol = 1:2), the reaction system is less viscous (7.23 ± 0.20 cP, Figure S5 in the
Supporting Information), which promotes the transfer of Ca2+ and PO43- ions from the
solution phase to liquid and solid phases (Figure S2, Supporting Information). The formation
of more nuclei accompanys with less ions left in the reaction mixture (Figure 1e2). During the
subsequent solvothermal treatment, the crystal growth is hindered by insufficient free ions.
The diffraction peaks of X-ray diffraction (XRD) pattern can be indexed to a single
phase of hydroxyapatite (JCPDF 73-0294, Figure 2a). The adsorption of oleic acid molecules
on the surface has no obvious impact on the crystallinity of hydroxyapatite nanowires.[54]
Both the structure and surface energy are responsible for the construction of the
superhydrophobic coating. Firstly, the parallel aligned nanowires of HNBs together with fine
nanogrooves build the special hierarchical structure (Figure 2b), which is similar to the leg’s
surface of the water strider.[56] The previous report has demonstrated that this kind of structure
contributes to superhydrophobicity.[57] Secondly, the presence of hydrophobic C-H groups on
the HNBs surface is characterized by elemental mapping and Fourier transform infrared
(FTIR) spectrum. The elemental mapping of HNBs shows the homogeneous distribution of
Ca, P, O, and C elements in the sample (Figure 2c, 2d, and Figure S6 in the Supporting
Information). In the FTIR spectrum (Figure 2e), the absorption peak at 3572 and 633 cm-1 are
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molecules to form calcium oleate precursor, and between the precursor and PO43- ions become
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Chemistry - A European Journal
assigned to the hydroxyl group, the characteristic peaks of PO43- locate at 1103, 1030, 962,
604, and 561 cm-1. In addition, the absorption peaks at 2924 and 2854 cm-1 are attributed to
the asymmetric and symmetric CH2 stretching vibrations. Two absorption peaks at 1556 and
1456 cm-1 are associated with the asymmetric and symmetric COO− stretching vibrations.[58, 59]
The experimental results demonstrate the adsorption of oleic acid molecules as a carboxylate
to calcium atoms.[59] The content of the organic constituent on the surface of HNBs is
estimated by thermogravimetric (TG) analysis. The weight loss of ~11.6 wt.% from 200 to
500 ºC in the TG curve is attributed to the decomposition of organics, and an exothermic peak
is observed at about 348 ºC in the differential scanning calorimetry (DSC) curve (Figure 2f).
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on the surface of HNBs, and two oxygen atoms of COO− may be symmetrically coordinated
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Chemistry - A European Journal
Figure 2. (a) XRD pattern, (b) SEM image, (c, d) elemental mapping, (e) FTIR spectrum, and
Figure 3. (a) A stainless steel autoclave with a volume of 10 litres. (b) A ~8-litre
solvothermal product suspension containing HNBs. (c) The large-scale production system
including a 100-litre stainless steel autoclave.
In consideration of the low-cost, commercially available, environmentally friendly, and
biocompatible raw materials together with green and facile synthesis, we have realized the
scaled-up production of HNBs up to 8-litre reaction system using an stainless steel autoclave
with a volume of 10 litres (Figure 3a and 3b). To the best of our knowledge, this is the first
report on the scaled-up production of the superhydrophobic paint based on HNBs. Recently,
we attempt to further scale up the production of HNBs, and a 100-litre stainless steel
autoclave with a streamline equipments of “blending-reaction-washing-ethanol recycling” has
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(f) TG-DSC curves of the as-prepared HNBs.
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been designed and set up (Figure 3c). After the solvothermal reaction, the product suspension
containing hydroxyapatite nanowires is transferred from the 100-litre autoclave into the
washing system through the pipeline. The liquid waste is separated and transferred into the
ethanol recycling system. The recycled ethanol can be used for washing hydroxyapatite
nanowires or as the reaction solvent.
there is still lack of report on the combined desirable characteristics including facile one-step
synthesis, fluorine free, substrate independence, and especially scaled-up production and
large-area applications. The HNBs-based superhydrophobic coatings demonstrated in this
work would satisfy these requirements and show promising applications as the low-cost,
environmentally friendly, high-temperature-resistant, and biocompatible superhydrophobic
materials.
Table 1. The comparison of superhydrophobic coatings reported recently
One-step
synthesis and
modification?
Fluorine
free?
Scaled-up
production?
Substrate
independence?
Large-area
applications?
Dip/spray
coating
No
Yes
Not shown
Yes
No
[60]
TiO2 NPs
Spray coating
No
No
< 200 mL
Yes
No
[3]
TiO2 NPs
Spray coating
No
Yes
< 50 mL
Yes
No
[31]
SiO2 NPs +
TiO2 NPs
Multiple
synthesis +
mixing +
casting
No
No
Not shown
Yes
No
[15]
CuO
nanoflowers
Wire cutting +
chemical
etching
No
No
Not shown
No
No
[61]
Carbon
microspheres
Supercritical
CO2 + vacuum
annealing +
dip coating
No
Yes
< 50 mL
No
No
[36]
Charcoal
Flattening +
fixation
Yes
Yes
Not shown
No
No
[26]
Carbon
nanotube
Spray coating
+ surface
fluorination
No
No
< 100 mL
Yes
No
[62]
CaCO3 NPs
Spray coating
No
No
< 100 mL
Yes
No
[25]
Mg(OH)2
Antideposition
No
Yes
Not shown
Yes
Yes
[20]
Materials
Method
SiO2 NPs[a]
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Ref.
Accepted Manuscript
Some recent reports on the superhydrophobic coatings are listed in Table 1. Up to date,
nanosheets
+ spreading
Ag NPs
Multiple
deposition
No
No
< 150 mL
No
No
[16]
Cu + TiO2
Hydrothermal
+ electroless
plating + selfassembly
No
No
Not shown
No
No
[4]
Si + ZnO
nanowires
Etching +
growth +
modification
No
No
150 mL
No
No
[63]
Silicone
Thermal
processing
Yes
Yes
Yes
No
Yes
[19]
Silicone
nanofilaments
Thiol-ene
reaction
Yes
Yes
< 200 mL
No
No
[64]
SAC + silica
sol[b]
Spray coating
Yes
Yes
< 100 mL
Yes
No
[32]
PAA + PAH +
SPEEK[c]
Spray layerby-layer
assembly
No
No
Not shown
Yes
Yes
[17]
FC + PUF
NPs[d]
Polymerization
+ mixing +
spray coating
Yes
No
Not shown
Yes
No
[10]
SiO2 +
PU/ER[e]
Polymerization
and hydrolysis
+ spray
coating
Yes
Yes
< 50 mL
Yes
No
[33]
MOFs arrays
(ZIF-7)
Hydrothermal
Yes
Yes
< 50 mL
No
No
[29]
MOFs particles
Coupling
procedure
Yes
Yes
Not shown
No
No
[28]
HNBs
Solvothermal
+ spray
coating
Yes
Yes
8 litres
Yes
Yes
This
work
[a] NPs: nanoparticles; [b] SAC: silicone-acrylic copolymer; [c] PAA: poly(acrylic acid);
PAH: poly(allylamine hydrochloride); SPEEK: sulfonated poly(ether ether ketone); [d] FC:
fluorinated copolymer; PUF: poly(urea-formaldehyde); [e] PU: polyurethane; ER: epoxy
resin.
Performance of HNBs-Based Superhydrophobic Coatings
As for practical applications, the substrate-independent feature is necessary for the
superhydrophobic coatings. The as-prepared HNBs-based superhydrophobic paint can be
coated on hard substrates (e.g., glass and metal) and soft substrates (e.g., fabric and paper) by
an easy syringe injection (Figure 4a-d). With the help of commercial spray adhesive, the
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Accepted Manuscript
10.1002/chem.201703894
Chemistry - A European Journal
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adhesion between HNBs and substrate is further enhanced, and the superhydrophobic paint
can be sprayed on the objects with arbitrary shapes (Figure 4e and 4f). The combination of the
hierarchical structure and hydrophobic long C-H chain of HNBs transforms the hydrophilic or
superhydrophilic substrate surface into superhydrophobic one. The water contact angles
(WCA) of the as-prepared HNBs coatings are above 150º. The sliding angle (SA) is evaluated
to be smaller than 5º. Stable water repellency is demonstrated by a water droplet standing on
the superhydrophobic HNBs coating for 10 min (Figure 4g).
Figure 4. (a-d) The water droplets on the uncoated (left) and coated (right) substrates, and
corresponding WCA measurements. (e-f) The water droplets are standing on and rolling off
the superhydrophobic HNBs coating on the plastic tube that is fabricated by “spray adhesive +
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Accepted Manuscript
according to the reported technique (Figure S7, Supporting Information),[11] and is estimated
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spray coating” method. (g) The evolution of a water droplet on the superhydrophobic HNBs
coating on the glass with time elapsing.
In the following investigation, the glass is selected as a representative substrate. The
superhydrophobic coating on the glass is prepared by syringe injection of HNBs. Before the
are continuously dropped onto the surface. Similar to the lotus effect, when the water droplets
travel across the superhydrophobic surface, the contaminants are picked up and removed, and
the surface is cleaned (Figure 5a). The self-cleaning test on the soft substrate
(superhydrophobic HNBs coating on the paper) is also shown in Figure S8 (Supporting
Information).
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self-cleaning test, the contaminants are put on the surface. Subsequently, the water droplets
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Figure 5. (a) The self-cleaning test on the superhydrophobic HNBs coating on the glass. (b)
The water droplets on the uncoated (left) and coated (right) glass that is immersed in oil
(cyclohexane). (c) The water droplets slip across the superhydrophobic HNBs coating on the
glass that is polluted by oil. (d) The self-cleaning test on the superhydrophobic HNBs coating
Stable water repellency in oil is essential for applications on lubricating gears and
bearings.[3] As shown in Figure 5b, the glass is half-coated with HNBs for investigation. The
water droplets are deposited on the glass that is immersed in oil (cyclohexane), and they stand
on the superhydrophobic HNBs coating on the glass steadily in the form of spherical balls. In
contrast, water droplets collapse on the uncoated glass due to its hydrophilic surface (Figure
5b). In the dynamic process, when a water droplet is rolling off the superhydrophobic HNBs
coating on the glass that is immersed in oil, it still keeps the spherical shape (Figure S9,
Supporting Information).
The experimental results indicate the stable water repellency of HNBs-based
superhydrophobic coating in oil. To understand this feature, the test on the oil-polluted
superhydrophobic HNBs coating on the glass is carried out, as shown in Figure 5c. Briefly,
the superhydrophobic HNBs coating on the glass is immersed in oil for 2 s, then it is extracted
and placed in air. At this time, the solid-liquid-oil interface replaces the solid-liquid-air
interface before immersion in oil. Therefore, the oil is trapped in the pores to serve as a
lubricating liquid. A slippery state is formed and then repels the water droplets.[65-67] Stable
superhydrophobic surface in oil is attractive for the removal of contaminants on the oilpolluted surface. In this work, the self-cleaning test on the superhydrophobic HNBs coating in
oil is conducted and shows that the contaminants are easily removed with the help of water
(Figure 5d).
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on the glass that is immersed in oil.
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Another issue is that the stability of the superhydrophobic coatings upon exposure to
corrosive and high-temperature environments. We have carried out the durability test against
long-time immersion in water. The WCA as a function of immersion time is shown in Figure
6a. The experimental results show that the long-time immersion in water does not degrade the
superhydrophobicity of the HNBs-based coating, and the WCA is still larger than 150o. The
coating under corrosive conditions. In a broad range of pH values, the HNBs-based
superhydrophobic coating shows high resistance to acidic/basic environments and preserves
high water repellency with the WCA > 150o (Figure 6b). In addition, the HNBs-based
superhydrophobic coating is thermally treated at different temperatures for various times to
evaluate its thermal resistance. The stable water repellency of the superhydrophobic HNBs
coating can be well maintained at a temperature as high as 200 ºC, as shown by the WCA
above 150º and SA below 5º after heat treatment (Figure 6c and 6d)
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pH value of water is adjusted to evaluate the durability of the HNBs-based superhydrophobic
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Chemistry - A European Journal
Figure 6. The WCA of the HNBs-based superhydrophobic coating on the glass: (a) after
immersion in water for different times; (b) after immersion in water with different pH values
for 30 min; (c) after thermal treatment at 100 ºC for different times; (d) after thermal
treatment at different temperatures for two hours. The SA is estimated to be smaller than 5º
The poor resistance to the physical damages is one of the greatest barriers for the outdoor
applications
of
superhydrophobic
coatings.
The
durability
of
the
HNBs-based
superhydrophobic coating is evaluated by some typical physical damages including fingerwipe, tape-peeling, knife-cutting, and sandpaper-abrasion.[68] The superhydrophobic HNBs
coating on the glass for the durability investigation is fabricated by the “spray adhesive +
spray coating” method, which is regarded as an efficient technique to promote the
robustness.[3,
25]
In the finger-wipe damage test (Figure 7a), a finger wipes across the
superhydrophobic coating. The experiments show that the WCA is larger than 150º and SA
smaller than 5º after the finger-wipe damage, and the water droplets can rebound and roll off
easily, indicating the high stability of the superhydrophobic HNBs coating (Figure 7a). In the
tape-peeling damage test (Figure 7b), a strip of adhesive tape is attached to the superhydrophobic surface and then peeled off. The test shows the similar result to the fingerwipe damage test.
The more serious damage test, knife-cutting, is conducted by cutting the surface along
the cross pathways (Figure 7c). After knife-cutting, the superhydrophobic HNBs coating on
the glass still has the high WCA (> 150º) and low SA (< 5º), which allows the easy rolling of
water droplets. To make the comparison of various superhydrophobic coatings possible, the
standardized durability test is necessary.[24] The linear abrasion test is commonly adopted. The
sandpaper-abrasion damage test is illustrated in Figure 7d. Briefly, the superhydrophobic
HNBs coating on the glass is transversely and longitudinally abraded by the sandpaper (grit
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according to the measurement technique shown in Figure S7 (Supporting Information).
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Chemistry - A European Journal
no. 280) for a distance of 10 cm, respectively. A 140 g load is placed on the bottom surface of
superhydrophobic glass to apply more serious damage. The above procedure is defined as one
cycle. Even after experiencing such severe abrasion, the superhydrophobic HNBs coating on
the glass can survive, as indicated by the stable WCA and SA (Figure 7d). The repeating
sandpaper-abrasion damage is conducted, and the experiments show that the HNBs-based
(Figure 7e). The excellent mechanical durability ascribes to the stable structure and properties
of HNBs (Figure 7f).
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superhydrophobic coating can endure the sandpaper-abrasion damage for at least 30 cycles
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Chemistry - A European Journal
Figure 7. The durability tests on the superhydrophobic HNBs coating on the glass. (a) Fingerwipe damage, WCA = 153.9 ± 0.5º. (b) Tape-peeling damage, WCA = 154.6 ± 2.0º. (c)
Knife-cutting damage, WCA = 154.5 ± 0.3º. (d) Sandpaper-abrasion damage, WCA = 154.9 ±
0.3º. (e) The WCA of the superhydrophobic HNBs coating on the glass after the sandpaperabrasion damage for different cycles. (f) SEM micrograph of the superhydrophobic HNBs
Large-area Applications of the HNBs-Based Superhydrophobic Coating
Figure 8. The water flow is poured onto half-coated wood (67.0 × 17.8 cm2) (a), full-coated
glass (45.5 × 24.4 cm2) (b), and half-coated curved plastic bottle (30.0 × 16.5 cm2) (c).
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coating on the glass after the sandpaper-abrasion damage for 30 cycles.
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Chemistry - A European Journal
As aforementioned, we have developed a low-cost and environmentally friendly method to
synthesize the biocompatible HNBs in a large scale, and the HNBs-based superhydrophobic
coating also shows the superior properties. We further investigate the application of HNBsbased superhydrophobic coating on the practical objects with large sizes. Both the flat (wood
and glass) and curved (plastic bottle) substrates are coated by “spray adhesive + spray
water repellency of the large-area superhydrophobic HNBs coating. It is easy for the water
flow to rebound or roll off the surface and no water stain is remained on the superhydrophobic
coating (Figure 8a-c, and Movies S1-S3 in the Supporting Information).
Furthermore, the mechanical stability of the large-area superhydrophobic HNBs coating
is evaluated via a previously reported method.[19] Briefly, a 70 kg man wearing the shoes
treads on the full-coated toughened glass (Movie S4, Supporting Information). Under this
condition, the superhydrophobic HNBs coating needs to resist the damage from three aspects
(Figure 9a): (1) the high applied pressure (a 70 kg man); (2) the shoes with textured soles can
pose extremely serious damage; (3) the contaminants attached on the soles can strongly
adhere to the coating under high pressure. Fortunately, when the water flow is poured onto the
damaged surface, there is almost no water stain remaining on the superhydrophobic HNBs
coating on the glass after 10, 50 and 100 steps (Figure 9b-d), indicating the stable water
repellency after treading damage. Even after 500 steps (Figure 9d), the water flow can roll off
the surface easily, and no obvious water stain is left on the HNBs coating. The testing process
for the mechanical stability of the large-area superhydrophobic HNBs coating is also shown in
Movie S5 (Supporting Information). In this work, we have successfully realized the
application of the HNBs-based superhydrophobic coating with superior properties on the
practical objects with large sizes and arbitrary shapes.
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coating” method (Figure 8). The water flow instead of water droplets is used to evaluate the
Figure 9. (a) A 70-kg man wearing the shoes is treading on the fully coated toughened glass
with superhydrophobic HNBs. (b-e) The water flow is poured onto the damaged
superhydrophobic HNBs coating on the glass after 10, 50, 100, 500 steps.
Conclusions
In conclusion, we have developed a facile and environmentally friendly method for onestep synthesis of the biocompatible hydrophobic HNBs, which are used as fluorine-free,
substrate-independent, eco-friendly superhydrophobic paint. Both the cheap raw materials and
easy-to-scale-up synthesis method contribute to the mass production of HNBs. The scaled-up
production of HNBs has been realized in an autoclave with a volume of 10 litres, which is the
largest scale for the superhydrophobic HNBs paint ever reported in the literature. In addition,
a 100-litre reaction system has been designed and set up. The as-synthesized hydrophobic
22
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Chemistry - A European Journal
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Chemistry - A European Journal
paint based on HNBs can be easily coated on any substrate with a large area and an arbitrary
shape by a simple spray coating. The superhydrophobic HNBs coating shows the desirable
features including high biocompatibility, fluorine-free, substrate-independence, self-cleaning
in air and oil, high-temperature stability, corrosion resistance, and excellent mechanical
durability. The large-area applications of the superhydrophobic HNBs coating on the practical
superior stability of water repellency. For the first time, we report the simultaneous scaled-up
production
and
large-area
applications
of
fluorine-free
and
substrate-independent
superhydrophobic HNBs coating based on biocompatible HNBs with superior properties.
Experimental Section
One-step Synthesis of Hydrophobic HNBs
HNBs were synthesized via the calcium oleate precursor solvothermal method but with totally
different mass ratio of oleic acid to ethanol.[54, 55] Taking 800 mL reaction system as a typical
example, CaCl2 (2.200 g) aqueous solution (200 mL), NaOH (10.000 g) aqueous solution
(200 mL), and NaH2PO4•2H2O (2.800 g) aqueous solution (100 mL) were added into the
mixture of oleic acid (80.0 g) and ethanol (160.0 g) under stirring, respectively. The resulting
reaction mixture was transferred into a Telfon-lined stainless steel autoclave with a volume of
1 litre, sealed, and then solvothermally treated at 180 ºC for 24 h. The obtained HNBs were
separated, washed with ethanol and water, and dispersed in deionized water at a concentration
of 10 mg g-1, which was used as the superhydrophobic paint for the following investigation.
Synthesis of ultralong hydroxyapatite nanowires
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objects with large sizes have been also demonstrated. The treading damage test exhibits the
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Chemistry - A European Journal
The synthesis procedures were the same as those for the HNBs. The initial concentrations of
CaCl2, NaOH, and NaH2PO4•2H2O were unchanged, the weight ratio of oleic acid to ethanol
increased from 1:2 to 1:1 (120.0 g oleic acid and 120.0 g ethanol).
Fabrication of HNBs-based superhydrophobic coating by “spray adhesive + spray
Spray adhesive (3M-67) was used to enhance the binding strength. Before spray coating of the
HNBs paint, the substrate was coated by spray adhesive at a distance of ~30 cm from the
surface. The whole spray process last 2~5 s. After 5~10 s, the HNBs paint (10 mg g-1) was
sprayed onto the adhesive surface using a spray gun (W-101, ANEST IWATA Corporation).
The spray gun with a 1.0 mm nozzle was placed at a distance of ~30 cm from the surface. The
whole spray process last about 10 s with the pump output of 2.5 g s-1 under 0.5 MPa. The
superhydrophobic HNBs coating was placed at the ambient temperature in air overnight for
complete water evaporation.
Characterization
Scanning electron microscopy (SEM) micrographs were obtained on field-emission scanning
electron microscopes (S-4800, Hitachi, Japan; or Magellan 400, FEI, USA). Energy
dispersive spectroscopy elemental mapping was performed on FEI Magellan 400 equipped
with X-MAXN (Oxford Instrument, UK). Transmission electron microscopy (TEM)
micrographs were collected on a Hitachi H-800 (Japan) microscope. Thermogravimetric
(TG)-differential scanning calorimetry (DSC) curves were recorded on a simultaneous
thermal analyzer (STA 409 PC, Netzsch, Germany) with a heating rate of 10 ºC min-1 in
flowing air. Fourier transform infrared spectroscopy (FTIR) spectra were recorded on a FTIR
spectrometer (FTIR-7600, Lambda Scientific, Australia). Powder X-ray diffraction (XRD)
patterns were recorded on an X-ray diffractometer (Cu kα, λ = 1.54178 Å, Rigaku D/max
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Accepted Manuscript
coating” method
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Chemistry - A European Journal
2550V). Water contact angle was measured using an optical contact angle system (Model
SL200B) at three different sites on each sample using a 3 μL deionized water droplet. Sliding
angle was evaluated according to the measurement technique in Figure S7 (Supporting
Information). The viscosity was measured on a rheometer (DV3T, Brookfield).
We acknowledge the financial support from the Science and Technology Commission of
Shanghai (15JC1491001), National Natural Science Foundation of China (21601199,
51702342, 21501188) and Shanghai Sailing Program (16YF1413000).
Received: ((will be filled in by the editorial staff))
Revised: ((will be filled in by the editorial staff))
Published online: ((will be filled in by the editorial staff))
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Chemistry - A European Journal
Entry for the Table of Contents
F. F Chen, Z. Y. Yang, Y. J. Zhu,* Z. C. Xiong,* L. Y. Dong, B. Q. Lu, J. Wu, R. L. Yang
Low-Cost and Scaled-up Production of Fluorine-Free, Substrate-Independent, Large-
Keywords: hydroxyapatite, nanowires, superhydrophobic coating, green chemistry, largescale preparation
Large-area superhydrophobic coating: The facile, low-cost, environmentally friendly, and
scaled-up production of the superhydrophobic coatings based on hydroxyapatite nanowire
bundles (HNBs) is demonstrated. The superhydrophobic HNBs coating shows the desirable
features including high biocompatibility, fluorine-free, substrate-independence, self-cleaning,
high-temperature stability, corrosion resistance, and excellent mechanical durability.
30
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Area Superhydrophobic Coatings Based on Hydroxyapatite Nanowire Bundles
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