Beeswax - Superhydrophobic For Latent Heat Storage

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Phase Change Materials

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Superhydrophobic Coatings from Beeswax-in-Water

Emulsions with Latent Heat Storage Capability
Sara Naderizadeh,* José Alejandro Heredia-Guerrero, Gianvito Caputo, Silvia Grasselli,
Annalisa Malchiodi, Athanassia Athanassiou, and Ilker S. Bayer*
1. Introduction
Beeswax particles are homogenously emulsified in commercial aqueous
polymer dispersion, without additional dispersing agents and surfactants. Natural wax in the form of wax tubules is
Emulsions display very good stability with wax droplet size distribution the key component of the lotus leaf struc-
ture that leads to superhydrophobicity or
around 350 nm. The wax to polymer ratio in the emulsions can be tuned the “lotus effect” that was demonstrated
without compromising emulsion stability. The emulsions are spray coated in the 1990s.[1] Since then, many different
in order to create either hydrophobic or superhydrophobic coatings. For and effective methods have been utilized to
superhydrophobicity, silica nanoparticles are dispersed in the emulsions produce hydrorepellent surfaces inspired
at different concentrations. Beeswax-rich coatings such as the ones with by the lotus leaf.[2,3] Recently, research and
development efforts have been intensified
1:1 beeswax:polymer ratio or more, including the superhydrophobic ones,
toward fabricating robust and functional
demonstrate promising latent heat storage characteristics, suitable for nonwetting surfaces and coatings using
thermal management applications. Electron microscopy studies show that sustainable means and materials, due to
as a result of emulsification, the polymer encapsulates the wax droplets/par- the environmental issues associated with
ticles as a nanothin shell, preventing a major problem related to low melting potential toxicity or bioaccumulation haz-
point phase change materials referred to as leaching. Hence, the coatings ards of some of the materials or solvents
used.[2,4–7] For instance, recently, fabri-
can be heated well above the melting point of beeswax (≈62 °C) and can still cating nonwetting surfaces using only
demonstrate effective heat storage during the cooling stage. This water-based water-based solutions or suspensions has
coating process using ecofriendly material constituents can easily be scaled been successfully demonstrated.[8,9] In this
up and used in responsive coating applications, ranging from electronics to concept, natural or synthetic waxes along
interior or exterior structural buildings requiring efficient energy management with some edible fatty acids have been
proved very promising since they can be
and thermal energy savings.
processed in certain innovative ways to
fabricate superhydrophobic surfaces or
coatings today.[6,10,11] Superhydrophobic
coatings and structures made solely by
waxes suffer from thermal instability (low melting point of
S. Naderizadeh, Dr. J. A. Heredia-Guerrero, Dr. A. Athanassiou, waxes), leaching, and mechanical fragility against certain degree
Dr. I. S. Bayer of wear and abrasion. For instance, when spray coated, carnauba
Smart Materials
Istituto Italiano di Tecnologia wax-alcohol emulsions spontaneously form the required hierar-
Via Morego 30, 16163 Genova, Italy chical surfaces textures and become superhydrophobic. How-
E-mail: sara.naderizadeh@iit.it; ilker.bayer@iit.it ever, under moderate heat exposure (≈60 °C) the wax melts and
S. Naderizadeh re-assembles into a smoother surface texture losing its superhy-
Dipartimento di Informatica Bioingegneria drophobicity. Hence, embedding waxes in a proper polymeric
Robotica e Ingegneria dei Sistemi (DIBRIS)
Universita Degli Studi di Genova
matrix could potentially eliminate or lower such drawbacks to
Via All’Opera Pia 13, 16145 Genova, Italy a certain extent.[12] Yet, impregnating waxes and fatty acids in
Dr. G. Caputo host polymer matrices pose additional problems, such as loss
Nanochemistry of hydrophobicity due to the fact that waxes can migrate to the
Istituto Italiano di Tecnologia bulk of the polymer rather than assembling at the surfaces in the
Via Morego 30, 16163 Genova, Italy form of hierarchical surface texture like the lotus leaf.[13] None-
Dr. S. Grasselli, Dr. A. Malchiodi theless, various waxes embedded in conventional polymers have
GEA Mechanical Equipment Italia S.p.A.
Via da Erba Edoari Mario 29, 43123 Parma, Italy proven to be effective agents for creating soft yet robust func-
The ORCID identification number(s) for the author(s) of this article
tional materials with latent heat storage capabilities.[14–16] In this
can be found under https://doi.org/10.1002/admi.201801782. work, we aim to combine superhydrophobicity with latent heat
storage capability into one coating, by following an alternative
DOI: 10.1002/admi.201801782 approach in which a natural wax (beeswax) constitutes at least
Adv. Mater. Interfaces 2019, 1801782 1801782 (1 of 11) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
half of the polymeric matrix, rather than being embedded in the 2. Results and Discussion
matrix as an additive. Beeswax is extensively used in food and
coatings industry, cosmetics, and drug delivery systems.[17–19] 2.1. Characteristics of the Oil–Water Emulsions
Moreover, we use water as the solvent of choice to ensure all-
sustainable coating fabrication. To achieve this, in other words, Review of literature indicates that the number of patent publi-
to solubilize or disperse the hydrophobic wax in water, we resort cations on the preparation and use of wax emulsion coatings is
to an oil-in-water emulsion system approach.[20] generally more than corresponding academic publications.[31,32]
There are several methods to produce wax emulsions in water This most likely is attributed to the large number of industrial
that utilize multiple surfactants/emulsifiers and stabilizers tai- applications of wax emulsions ranging from automotive market
lored toward the intended application, such as drug delivery,[21,22] to paints industry and cosmetics. Most of these emulsions rely
inks,[23] and paints.[24,25] In these formulations, emulsifiers are on wax-in-water dispersions stabilized with various surfactants
absorbed in oil–water interfaces, to decrease the interfacial tension or surfactant combinations. Herein, beeswax dispersions in
and prevent wax from agglomeration and separation.[26,27] Further- water are mixed and homogenized with aqueous fluoropolymer
more, beeswax can absorb and release heat in a small temperature dispersion (Capstone ST-100). Hot beeswax dispersions in
gap that makes it ideal as a latent heat storage material.[28] Herein, water are not stable; however, rapid addition of the polymer dis-
we demonstrate that when hot beeswax/water solutions are persion into these unstable emulsions, before the wax separates
directly mixed with commercial waterborne perfluorinated acrylic out, form very stable wax/polymer emulsions. Perfluorinated
copolymer dispersion (Capstone ST-100), highly stable wax emul- acrylic copolymers having C-6 chemistry (see Figure 1c) have
sions can be formed. In these emulsions, the copolymer acts as a been approved as an environmentally friendly fluoropolymer
nonionic fluorosurfactant, eliminating the need to use additional due to their nontoxic degradation by-products. They can also
dispersants, efficiently encapsulating wax. Note that according to act as fluoro-surfactants not only to disperse beeswax drop-
the Environmental Protection Agency (EPA) 2010/2015 perfluo- lets in water, but also to create a polar shell around beeswax.
rooctanoic acid (PFOA) stewardship program, the waterborne Emulsions containing the 1:1 wax:polymer concentration ratio
acrylic copolymer dispersion utilized in this work does not contain were selected in this work. TEM image of such a polymer
any C-8 fluorochemistry and does not breakdown into PFOAs in encapsulated/coated wax particle is displayed in Figure 1a.
the environment.[29,30] The copolymer not only acts as an emulsion Size distribution plots of pure wax in water dispersion (before
stabilizer but also as an effective wax encapsulation agent and as destabilization), commercial fluoropolymer dispersion, and
substrate adhesion enhancer for beeswax. Moreover, hydrophilic the 1:1 emulsions measured with dynamic light scattering
(surface unmodified) silica nanoparticles (NPs) can easily be sus- (DLS) are shown in Figure 1b. Pure beeswax dispersion
pended in these stable emulsions and by doing so the resultant (B1 in Table 1), after homogenization process, displays a
coatings demonstrate self-cleaning superhydrophobicity. Gaussian distribution centered around 350 nm with a broad
Figure 1. a) TEM image of the core–shell structured particle (scale bar corresponds to 0.2 µm). b) Size distribution of the B1 (pure beeswax), B2 (pure
capstone), and B3 (a 1:1 blend of the two components) samples by DLS. c) Chemical structure of perfluorinated acrylic copolymer.
Table 1. Sample’s formulation (all the samples were prepared in 50 mL gentle bath ultrasonication. This may be attributed to the core–
Mili-Q water). shell structure formation between the wax and the polymer as
demonstrated in Figure 1a. This stable emulsion morphology
Code Beeswax [wt%] Capstone [wt%] Silica NPs [wt%] is very important because it allowed us to disperse various
B1 1 – – amounts of hydrophilic silica nanoparticles in these blend
B2 – 1 – emulsions to create superhydrophobic nanocoatings, but also
to encapsulate of an easily liquefying wax into a polymer shell
B3 1 1 –
to enable reversible latent heat storage coating. Chemical struc-
B4 1 1 0.3
ture of perfluorinated acrylic copolymers are given in Figure 1c.
B5 1 2 – The side chain number, n, (side chain length) should be 6 or
B6 1 3 – less in order to comply with environmental regulations.
B7 2 1 – Generally, perflurinated acrylics are not very long chain or
high molecular weight polymers that are also surfactant-like
B8 3 1 –
macromolecules due to perfluorinated side chain structure and
the copolymeric nature of the acrylic backbone. Interchange-
distribution function ranging from 100 nm up to a micrometer. ably, they are known as perfluorinated surfactants.[33] These
Note that this measurement was made before the wax dispersion macromolecules are quite efficient as dispersing agents for
becomes unstable, after about 10 min. Before destabilization, hydrophobic or oily inclusions in water-based formulations
the pure wax dispersion can be regarded as a microemulsion such as paints and even in pharmaceutical preparations.[34]
prone to rapid wax droplet agglomeration and segregation. The
diluted commercial fluoropolymer dispersion (B2, Table 1),
on the other hand, has double distribution pattern such that 2.2. Chemical Analysis of the Emulsion Coatings
some polymeric micelles are centered around 100 nm with a
narrow distribution and other micellar structures span a much Beeswax (B1), capstone (B2), and the 1:1 blend emulsion (B3)
broader droplet distribution (up to 1.5 µm) in the dispersion. were sprayed onto silicon wafer substrates and the formed coat-
Nonetheless, this commercial dispersion was very stable for a ings were chemically characterized by attenuated total reflec-
period exceeding 3 months of shelf life. The blended dispersion tion (ATR)-Fourier transform infrared (FTIR) spectroscopy.
with the 1:1 wax/polymer phase in water (B3, Table 1) was also Figure 2a shows the ATR-FTIR measurements of the samples.
found to be very stable with a droplet distribution function cen- Main peaks of beeswax were ascribed to methylene (asymmetric
tered on 250 nm with a maximum droplet size span of 750 nm. and symmetric CH2 stretching modes at 2915 and 2849 cm−1,
Presence of the fluoropolymer enabled almost 50% reduction respectively, scissoring and rocking bending doublets at ≈1468
in droplet size distribution in beeswax and no segregation was and ≈725 cm−1, respectively) and ester (CO and COC
observed even after 10 d of shelf life. The blend emulsion was stretching modes at 1736 and 1171 cm−1, respectively) groups
in fact stable for several weeks without major destabilization in crystalline form.[35] On the other hand, capstone showed
and could be spray coated after simple mechanical mixing or the characteristic peaks of ester (CO and COC stretching
Figure 2. a) ATR-FTIR spectra of B1 (pure beeswax), B2 (pure capstone), and B3 (a blend with the same amounts of both components) samples in the
3800–600 cm−1 region. The main assignments are included for beeswax (black) and capstone (red). b) CH2 stretching mode infrared spectral region
for B1 and B3 samples at 28 °C (black), 45 °C (red), and 89 °C (green). c) Variation of the wavenumber (top) and FWHM (bottom) of the asymmetric
(filled symbols) and symmetric (empty symbols) methylene stretching modes of B1 (black) and B3 (red) with the temperature.
Figure 3. XPS high-resolution C 1s spectra related to coatings a) B3 and b) B4. Elemental composition of the samples with atomic percentages (Table).
modes at 1730 and 1188 cm−1, respectively) and perfluoro- ranges between 16.7% and 14.3% as shown in the table in
methylene (asymmetric and symmetric CF2 stretching modes Figure 3. The lower amount of fluorine in sample B4 could be
at 1233 and 1142 cm−1, respectively) functional groups.[30] ascribed to the presence of silica on the outer surface of the
B3 sample did not display any significant shift or appearance of coating that is essential for superhydrophobicity. As a matter of
new band different from the ones associated with the wax and fact, Si 2p band at 103.7 eV (not shown for brevity) typical[37] of
the fluorinated polymer, indicating that both components do SiO2 was detected with a silicon amount of 3.8% (see the table
not interact by chemical bonding. However, interestingly, the in Figure 3).
bands attributable to methylene groups (asymmetric and sym-
metric CH2 stretching, and scissoring, and rocking bending
modes) of pure beeswax and beeswax–capstone blend shifted 2.3. Wetting Characteristics of the Coatings
in a different way with temperature. For simplicity, only the
asymmetric and symmetric CH2 stretching modes for B1 and Coatings obtained from the 1:1 blend emulsions were hydro-
B3 samples are shown in Figure 2b. As observed in Figure 2c, phobic, but did not display superhydrophobicity. Their static wet-
there is an increase of the wavenumber from 34 to 66 °C, which ting properties were similar to pure wax (B1) and pure polymer
is indicative of a solid–liquid phase change in waxy materials.[36] coatings (B2) as seen in Figure 4a with contact angle (CA)
In general, both asymmetric and symmetric CH2 stretching values somewhat exceeding 110°. All three coatings (pure and
modes for beeswax–capstone showed higher wavenumbers and blended) demonstrated droplet mobility in the form of sliding
full width at half-maximum (FWHM) values than the respec- droplets[38] (droplets slide rather than roll away) at tilt angles
tive peaks of pure beeswax. This behavior is characteristic of of 90° as opposed to some very hydrophobic surfaces such as
an increase in the number of gauche conformers, revealing a silicones which do not demonstrate droplet mobility even at tilt
higher alkyl beeswax aliphatic chain disorder with tempera- angles >90° . The sliding angle concept should not be confused
ture[32] in the case of the blend coating, possibly induced by the with free droplet roll away motion.[39] To obtain self-cleaning
fluorinated copolymer. superhydrophobicity and to optimize the silica nanoparticles’
Similarly, chemical characteristics of the coatings made from concentration, various amounts of silica nanoparticles were
B3 and B4 (B3 containing 30 wt% silica nanoparticles) were dispersed in B3, namely, the 1:1 blend emulsion. Five different
analyzed by X-ray photoelectron spectroscopy (XPS) as shown emulsions with various silica nanoparticles’ concentrations
in Figure 3. The high-resolution C 1s spectra revealed the pres- were prepared to optimize for spray coating, namely, 0.1, 0.2,
ence of a fluorinated surface for both samples as evidenced 0.3, 0.4, 0.5 wt% in solution. As is discussed in the Methods
by the typical CF2 (294.0 ± 0.1 eV) and CF3 (292.4 ± 0.1 eV) Section (Table 1), this means silica nanoparticle concentration
components (Figure 3a,b), consistent with the fluorinated wax in the dry coatings ranges from 10 to 50 wt% with respect to the
particles in emulsions. The fluorine content, as derived from polymer/wax blend matrix. Wetting properties of all the nano-
the quantification of the corresponding high-resolution spectra, composite coatings were investigated and the results are shown
Figure 4. a) Wetting properties of the coated samples. b) The comparison of static contact angle (CA) and water droplet roll-off angle (RA) values as
a function of silica NP concentration in the coatings.
in Figure 4b. The graph illustrates that superhydrophobic 2.4. Morphological Characterization
threshold (CA ≥ 150°) can be obtained by using 0.3 wt% silica
NPs or more in the emulsions. Also, droplet roll-off angles (RA) Scanning electron microscope, SEM, surface, and cross-sec-
for these nanocomposites were recorded to be below <10°. As tion morphology images of B3 and B4 coatings are shown in
a result, the nanocomposite B4 having the lowest amount of Figure 5. The sample B3 shows a very smooth surface morpho
silica NPs concentration (30 wt%) along with superhydropho- logy with some craters on the surface as seen in Figure 5a,
bicity and low RA was selected as sample of interest for further which are related to the micrometer-sized wax droplets that
thermal testing. More specifically, on B4, 5 µL droplets readily solidified as embedded spheres in the polymer matrix. This is
rolled away at 5.5° tilt angles. better visible in the cross-section image in Figure 5b. However,
Figure 5. SEM images of the surface a) B3 and b) B4. Cross-section SEM images of c) B3 and d) B4.
Figure 6. AFM topography: 3D images of a) B3 and c) B4. Watershed grain analysis of b) B3 and d) B4. (Zones with different colors designate surface
sections with uniform topography assigned to a specific roughness value).
dispersed nanosilica in the emulsion causes coating surface easurements. At the same time, to understand the thermal
m
morphology to change drastically as seen in Figure 5c. In fact, properties of the fabricated coatings, differential scanning
the morphology resembles the submicrometer vascular struc- calorimetry (DSC) was applied and the results are shown in
ture of the rose petal or similar flowers.[40] This morphology is Figure 7a. Calculated melting temperatures and enthalpy
quite different from superhydrophobic microstructure of fluori- of fusion values are also summarized in Figure 7 (in tabular
nated acrylic copolymer–nanosilica coatings reported earlier by form). The melting temperature of the beeswax was meas-
our group.[41] The cross-section morphology of the sample B4 ured to be 62.4 °C, which is in agreement with the other
(Figure 5d) also demonstrates a random, rough texturing rather studies.[43,44] The melting temperature of the wax embedded
than a wax particle embedded polymer matrix structure. in the polymer/wax blend coating, B3, is slightly lower at
Effect of nanosilica inclusion on the surface roughness 60.8 °C that can be attributed to the deformation or partial
was also studied by atomic force microscopy (AFM) measure- amorphization of crystalline structure of beeswax. The original
ments that are displayed in Figure 6. Average surface rough- crystalline structure of beeswax was measured by X-ray diffrac-
ness of the B3 and B4 samples was estimated from several tion (XRD) and the corresponding XRD pattern is shown in
AFM measurements. Watershed grain algorithm[42] was applied Figure 7b. The diffractogram presents reflections centered at
to analyze and estimate the surface roughness as explained in 19.1, 21.3, 23.6, 29.8, and 40.3° that can be attributed to the
the Experimental Section (see Figure 6b,d). Average roughness orthorhombic structure of beeswax.[45,46] Due to the forma-
for the blend coating designated as B3 was measured to be tion of fluoroacrylic shell around beeswax, some rearrange-
120 ± 40 nm. B4 sample on the other hand had higher average ments can take place in the crystalline structure of beeswax,
roughness of 420 ± 50 nm. This could be attributed to the crea- for instance, lower intensity crystalline peaks at 2θ 19.1° and
tion of flower petal-like submicro surface structure, such as 40.3° disappear (Figure 7b). This could potentially cause reduc-
rose petal, due to dispersion of nanosilica in the emulsions. tion in melting temperatures measured in samples B3 and B4
compared to pure beeswax (see the table in Figure 7). Heat of
fusion of pure beeswax was measured to be 155.3 J g−1 during
2.5. Latent Heat Storage Characteristics of the Coatings its melting. The measured value is very similar to waxes col-
lected from cavity resting honeybees (i.e., Apis cerana, Apis mel-
Latent heat storage or phase change material-like prop- lifera, etc.).[47] The value is higher than the heat of fusion of
erty of the coatings was analyzed by infrared (IR) camera industrial semicrystalline polymers such as polyesters,[48] but
Figure 7. a) DSC thermogram of the beeswax, B2, B3, and B4 samples. b) XRD pattern of pure beeswax. The table summarizes thermal properties of
the pure beeswax and the B3 and B4 coatings.
occurring at much lower temperatures that is ideal for envi- s amples listed in Table 1, after transferring them from 100 °C
ronmental phase change material applications. to a surface at room temperature. The curve labeled as the
Heat of fusion of samples B3 and B4 were measured to be “bare substrate” denotes the stainless steel substrate over which
around 84 J g−1 (see the table in Figure 7) that is about a 46% the coatings were applied. As other controls, pure beeswax and
less than pure wax due to polymer presence. This could be pure fluoropolymer coatings on stainless steel were also tested.
related to the encapsulation of wax particles by the polymer and The cooling patterns can readily indicate latent heat storage
the fact that the acrylic polymer is not a phase change material. potential of each coating[50] in the sense that rapid cooling or
Polymer encapsulation can cause disruption of onset and end quenching-like behavior indicates no heat storage capability,
temperatures related to melting of wax, reducing its enthalpy of whereas slow, stepwise cooling indicates phase changes during
fusion. However, other natural beeswaxes with lower enthalpy cooling and ability to store heat. According to Figure 8a, for
of fusion exist such as the ones synthesized by common the bare metal substrate and pure fluoropolymer (B2), a rapid
Melipona bee species with almost identical heat of fusion cooling occurs within the first 50 s and after 300 s both sur-
values.[47] Nonetheless, the emulsion coatings encapsulate the faces cool below 40 °C. However, cooling of the coatings B1,
wax very well and prevent leaching of the wax upon heating B3, and B4 is quite different and for instance after 100 s the
them above the melting point of wax. Therefore, a tradeoff coatings are about 15 °C warmer than the bare or fluoropol-
between high heat of fusion but poor structural stability (pure ymer coated surfaces. Between 100 and 300 s, cooling of these
wax) and good structural stability (encapsulated wax) but some- coatings still advances slower and they maintain warmer tem-
what lower heat of fusion was established by this emulsion peratures than both the bare substrate and the fluoropolymer
coating approach. coating (B2). In fact, coatings dominant in beeswax concentra-
Note also that according to a recent comprehensive study,[49] tion (i.e., B7 and B8) remain the warmest during the cooling
accelerated degradation of beeswax coatings maintained at 60 process as seen in Figure 8a with two step-like or stepwise
and 100 °C for up to a year in controlled chambers show that cooling profiles (two quasithermal arrest zones),[51] with the
the coatings do not degrade or delaminate except that some first quasithermal arrest zone appearing between 0 and 150 s.
heavy alcohols may evaporate depending on the origin of All other beeswax containing coatings including the optimized
beeswax. We have observed that due to use of perfluorinated superhydrophobic one, demonstrate single step cooling trends
acrylic polymer, the coatings have good substrate adhesion and between 100 and 300 s, with the step size and shape controlled
did not delaminate for more than 3 months under ambient by the relative concentration ratio between beeswax and the
conditions. Finally, to examine the heat storage and release fluoropolymer. Note that these regions with very slow cooling
properties of the fabricated samples, temporal cooling profiles profiles are considered as quasithermal arrest zones[51] due to
of different coatings on stainless steel substrates were recorded. the fact that thermodynamically ideal thermal arrest zones have
Figure 8a shows the cooling temperature profiles of all the zero slope (cooling rate). When the fluoropolymer is dominant
Figure 8. a) Temperature profiles as a function of time for different samples. b) Cooling rate as a function of time e. c) IR-camera observations in
different times for bare substrate (stainless steel), and B2 and B8 samples.
with respect to wax (B5, B6), the stepwise cooling takes place which thermal energy management is needed. The process is
faster and the thermal arrest zone is smaller (Figure 8a). In such that the natural beeswax could be homogenously emulsi-
fact, estimated cooling rates (°C s−1) of some selected coatings fied in environmentally approved commercial aqueous fluoro-
are shown in Figure 8b. Cooling rates were estimated from the polymer dispersion. The emulsion formation was spontaneous
slope of the cooling curves in Figure 8a and interpretation of with the help of a desktop sized homogenizer and emulsions
Figure 8b is somewhat easier than Figure 8a in the sense that remained stable for weeks. Wax to polymer ratio in the emul-
high cooling rates with sudden jumps/falls indicate poor or no sions could be easily changed without compromising stability.
latent heat storage effect. The emulsions were spray coated on metal or glass surfaces. For
Note that cooling rates of B3, B4, and B8 are much reduced superhydrophobicity, silica nanoparticles were directly dispersed
compared to the bare substrate or the fluoropolymer coated in the emulsions. Coatings rich in beeswax, including the supe-
substrate and that these wax/polymer coatings (with or without rhydrophobic ones, demonstrated promising latent heat storage
nanoparticles) still demonstrate residual heat release after 200 s characteristics. Due to effective polymer encapsulation of
of substrate transfer, whereas the metal substrate and sample B2 beeswax, the major problem of phase change material leaching
have practically reached the room temperature. This can be was eliminated. Hence, the coatings can be heated well above
better illustrated if some selected IR images are inspected in the melting point of beeswax (≈62 °C) and used for latent heat
Figure 8c, where a wax dominated wax/polymer coating, B8, storage during their cooling phase. This water-based coating
remains much warmer than the bare metal or fluoropolymer process along with eco-friendly material constituents can easily
coated substrates after 5 min of cooling. be scaled up and used in any responsive coating applications
ranging from electronics to structural buildings requiring effi-
cient energy management and thermal energy savings.
3. Conclusions
Eco-friendly (all water-based), hydrophobic, and superhydro-
phobic coatings with thermal energy storage properties based 4. Experimental Section
on beeswax/polymer emulsions were fabricated for the first Materials: Chunks of beeswax was purchased from Sigma-Aldrich and
time. The coatings can be used in many diverse applications in used as received. A commercial water-dispersed perfluorinated acrylic
copolymer (C6-fluoroacrylic) (PFAC; Capstone ST-100) was purchased avoid aggregation and multiple scattering effects. Dilute dispersions
from DuPont, USA. It consisted of ≈20 wt% cationic fluoroacrylic were kept in quartz cuvettes with 10 mm path length. Size distribution
copolymer dispersed in water. Hydrophilic fumed silica nanoparticles curve as a function of number (%) and average particle size (z-average,
(Silica NPs), Aerosil R-300) was kindly donated by Evonik Industries, nm), were valuated to characterize the emulsions. Three different
Germany. Ultrapure Mili-Q water was used as solvent in all the samples were analyzed in order to confirm the repeatability of the
experiments. measurements.
Preparation of the Coatings: All coatings were fabricated via spray Morphology of the droplets/particles was assessed by transmission
deposition method from water-based emulsions. For preparation of electron microscopy (TEM) using a Jeol Jem-1011 microscope under
beeswax emulsion, beeswax was melted in boiling water and dispersed an accelerating voltage of 100 kV. The emulsions were deposited onto
in it further by probe sonic processing (Sonics, Vibra cell, USA) for 1 min carbon-coated copper TEM grid by drop casting and dried under light
to make a 1 wt% emulsion. This pre-emulsion (white in color) was not vacuum before imaging.
stable and phase separated into a solid and oily wax phase and water Wetting Analysis: To study the surface wettability, static water CAs
after a few minutes. However, before this happened, the commercial and RAs were measured at room temperature using a contact angle
water-dispersed PFAC was combined with the wax emulsion. In order goniometer (DataPhysics OCAH 200, Germany). 5 µL water (Mili-Q
to create a 50/50 or (1:1), the commercial polymer solution was diluted water) droplets were dispensed on the coating’s surface and side view
with water to 1 wt% concentration before mixing. The mixture (≈300 mL images of them were captured. For measuring water RAs, 5 µL water
in volume) was homogenized further by using a commercial tabletop droplets were deposited onto the surface followed by continuous stage
laboratory homogenizer (Panda Plus 2000, GEA Niro Soavi, Italy). The tilting with 1.42° s−1 angular velocity. RAs were recorded as a stage tilt
homogenizer was operated at about 275 bar with a flow rate of 9 L min−1 angle at which all the droplets started roll away from the coatings. To
and the wax/polymer mixture was homogenized by passing through the prove the reproducibility of the results, five different measurements
homogenizer four times. To make nanocomposites, different quantities were done on five different samples that were fabricated under identical
of silica NPs were dispersed in the emulsion followed by the similar conditions.
homogenization process (see Figure 9). Morphological Characterization: SEM images of fabricated coatings
In order to make coatings from emulsions that were stored for more were obtained using a JSM-6490LA microscope (Jeol, Japan) with 10 kV
than a week, the stored emulsions were ultrasonic processed for 2 h acceleration voltage. In order to prepare samples for SEM imaging, the
in ultrasonic bath at 59 Hz (Savatec, Strumenti scientifici, LCD Series, emulsions were sprayed onto conductive aluminum foils instead. Before
Italy) to ensure proper redispersion before spray. imaging, samples were sputter-coated with a 10 nm gold layer, to reduce
The emulsions were sprayed onto glass or metal substrates using charging effects. For cross-section SEM imaging, the specimens were
an internal mix airbrush spray system (model VL-SET, Paasche, USA), cryogenically fractured in liquid nitrogen, followed by sputter-coating
with 200 kPa pressure. In order to facilitate rapid evaporation of with gold on the fracture surface (10 nm) as well.
water, the substrates were placed on a hot plate maintained at 100 °C. AFM images were acquired by using Park system AFM instrument
The distance between the substrate and nozzle head was kept (XE-100) in noncontact mode. Areas of 10 × 10 µm2 were scanned
approximately at 15 cm. Table 1 shows different types of emulsions and using single-beam silicon cantilever tips (PPP-NCHR-10) for data
their compositions that were spray coated in order to find the optimum acquisition with less than 10 nm nominal tip diameter and 42 mN m−1
coating conditions. Note that for silica NPs 0.3 wt% in emulsion meant elastic force constant for high sensitivity. The measurements were
that B3 emulsion contained 0.3% nanoparticles by weight compared to done in air in a vibration-insulated environment and an acoustic
the total weight of the polymer and wax in the emulsion. This, on a dry enclosure. The relative set point was set at 500 nN. The roughness
basis, translated into 30 wt% nanoparticles in the coating and the rest is properties of the surfaces were investigated through a built-in grain
70 wt% polymer/wax blend or 35 wt% polymer and 35 wt% wax. analysis statistical algorithm known as watershed algorithm. AFM
Emulsion Characterization: The average droplet size of the emulsions topography images were divided into different regions identified with
was determined using a Malvern Zetasizer Nano ZS by Dynamic light a certain average roughness values. Finally, the mean roughness of the
scattering (DLS) method working at 632.8 nm and at 25 °C, with a He/ samples was calculated by averaging the roughness values of these
Ne laser. Different emulsions were prediluted with deionized water to different areas.[52]
Figure 9. Schematic illustration of emulsion fabrication and superhydrophobic coating application.
Figure 10. Schematic of IR-camera experimental setup to obtain cooling profiles.
Fourier Transform Infrared Spectra Measurements: Infrared spectra Conflict of Interest

were obtained with a single-reflection ATR accessory (MIRacle ATR,
Pike Technologies) coupled to an FTIR spectrometer (Equinox 70 FT-IR, The authors declare no conflict of interest.
Bruker). All spectra were recorded in the range from 3800 to 600 cm−1
with a resolution of 4 cm−1, accumulating 128 scans.
For the measurements at different temperatures, a VeeMAX III ATR
device with a heating conversion plate (Pike) was employed. After the Keywords
temperature was stabilized, the samples were placed on the hot crystal
in order to perform the measurement (4 cm−1 resolution, 128 scans). beeswax, homogenizer, latent heat storage, phase change material,
The wavenumbers and full width at half-maximum of the peaks were superhydrophobic
determined by using a commercial software Spectra Manager v.2.
Thermal Analysis: DSC thermograms were obtained using a Diamond
Received: November 8, 2018
DSC-Perkin Elmer instrument from −50 to 160 °C under dry nitrogen flow
Revised: December 17, 2018
(20 mL min−1) at heating rate of 20 °C min−1. Accurately weighed samples
Published online:
with an approximate weight of 18 mg were placed in an aluminum pan and
preprogrammed heating–cooling–heating cycle was recorded. The melting
temperatures and enthalpy of fusion of the beeswax and coated samples
were calculated through built-in software assisted numerical integration.
X-Ray Analysis: Crystalline structure of the materials was studied [1] H. J. Ensikat, P. Ditsche-Kuru, C. Neinhuis, W. Barthlott, Beilstein J.
using X-ray diffraction analysis with a PANalytical Empyrean X-ray Nanotechnol. 2011, 2, 152.
diffractometer. The experiments were performed using CuKα anode (λ = [2] Q.-Y. Cheng, X.-P. An, Y.-D. Li, C.-L. Huang, J.-B. Zeng, ACS Sustain-
1.5406 ˚A) operated at 45 kV and 40 mA from 5° to 50° 2θ. able Chem. Eng. 2017, 5, 11440.
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Latent Heat Storage Characteristics: The latent heat storage characteristics [5] A. Milionis, C. S. Sharma, R. Hopf, M. Uggowitzer, I. S. Bayer,
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Beeswax - Superhydrophobic For Latent Heat Storage

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Phase Change Materials

Superhydrophobic Coatings from Beeswax-in-Water

Figure 9. Schematic illustration of emulsion fabrication and superhydrophobic coating application.

Figure 10. Schematic of IR-camera experimental setup to obtain cooling profiles.

Fourier Transform Infrared Spectra Measurements: Infrared spectra Conflict of Interest

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