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Corrosion-Resistant Hydrophobic Thermal Barrier Composite

Coating on Metal Strip: A New Dimension to Steel Strips for Roofing
Segment
S. S. Ananthapadmanabhan, Tapan Kumar Rout, Sudin Chatterjee, Titas Dasgupta,
and Smrutiranjan Parida*
Cite This: ACS Appl. Mater. Interfaces 2023, 15, 51737−51752 Read Online
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ABSTRACT: This study demonstrates a cost-effective, thin, multifunctional

composite coating system with outstanding thermal insulation for thermal
management and heat shield applications, such as roofs, as well as outstanding
resistance to corrosion. The hydrophobic multifunctional epoxy composite coating
systems were designed with surface-modified fillers to impart both reduced heat
conduction and high infrared reflectance in a thin coating with a 65−100 μm dry
film thickness (DFT). With a judicial combination of hollow microspheres (HMS)
activated and modified with silica (sHMS) and stearic acid-modified TiO2 (sMO),
the developed composite coating attained the highest thermal insulation property
with a temperature drop of 21−31 °C at different distances below the coated panel,
which is superior to the values of temperature drop reported earlier. The high solar
reflectance of the composite coating in the near-infrared (NIR) region exceeds 72%
with a low thermal conductivity of 0.178 W m−1 K−1. After 720 h of exposure in a 3.5
wt % NaCl solution, the composite coating revealed a corrosion protection efficiency of 99%. The work demonstrates that high solar
reflectivity and low thermal conductivity must be active simultaneously to achieve superior thermal shielding in a thin coating on a
metal. A careful selection of fillers and appropriate surface modifications ensures hydrophobicity and proper distribution of the fillers
in the coating for a high barrier effect to prevent environmental deterioration. With these superior performance parameters, the
developed composite coatings make an essential contribution to energy sustainability and the protection against environmental
degradation.
KEYWORDS: thermal insulation, hollow microsphere, infrared reflection, hydrophobic, composite coatings, anticorrosion coating

1. INTRODUCTION coatings work by radiating absorbed solar energy in a specific

Temperature increase due to climate change has forced many wavelength into the atmosphere. This allows the object to emit
applications to look for materials and coatings for thermal or more energy than it absorbs, resulting in a decrease in
heat shielding for temperature control. Areas, such as housing temperature. These coatings take advantage of the “atmos-
roofs, defense installations, warehouses, data centers, etc., pheric window” in the 8−13.5 μm wavelength range, where
require proper thermal management for sustainability. For such moisture and CO2 absorb a small fraction too.8,9
application areas, surface engineering through a novel coating In addition, composite coatings, with combination mecha-
can give an economically viable option than developing bulk nisms, have been researched in order to achieve higher heat
thermal insulating materials. Thermal insulating coatings sealing.1,10,11 However, such coatings have not been exten-
(TICs) are coatings that can prevent heat transfer. They can sively researched extensively. In many reported works,
be categorized as a barrier, reflecting, radiative, or composite attempts have been made to achieve thermal insulation by
based on how they work.1,2 Barrier thermal insulation coatings maximizing solar reflectivity, such as by using additives such as
prevent heat conduction by using fillers or resins with low BaSO4 up to very high 60 wt % in an acrylic coating.12 Even
thermal conductivity. Fillers such as asbestos fibers, expanded
perlite, sepiolite, closed-cell perlite, and diatomaceous earth Received: August 8, 2023
have been used for such purposes.3−5 Reflective thermal Revised: October 7, 2023
insulation coatings are designed to reflect solar radiation, Accepted: October 9, 2023
specifically visible and near-infrared radiation. They use fillers Published: October 24, 2023
with high reflectivity in the 400−2500 nm band of the solar
spectrum.6,7 On the other hand, radiative thermal insulating

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after using a very thick coating of up to 400 μm and achieving a distribution in the coating and inherent thermal conductivity
solar reflectance of roughly 98.1%, a moderate temperature is important.
reduction of 4.5 °C has been reported.12 In a similar attempt The majority of the reported work used coatings with a
using 700 μm thick coating with 95 wt % BaSO4 and achieving thickness greater than 200 μm. Thicker coatings demand
a solar reflectance of 98.6%, the temperature reduction higher material consumption per unit surface, thereby
reported was 2.5 °C.13 These reports did not discuss the increasing the cost. In the case of thicker coatings maintaining
results through a reduction in the thermal conductivity and an good adhesion to the metal’s surface (increasing the demand
increase in the interfacial thermal resistance through for the specific surface preparation), monitoring undercoating
optimizing the coating composition. As a result, it appears corrosion and substrate degradation will be a challenge.
that high solar reflectance and thicker coatings can give a Therefore, thin coatings with better thermal insulation and
moderate temperature drop (less than 5 °C) across the coated anticorrosion qualities would be more desirable, and their
surface. Similar other reports exist such as using solid fillers demand will increase over time, emphasizing systematic
PVDF and Al2O314 and dual reflecting pigments Y2O3 and research focus on “thin thermal shielding coatings”, which is
TiO215 where thicker coatings 500 and 150 μm have been the focus of this report. In these coatings, multiple mechanisms
used, respectively. On the other hand, the use of hollow of thermal shielding must operate optimally, necessitating
particles such as Sb-doped SnO2 microspheres in the cast film attention to the selection of particles (fillers), composition, and
(millimeter thick films), higher particle loading, and a higher- coating microstructure.
temperature drop of 12 °C has been reported with a solar In addition to thermal shielding, coatings need to have
reflectivity of just 48.3%.16 Transparency in the visible and strong barrier performance for long-term protection. Compo-
NIR spectra was shown to decrease with increasing the film site coatings are therefore a good choice for enhanced barrier
thickness, which may have reduced the temperature drop.16 performance by creating a highly tortuous diffusion path for
A coating system with TiO2-coated light hollow polymer the penetration of the water and other corrodent species.22
microspheres and rutile TiO2 of 500 μm thickness was Here, we have demonstrated that by a suitable surface
reported to show a temperature decrease of roughly 5.8 °C, modification of the fillers the coatings can be made
whereas the thermal conductivity of 0.1687 W·m−1·K−1 and hydrophobic. The imparted hydrophobicity can act as a
reflectivity of ∼87% were reported.17 Despite having low primary corrosion protection method, as the coating will
thermal conductivity and reasonably high solar reflectivity, the prevent water wetting. When combined with the composite
achieved low-temperature drop was comparable to those effect of all fillers in the coatings, it will enhance the overall
achieved in the case of solid particles in the coating,12−15 corrosion protection performance of the coating.23
obscuring the benefit of using hollow particles. There has been The goal of this study was to develop a “thin” hydrophobic
an effort to use thick coatings (400 μm) with multiple low thermal insulation composite coating for metallic surfaces with
conducting particles such as diatomite, hollow glass bead, an industrially acceptable 65 (±5) μm dry film thickness
ATO, mica, and TiO2, which provided a temperature drop of (DFT) and superior corrosion resistance. Modified hollow
16.4 °C when applied on an aluminum panel.18 However, how microsphere (HMS) and nanometal oxide (MO) particles
the incorporated multiple fillers help in achieving thermal were coupled with epoxy resin to offer a “thin coating” system
insulation was not discussed with the help of a change in with high thermal shielding indicated by the highest reported
thermal conductivity or solar reflection property of the thick temperature drop (21 °C) across a coated metal panel. The
coating. Bao et al. produced a hollow SiO2 sphere deposited dual mechanism of high reflectivity and low thermal
with TiO2 with a hierarchical flower-like structure and conductivity operating in the coating is responsible for this
incorporated in polyacrylate.19 The developed coating’s superior performance at only 65 (±5) μm thickness, which is
thermal insulation characteristics were studied at a thickness about 95% thinner than the reported coatings. Additionally, its
of 200 μm with a filler loading of 5 wt %, which offered an IR low surface energy combined with the composite effect
reflectance of ∼55% and a thermal conductivity of ∼0.16 W· provides excellent long-term corrosion protection. To the
m−1·K−1. The temperature drop reported for the thick coating best of our knowledge, such multifunctional high thermal
was only 10 °C. In all of these reports, the specific heat shielding thin coatings have been reported here for the first
capacity of the coatings was not measured, and the reason for time. The report embodies a discussion on the plausible
the lower-temperature drop with respect to important factors, mechanism of the origin of the high-temperature difference in
such as change in interfacial thermal resistance, particle the thin composite coating applied on a steel surface.
distribution in the matrix, crystallinity of the composite
coating system, etc., was not discussed. Chen et al. created a 2. METHODS
thermal insulation coating by combining an epoxy-modified 2.1. Materials. The epoxy resin and hardener used in this study
acrylic resin with a zinc phosphate-modified hollow glass were obtained from Jotun India Pvt Ltd. (Mumbai, India). The epoxy
microsphere.20 The thermal insulation performance of the 2.5 resin was composed of diglycidyl ether of bisphenol A with an epoxy
mm thick coating on a tin plate reported a temperature equivalent of 183−189 g/eq and a density of 1.17 g/cm3. Aliphatic
difference of 38.4 °C and a thermal conductivity of 0.157 W· amines were used as a curing agent. The mass ratio (v/v) of epoxy
m−1·K−1 (thermal conductivity of bare epoxy ∼0.2 W·m−1· resin (UN 3082) and curing agent (UN 2735) was 2:1. The hollow
K−121). In this study, the solar reflectance characteristics were microsphere (HMS) employed in the study had a particle size of 10−
100 μm and a spherical form and was obtained from Kulin
not studied; the focus was on developing a coating having low Corporation (Nagpur, India). Merck Specialties Private Limited
thermal conductivity and using a thick coating. Comparing the (Mumbai, India) provided Degussa P25 TiO2 nanoparticles (MO),
temperature drop in this report with the previous stud- tetra ethyl orthosilicate (TEOS), ammonia solution (25%), stearic
ies12−15,19 indicates that the use of hollow spheres does not acid (SA), and sodium hydroxide (NaOH). The solvents xylene and
always give a higher-temperature drop; probably, their butanol were employed to lower the viscosity of the resin and

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Figure 1. (a) Schematic design of the model thermally insulated wooden enclosure (10 mm thick wall) used to measure the thermal shielding effect
of different composite coatings on mild steel. In the model, the steel sheet with different coatings covers one 6 × 3 in. opening in the roof. The
placement of the thermal sensors is indicated in the figure such as A, B, L1, and L2. The temperature data were collected from the L1 and L2
locations for analysis. L1 sensor is located behind the back surface (uncoated) of the front-coated steel panel and inside the wooden enclosure. “C”
is the insulated collimating tube to direct the radiation on the coated metal panel. (b) Photograph of the experimental setup.

facilitate processing. Mild steel (MS) panels served as the substrates resin, along with xylene and butanol, and homogenized for about 30
for the coatings. min in a high shear Ultra Turrax T18 homogenizer (at 3000 rpm).
2.2. NaOH Activation and Silica Modification of HMS. The The hardener was then added to the mix in the recommended ratio
HMS was activated using NaOH as follows. A 5 g portion of HMS (2:1 v/v) and stirred for around 20 min in the magnetic stirrer at 700
washed in water and ethanol in sequence was added to 50 mL of 0.5 rpm. The coating was then allowed to settle for the elimination of air
M NaOH solution and stirred at 500 rpm in a magnetic stirrer at 50 bubbles before being sprayed onto the mild steel substrate. In the case
°C for around 90 min. The mixture was allowed to cool before being of aHMS-MO systems, the desired weighted amount of MO (TiO2
filtered through a Whatman filter paper. It is washed multiple times nanoparticle) (10 wt % w.r.t. epoxy) was mixed with a hardener in an
with DI water and dried in an oven at 105 °C for 3 h. The resulting ultrasonicator for 1 h before being added to the aHMS−resin mixture.
activated HMS is denoted as aHMS. The silica-modified aHMS was The aHMS and MO powders were substituted with sHMS and sMO
produced by using tetra ethyl orthosilicate (TEOS) as a precursor. powders to develop the sHMS−sMO coating system. Before coatings
Two grams of aHMS were dispersed in an ultrasonicator for 1 h in a were applied, mild steel (MS) panels with dimensions of 152 × 76 × 1
mixture of 160 mL ethanol, 40 mL DI water, and 5 mL NH4OH mm3 were polished with silicon carbide paper (emery paper) ranging
solution. Then, 4 mL of TEOS was added dropwise to the from 100 grit to 600 grit to eliminate rust and other contaminants
aforementioned mixture and stirred with a magnetic stirrer. After 6 from the surface. After that, the panels were cleaned by being rinsed
h of stirring, the product was filtered through Whatman filter paper with acetone. The coatings with a dry film thickness (DFT) of 65 ± 5
(grade 42) and washed multiple times with ethanol and DI water. It μm were prepared. The process flow of the preparation of the coating
was then dried in an oven at 60 °C for 8 h. The resulting material is is depicted in Figure S1.
denoted sHMS. 2.5. Characterization Techniques. For the characterization of
2.3. Stearic Acid Modification of MO. Two grams of TiO2 HMS and MO before and after surface modification, Fourier
nanoparticles (particle size 21 nm) were added to 40 mL of ethanol transform infrared spectroscopy (FTIR) was used. FTIR experiments
and agitated for 15 min with a magnetic stirrer before being were carried out using a PerkinElmer Spectrum GXA FTIR
ultrasonicated for 30 min. One g of stearic acid was added to the spectrometer with a wavenumber range of 4000−400 cm−1. The
aforesaid mixture and magnetically stirred for 15 min, ultrasonically crystalline phases of the HMS and MO were studied using an X’pert
dispersed for 30 min, and then agitated for 2.5 h at 70 °C in a Pro PANalytical diffractometer (Syn Master793s) with copper (Cu)
magnetic stirrer. After allowing the mixed solution to stand for radiation (λ = 1.5406) at 30 mA and 40 kV. The continuous scanning
stratification, the supernatant was collected and dried in an oven at 80 was performed at a scanning speed of 10° min−1 with a scan range of
°C for 8 h. The resulting solids were ground to powder and 5−80°. The FE-scanning electron microscope was used to examine
designated as sMO. the surface morphology of the aHMS and sHMS (JEOL JSM-7600F,
2.4. Preparation of Epoxy Composite Coating. The following Japan). To avoid the charging effect caused by the nonconductive
process was used to prepare the composite coatings. First, a weighed nature of HMS, the sample was sputter-coated with gold. MO and
amount (15 wt % w.r.t. epoxy) of aHMS was added to the epoxy sMO were observed under high-resolution transmission electron

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Figure 2. XRD of (a) HMS before and after silica modification (inset shows a peak corresponding to the (120) plane) and (b) MO before and after
stearic acid modification (inset shows stearic acid peaks).

microscopy (HR-TEM) conditions to evaluate their structure, particle the coated panel was represented as an effective temperature drop and
size, and diffraction pattern before and after modification using an FEI is determined using eq 2
Tecnai G2, F30 HR-TEM (US) at 300 kV. The degree of dispersion
o Tin Tout |
l o
of aHMS and sHMS filler in the coating system was confirmed using a percentage temperature decrease = 100 × o
m
o T
o
}
o
confocal laser scanning microscope (IX 81 FV-500 Olympus, Tokyo, o
n in
o
~ (2)
Japan) by applying the coating system over a mild steel sample. The
images were captured at a 10× magnification and analyzed with the where Tin is the input temperature (surface temperature), and Tout is
help of ImageJ software. the temperature measured by the thermal sensor. The thermal
The hydrophobic properties of the coating samples were assessed conductivity and specific heat capacity of the coating samples were
by measuring the contact angle at room temperature with a Digidrop measured using a laser flash apparatus (Netzsch LFA 467 HT
GBX Goniometer. The contact angle was calculated by using the HyperFlash, Germany). In this method, a light pulse is used to heat
average of five measurements performed at various positions on the the front surface of a coating sample (freestanding film), and the
surface of the coating samples. A total of 5 μL of water was gently temperature increase at the rear face of the sample is measured as a
dropped onto the surfaces of the coating samples. The surface energy function of time. Pyroceram 9606 was used as the reference standard
was calculated using Neumann’s equation of state theory eq 1, which material for the thermal conductivity measurement. In addition, an
links the contact angle and solid surface energy24,25 integrating sphere-equipped ultraviolet/visible/near-infrared (UV/
vis/NIR) spectrophotometer (PerkinElmer Lambda 950, Waltham,
s ( 2 MA) was used to measure the spectral reflectance of the various
cos = 1+2 e l s)
coatings. BaSO4 plates were used as the reference standard reflectance
l (1) material.
2.7. Corrosion Performance by Electrochemical Impedance
where γl is the liquid surface energy and is 72.8 mN/m for water, γs is Spectroscopy (EIS). The corrosion performance of the coating was
the solid surface energy, θ is the contact angle and the constant, and β studied by using electrochemical impedance spectroscopy (EIS). EIS
is taken as 0.0001234 (mJ/m2)−2 for a variety of solid surfaces.25 tests were executed by using a potentiostat and an electrochemical
2.6. Study of the Thermal Insulation Effect of Coating. Using cell. The electrochemical cell was a three-electrode system in which
a model thermally insulated wooden enclosure,17,19 with a 10 mm wall the coated panel with a 1 cm2-exposed area was the working electrode,
thickness, the thermal shielding effect of the coating was investigated. the saturated calomel electrode (SCE) was the reference electrode,
It was ensured that the only channel of heat into the enclosure was and the platinum wire mesh was the counter electrode. A 3.5 wt %
from the coated metal panel and not from the surroundings. The test NaCl solution was used as the electrolyte. The potentiostat PGSTAT
panels of dimensions of 6 × 3 in were placed at the sloping roof of the 30 Autolab (Metrohm) with Nova FRA software was used for EIS
model as indicated in Figure 1. The purpose of this coating was to measurement. The frequency range used for EIS measurement was
reflect and/or shield the thermal radiation, especially the IR radiation 100 kHz to 10 mHz with an amplitude of 10 mV. All measurements
from the sun. Therefore, an infrared (IR) heat lamp with a 150 W were taken at room temperature. The EIS on the coatings was
power rating was used to simulate the heat radiation source. The IR performed periodically (every 24 h) until 720 h, and the data were
lamp was placed 30 cm away from the coated test panel, which analyzed using the built-in Nova FRA software. The protection
generated an external temperature of 60 °C on the exposed surface of efficiency (PE) of the coatings was calculated.
the panel, which is the typical surface temperature on a hot tropical
summer day. The measurement of the temperature outside and inside 3. RESULTS AND DISCUSSION
the model enclosure was carried out at various locations using thermal
sensors, as shown in Figure 1. The thermal sensors (ESD sleek 100) 3.1. Characterization. X-ray diffraction was utilized to
used were with an accuracy of ±0.25% of full scale ±1 digit. Four determine the crystalline phases of the modified (sHMS) and
thermal sensors were placed at the exposed surface of the panel (at activated (aHMS) HMS, as well as the modified (sMO) and
the top, A, to measure the incident temperature at the exposed unmodified MOs (Figure 2a,b). Figure 2a shows that HMS,
surface), and one at the bottom, inside the model enclosure (L1), to aHMS, and sHMS are predominantly composed of the
measure the temperature at the bottom surface of the coated panel. crystalline phases quartz and mullite (JCPDS 46−1045 &
Other sensors were placed at five (B) and at 15 cm below the coated JCPDS 15−0776). Because the 22° silica peak was already
metal panel (L2) inside the model enclosure to measure the distance
effect on the temperature drop. At regular intervals of 30 min, the present in aHMS, adding silica to sHMS did not result in the
temperatures were recorded at the locations L1 and L2, and the appearance of a new XRD peak. However, the intensity of the
apparent temperature, percentage temperature difference, and peak was slightly increased by approximately 21% (inset,
effective temperature decrease were measured for various coatings Figure 2a). The XRD spectra of MO and sMO confirmed that
on the steel panel. The temperature difference between bare steel and MO had been modified by stearic acid (Figure 2b). The peaks
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Figure 3. FE-SEM images of aHMS (a−c) and sHMS (d−f). A broken sHMS shows the varying shell wall thicknesses (f).

at 22 and 24° (JCPDS 38−1923) are the characteristic of in Figure 4c,g. The SAED pattern for sMO was more diffused
stearic acid (Figure 2b, inset). The remaining sMO peaks are than MO due to the long carbon chain of the stearic acid in the
consistent with the TiO2 XRD spectra (JCPDS 88−1175 and former. SAED pattern affirms the results obtained from XRD,
84−1286). The rutile phase refers to the peaks at 27.3, 35.8, with additional peaks arising from the stearic acid in sMO.
and 41.1°, while the anatase phase matches up to the Using ImageJ software, the average size and size distribution
remaining peaks. of the MO nanoparticles were determined from TEM
Field emission scanning electron microscopy (FE-SEM) micrographs (Figure S3). Before SA modification, the average
analysis was used to assess the surface morphology and particle size of MO was around 21 ± 2 nm. The formation of
modification of the HMS used in the coating. Figure 3 shows an outer sheath layer in sMO corroborated the stearic acid
the FE-SEM images of the aHMS particle before and after modification of MO (Figure 4e) through the scheme shown in
silica treatment. The hollow microspheres in the aHMS and Figure S4. The typical thickness of the sheath of the stearic
sHMS particles have an average particle size of about 30 ± 5 acid outer layer in sMO varied between 2 and 4 nm. In sMO,
μm. Figure 3 depicts pores on the aHMS particle surface. Pores the average particle size increased to 23.8 ± 2 nm due to the
can also be seen across the thickness of the HMS shell, as presence of the SA sheath.
shown in Figure 3f. The surface of sHMS became even rougher The surface modification of HMS and MO particles and
after silica modification (Figure 3e), and the pores on the their interaction with resin and hardener were examined using
surface of the aHMS particle were covered by silica particle Fourier transform infrared FTIR spectroscopy. Figure 5 shows
deposition (Figure 3e, inset). From a broken HMS micro- the FTIR spectra of HMS (modified and unmodified) and MO
graph, Figure 3f, the shell thickness was found to not be (modified and unmodified). FTIR spectra for HMS, aHMS,
uniform. The average shell thickness was measured to be 6.65 and sHMS (Figure 5a) revealed an increase in the peak at 3440
± 2.3 μm. The surface and cross-sectional morphology of the cm−1 associated with the stretching vibration mode of the
coating were also analyzed using FE-SEM (Figure S2). The hydroxyl group (−OH) in aHMS and sHMS. The NaOH
surface micrographs are typical of the polymer-coated surfaces activation of HMS is what triggers this increase in aHMS. The
(Figure S2a,c) with variable roughness. From the cross- −OH stretching peak in sHMS has increased further following
sectional SEM (Figure S2b,d), the uniform distribution of the the silica modification because of the presence of adsorbed
HMS particles across the thickness of aHMS-MO and sHMS− water on silica, as shown in Figure 5a. The symmetric and
sMO coatings is revealed. Due to its very small size, MO asymmetric T−O (T = Al, Si) stretching vibrations, both of
particles are not visible in the SEM. This indicates the which have increased in the aHMS and sHMS, correspond to
consistency of the coating preparation method to prepare a the two major bands in the HMS particles. These two bands,
well-dispersed coating. which appear at 1081 and 457 cm−1, respectively, indicate
HR-TEM was used to examine the surface morphologies of typical bending vibrations and symmetric stretching vibrations
MO and sMO. Figure 4 depicts TEM micrographs and of Si−O−Si bonds. Because of the presence of alumina and
selected area electron diffraction (SAED) patterns. According silicate components in HMS, the peak at 511 cm−1 was
to the HR-TEM pictures and SAED patterns, the MO particle attributed to the Si−O−Al stretching. Due to the extra −Si−O
was polycrystalline and had a quasi-spherical morphology. bond of the silica present in HMS following the alteration, the
Figure 4 depicts typical high-resolution TEM images of MO intensity of the peak at 1081 cm−1 increases higher in sHMS
particles. The lattice fringes with a d-spacing of 0.374 nm than in aHMS. The FTIR spectrum of epoxy, epoxy−aHMS,
correspond to the (101) plane of the anatase phase along with and epoxy−sHMS is shown in Figure 5b. In epoxy resin, peaks
other planes and are observed by the SAED pattern displayed between 3100 and 2800 cm−1 correspond to the −C−H−
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Figure 4. TEM micrographs of MO (a), sMO (d), and HR-TEM of MO (b) and sMO (e, f) along with the corresponding SAED pattern (c, g),
respectively. The stearic acid sheath around sMO is visible and marked in panel (e).

stretching peaks associated with the epoxide group (3084 hydroxyl groups on the surface of the HMS are more likely to
cm−1), aromatic ring (3050 cm−1), asymmetrical stretch in form hydrogen bonds with the oxygen in epoxy resin.26 This
−CH3 (2966 cm−1), and asymmetrical stretch in −CH2 (2871 improves the interaction between epoxy and HMS and helps in
cm−1). The peaks at 1614 and 1512 cm−1 correspond to the the uniform dispersion of the filler on the matrix.
C−C stretching vibration in the aromatic ring. Asymmetrical FTIR spectrum of MO and sMO is shown in Figure 5c; the
aromatic C−O stretch, asymmetrical aliphatic C−O stretch, peak centered at 3410 and 1610 cm−1 corresponds to the
and symmetrical aromatic C−O stretch were indicated in hydroxyl group (−OH) stretching and bending vibration,
peaks at 1244, 1175, and 1033 cm−1, respectively. The epoxide respectively, which confirms the presence of adsorbed water.27
ring vibrations were shown between 984 and 790 cm−1. The After the MO was modified with stearic acid (SA), both peaks
peak at 578 cm−1 corresponds to the characteristic peaks of the decreased drastically. After the modification, the stearic acid
C6H4 para vibration of the aromatic ring. The peak between replaced the adsorbed water and became bonded to the MO
3640 and 3350 cm−1 corresponds to the −OH stretching. The surface by producing a covering layer. In sMO, peaks at 2910,
additional peaks at 1061 and 522 cm−1 in epoxy−aHMS and 2840, and 1440 cm−1 correspond to the SA’s C−H stretching
epoxy−sHMS correspond to the Si−O−Si symmetric stretch- vibrations and −C�O stretching vibration, respectively. This
ing and Si−O−Al stretching of HMS, respectively. Epoxy resin demonstrates that stearic acid successfully modified the MO.
is somewhat polar because it has two epoxide groups at either The −M−O− stretching and −M−O−M− bridging vibrations
end and two ether groups in the middle. Due to this, any free are represented by the broad peak centered at 615 cm−1.
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Figure 5. FTIR spectrum of (a) HMS before and after modification, (b) epoxy and modified HMS, and (c) MO before and after SA modification.

Figure 6. Confocal laser scanning micrographs of (a) aHMS, (b) aHMS−MO, (c) aHMS−sMO, (d) sHMS, and (e) sHMS−sMO coating systems.

Figure 6 depicts confocal laser scanning microscope images particles (aHMS and sHMS) are uniformly distributed
of the composite coating system. In the CLSM images, the throughout the coating. The visibility of the HMS particle
HMS particles are depicted as black dots. Figure 6 indicates was reduced when the MO particles were added to the coating,
that no HMS agglomerates were formed and that the HMS as seen in Figure 6b,c,e. This shows that throughout the
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Table 1. Contact Angle and Surface Energy of the Coating Systems

Figure 7. Time vs effective temperature decrease of the coating (a) at the bottom surface of the coated panel and (b) at 15 cm below the coated
panel inside the model insulated enclosure (L2). (c) Percentage temperature decrease in various coatings after 180 min of exposure.

coating, the HMS particles were surrounded by a uniform HMS particle, they disguise their appearance, as seen in Figure
distribution of MO particles. The CLSM pictures do not 6b,c,e. The CLSM results also show that the silica-modified
highlight the MO particles since they have a smaller particle HMS and SA-modified MO disperse fillers better than
size (∼21 nm) and do not exhibit fluorescence activity. activated HMS- and SA-modified MOs, as well as any
Furthermore, because they are evenly dispersed and cover the combination of them. It is evident from this that the mixing
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Figure 8. (a) Thermal conductivity of composite coatings, (b) specific heat capacity of composite coatings, and (c) UV−vis−NIR reflectance plot
of composite coatings.

processes involved in the coating preparation stage are efficient evaluated by exposing the coated panel to an infrared (IR)
enough to produce a properly dispersed coating system, as light source using the model setup shown in Figure 1. The
dispersion is critical in the final performance properties of the apparent temperature, effective temperature decrease, and
coatings. percentage temperature decrease were measured below the
The hydrophobic properties of the coating were investigated coated panel (L1, inside the box model) and 15 cm below the
by measuring the contact angle of a water drop on the coating coated surface (L2) by using thermal sensors (Figure 1), and
surface. The contact angle and surface energy values for the the findings are shown in Figure 7. At both locations within the
prepared coatings were recorded and are shown in Table 1. model enclosure, the apparent temperature of uncoated and
The presence of aHMS and MO in the coating system reduced epoxy-coated steel increases steadily as exposure time has
the contact angle of bare epoxy from 79.76 to 75.34° and passed. During the exposure, the temperature of uncoated steel
increased the surface energy to 34.31 mN/m from 31.24 mN/ approached the input temperature, which was approximately
m. Because aHMS and MO are both naturally hydrophilic, 60 °C. At L1 and L2 locations, only a 23 and 35% drop in
their presence renders the coating hydrophilic and results in a temperature was observed for the uncoated and neat epoxy-
decrease in the contact angle of the coating. When sMO was coated steel, respectively. In the case of composite coatings, the
used as a filler, the contact angle went up to 94.5°. This was use of various fillers enhanced thermal protection to varying
caused by the stearic acid modification of MO, where the OH degrees. In the case of the aHMS−MO-coated panel, the
group in MO interacts with the COOH group in SA, making bottom surface of the coated panel (L1) showed a 14 °C
the outer surface of MO consist of long hydrocarbon chains of decrease in apparent temperature compared to the uncoated
SA (as shown in Figure S4). So, the coating was hydrophobic steel (i.e., a 20 °C decrease from the input temperature and a
because of the hydrophobic sMO. The contact angle of the 33% temperature difference). In the case of the sHMS−sMO-
coating was increased to 96.4° when sHMS was used instead of coated panel, the apparent temperature at L1 was around 15
aHMS in conjunction with sMO. The silica coating on sHMS °C lower than that of uncoated steel (i.e., a 21 °C decrease
increases the surface roughness (Figure 3e) and thus the from the input temperature and a 35% temperature difference).
hydrophobicity of the coating.28 Surface energies for epoxy However, at 15 cm below the coated panels, i.e., at L2, the
composite coatings with mixed fillers such as aHMS−sMO and apparent temperature for the aHMS−MO, aHMS−sMO, and
sHMS−sMO were 21.44 and 20.12 mN/m, respectively, which sHMS−sMO systems decreased to approximately 17 °C with
are within the range for conventional epoxy coatings respect to the uncoated steel (i.e., a 31 °C decrease from the
containing an SA-modified filler.29,30 input temperature), which represents a 51% decrease in
3.2. Thermal Insulation Performance of the Coating. temperature after 180 min of exposure. These results
The thermal shielding performance of the coatings was demonstrated that using the composite coatings (aHMS−
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Figure 9. Schematic of the thermal insulation mechanism and thermal conduction through the composite coating (a), schematic of heat dissipation
through MO and sMO (b). The reduced boldness of the arrow is indicative of the reduced magnitude.

MO, aHMS−sMO, and sHMS−sMO), the apparent temper- seen in Figure 4e) reduces the thermal conductivity of the
ature inside the model enclosure can be maintained at a very sMO particle because of the low thermal conductivity of SA
low level for a longer period, resulting in an effective (0.29 W·m−1·K−1).32 The thermal conductivity of the
temperature decrease of approximately 15−17 °C (Figure composite coating systems (aHMS−sMO and sHMS−sMO)
7a,b). In addition, as shown in Figure S5a,b, there is a was lower than that of the bare epoxy coating system. This
negligible change in apparent temperature with exposure demonstrates that the surface modification of the MO using
duration, demonstrating that these composite coatings have an SA can lower the thermal conductivity of the MO, which in
efficient thermal shielding function to keep a constant turn helps achieve coatings with lower thermal conductivity.
temperature inside the model enclosure. This demonstrates The lower thermal conductivity and higher cp value of the
the superior thermal shielding effect of the used coatings. composite coatings indicate that they have excellent thermal
Figure 7c depicts the percentage temperature reduction after insulation and heat storage capability.
180 min determined using eq 2. The specific heat capacity (cp) of all of the composite
The thermal conductivity and specific heat capacity of the coatings was found to be higher than that of the bare epoxy
various coatings were measured at room temperature and are coatings, as shown in Figure 8b. The specific heat capacity (cp)
presented in Figure 8a,b. From Figure 8a, the thermal of a material is the quantity of heat that must be supplied to
conductivity of the bare epoxy was 0.210 W·m−1·K−1, which the unit mass of a substance to achieve a unit increase in
was decreased to 0.166 W·m−1·K−1 by adding only aHMS to temperature. So, the higher the cp, the higher the heat
the epoxy (aHMS coating system), which is about 0.044 W· requirement for increasing the temperature. From Figure 8b, it
m−1·K−1 less than that of the bare epoxy. This decrease is due is clear that all of the composite coatings have higher cp values
to the lower thermal conductivity of the aHMS filler. Addition than the bare epoxy, and the sHMS−sMO composite coating
of MO to the latter coating (aHMS-MO) increased the system has the highest cp. This means for the same thickness of
conductivity to 0.216 W·m−1·K−1. The increase in the thermal the coating, sHMS−sMO composite coatings can absorb more
conductivity of the coatings was due to the higher thermal heat compared to other systems. Therefore, the developed
conductivity (4−11.8 W·m−1·K−1) of MO.31 However, the sHMS−sMO composite coating system provides excellent
addition of sMO showed a significant effect on the thermal thermal insulation due to its lower thermal conductivity and
conductivity of the coating. For the composite coating systems high cp value. The result corroborates the temperature drop
aHMS−sMO and sHMS−sMO, the thermal conductivity was results in Figure 7a,b.
0.178 and 0.181 W·m−1·K−1, respectively. From these values, The UV−vis−NIR spectrophotometry examination of the
stearic acid modification of the MO was effective in the coatings was also carried out to estimate the reflectance, as
reduction of the thermal conductivity of the coating. The presented in Figure 8c. The graph clearly shows that composite
presence of a stearic acid layer over the MO particle (as can be coatings have higher reflectance over the whole spectrum
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(300−2500 nm) than bare epoxy coatings. In the NIR range, low temperatures (∼60 °C), thermal radiation accounts for a
the bare epoxy coating has a reflectivity of around 37.03%, negligible proportion of the total heat transmission. As a result,
while in the VIS region, it has a reflectivity of about 37.92%. only the heat transport through the conduction will be
The presence of the reflective MO particle in the composite relevant, which is principally dependent on the material’s
coating boosts the coating’s reflectivity. The average thermal conductivity. Due to the HMS filler’s lower thermal
reflectance of the aHMS−MO, aHMS−sMO, and sHMS− conductivity, the thermal conductivity of the composite
sMO coatings in the NIR (700−2500 nm) region is coating is lesser than that of bare epoxy (Figure 8a), providing
approximately 72.72, 63.08, and 67.33%, respectively, and in better thermal insulation. The schematic of heat transfer
the vis (400−700 nm) region, the reflectance is approximately through the aHMS coating system is represented in Figure
90.12, 79.12, and 84.18%, respectively. This shows that S6b.
composite coatings had very good solar reflectance. The In addition to increasing reflectivity, the addition of MO,
aHMS−MO system has the highest reflectivity among the and especially sMO, to the composite coating also increases
composite coating systems. The stearic acid modification of the interfacial thermal resistance between the MO and resin.
the sMO particles influenced its intrinsic reflectivity and was Therefore, even though the thermal conductivity of MO was at
responsible for the modest decrease in the reflectivity of sMO- least 20 times higher than epoxy, the increase in the thermal
containing coatings compared to those containing MO conductivity in the aHMS−MO coating system was at par with
nanoparticles. Long carbon chains and polymers absorb the bare epoxy coating (Figure 8a). The interfacial thermal
infrared light, particularly those with aromatic rings, as found resistance also developed between HMS and resin.40 Due to
in sMO.33,34 Since IR is the heat-carrying radiation of the solar the difference in the thermal conductivities of epoxy and HMS
spectrum, the higher the reflectivity of the coatings in the IR (and MO), and anharmonicity in vibration normal modes, the
region, the lower the absorption and hence the better the phonon scattering would occur across the two-phase interfaces,
thermal insulation observed. which give rise to the interfacial thermal resistance in the
Thus, the observed high thermal insulation effect in the composite coating systems.41,42 In addition to this, the uniform
studied epoxy nanocomposite coatings was due to the dispersion of aHMS and (s)MO in the epoxy matrix (as seen
synergistic effect of the HMS and MO particles. The schematic in Figures 6 and S2b,d) also contributed to the increased
of the mechanism of thermal insulation in each coating system thermal contact resistance uniformly across these coatings. The
is depicted in Figures 9 and S6. Thermal insulation achieved in dispersion of fillers in the matrix isolated particles of the aHMS
these coating systems was due to a dual mechanism integrated and MO, which were now surrounded by low conducting
into the coating system: the mechanism of formation of a polymer chains, results in lower thermal conduction in the case
thermal conduction barrier by the lowering of the thermal of the composite coatings.36,37,43 The dispersion of HMS and
conductivity and high reflection of solar radiation (Figure 9a). MO particles also prevents the formation of a continuous heat
When solar radiation struck the coating surface, the majority of conduction path between fillers, which decreases heat
the IR component of the radiation was reflected due to the conduction. Besides, in all of these coating systems, the
presence of reflective MO nanoparticles. The NIR reflectance interaction between the fillers and matrix was mainly the
value of the TiO2 was approximately 85%,35 while that secondary interactions such as van der Waal forces and
measured in the coatings was approximately 72% (Figure 9c). hydrogen bonding (as discussed in the FTIR section (Figure
The absorbed portion of the radiation was diffused in the 5b)), which further decreased the thermal conduction.36,37,43
coating owing to the low thermal conductivity of resin, HMS, The schematic of the mechanism of heat conduction through
and stearic acid-modified MO, and the high cp of the aHMS−MO and sHMS−sMO systems, with all of the
composite coatings, which subsequently restricted the heat aforementioned effects, is shown in Figure 9a,b.
transmittance through the coating. Although the majority of The thermal conductivity of coating using sMO fillers is
the solar spectrum was absorbed in the UV−vis−NIR much lower than that of MO (Figure 8a) due to the decrease
reflectance spectra of bare epoxy (Figure 9c), they exhibit in the inherent thermal conductivity of sMO and the existence
thermal insulation efficiency superior to that of bare steel of interfacial thermal resistance. Due to the SA sheath, the
(Figure 7). This is due to the epoxy resin’s low thermal difference in thermal conductivity at sMO−epoxy interface was
conductivity, which is typically around 0.210 W·m−1·K−1. reduced. However, the contribution of the decrease in the
Usually, the thermal conductivity in polymers is low due to inherent thermal conductivity of sMO on the overall coating
amorphous and disordered structures, which is corroborated conductivity was more dominant than the decrease in the
by the low degree of crystallinity index (CI) of ∼38% in the interfacial thermal resistance sMO−epoxy interface.37 Hence,
case of the bare epoxy coating system (Figure S7). The ultimately, incorporating sMO fillers into the coating resulted
anharmonic vibrations and internal flaws in crystal lattices in a lowering of thermal conductivity with higher heat
along with the amorphousness produce phonon scattering,36,37 deflection at the sMO−epoxy interface, Figure 9b. When
which results in lowered thermal conductivity. The schematic heat radiation reaches MO, some gets scattered and most of
of the heat transport through the epoxy matrix is depicted in them pass through it, whereas when heat radiation reaches
Figure S6a. sMO, most of the radiation is blocked/scattered and very few
The HMS fillers have lower thermal conductivity (0.08−0.2 only go through it. From several works and Cheiw and Glandt
W·m−1·K−1) due to the presence of air in their hollow structure model analysis, it was found that the chemical functionalization
and, hence, function as a barrier for heat transfer through the and the size distribution of hollow spheres do not seem to
coating in the case of composite coating.38 Heat transport in a appreciably impact the thermal conductivity of the compo-
medium occurs primarily through three mechanisms: con- sites.42,44 That is why the aHMS−sMO and sHMS−sMO
duction, radiation, and convection. Natural thermal convection coating systems showed negligible differences in thermal
via the gas inside hollow fillers is not feasible if their diameter conductivity. Also, the higher specific heat capacity of the
is less than 4 mm.39 Furthermore, since we are dealing with composite coatings indicates that they need more heat to
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Table 2. Comparison of Different Thermal Insulation Coating Systems

coating
coating system filler thickness temperature decrease (°C) refs
poly(vinylidene closed pore perlite, hollow glass microsphere, nano-ATO 0.5 mm 6.7 °C for ATO, 5.2 °C for hollow glass 4
fluoride) powder microsphere, 4.2 °C for perlite
waterborne Sb-doped SnO2 microspheres mm thick film 12 °C 16
polyurethane
silicon acrylic light hollow polymer microsphere (LHPM) with titanium 500 μm 5.8 °C 17
emulsion dioxide nanoparticles (nano-TiO2), TiO2
waterborne acrylic diatomite, hollow glass bead, ATO, mica, TiO2 0.4 mm 16.4 °C 18
emulsion
polyacrylate hollow SiO2 sphere deposited with TiO2 200 μm 10 °C 19
epoxy-modified zinc phosphate-modified hollow glass microspheres 2.5 mm 38.3 °C 20
acrylic resin
polystyrene hollow glass microsphere/BiOCl1−xIx 120 μm 8 °C 45
acrylic emulsion hollow glass microsphere, TiO2, silica, talcum, CaCO3, BaSO4, 300 μm, 3-layer 30.1 °C (measured at 30 cm away) 46
ferrotitanium powder coating
waterborne hollow glass microspheres, titanium dioxide, silicon dioxide, 290 μm, 3- layer 20.1 °C 47
polyurethane and aluminum oxide coating
fluorocarbon resin hollow glass microsphere, TiO2 NA 31.1 °C 48
emulsion
redispersible hollow silica nanosphere 0.5 mm 5 °C lower than bare coating 49
acrylic powder
epoxy resin sHMS and sMO 65 μm 21 °C at the bottom surface of the panel, 31 °C this
at 15 cm below the panel work

increase their temperature, i.e., the coating can store more heat and the decrease in the thermal conductivity of the coating are
when the temperature increases by 1 °C. The dual mechanism also related (Figure S9b). The latter is apparent as the addition
operating in the developed coating systems, i.e., the synergistic of fillers has generated additional interfaces, which increased
effect of the thermal barrier and reflecting effect, contributed to the electron scattering,41,42 and hence reduced the electronic
the high thermal insulation performance, presented in Figure 7. conductivity. The increased interface also increased the
The crystallinity of the matrix phase also impacts the thermal interfacial thermal resistance and hence decreased the thermal
conductivity. As crystallinity increases, so does the degree of conductivity. The increase in the equivalent series resistance
order, resulting in an increase in thermal conductivity.36 has a bearing on the improved barrier performance of
Therefore, the crystallinity index of the matrix phase was composite coatings, which is thoroughly addressed in the
measured. As shown in Table S1, though the overall succeeding section.
crystallinity of the composite coating systems has increased Table 2 lists a comparative account of the performance of
with the addition of fillers, the crystallinity of the epoxy matrix thermal insulation coatings similar to this work, which showed
decreased with the addition of fillers (Table S2 and Figure S8), the superiority of the sHMS−sMO coating system developed
which was inevitable in a composite and contributed to the low in this work when the performance at lower thickness is
thermal conduction. In any case, the effect of the overall concerned. The published works, as presented in Table 2,
increase in the crystallinity of the composite coatings was offset which show comparable or higher-temperature drop than the
by the use of thermal insulating fillers such as HMS in this developed sHMS−sMO system, are 4−8 times thicker or have
study and also due to the effect of factors such as surface multiple reflecting fillers in their formulation.20,45−47 Besides in
modification and increase in interfacial thermal resistance. some reported works (46 in Table 2), the temperature drop has
Figure S8 depicts the thermal conductivity versus crystallinity been measured at a larger distance from the coated surface
for the composite coating, and it can be seen that when (greater than 15 cm used in this work). This demonstrates that
crystallinity increases, there is an increase in thermal the developed sHMS−sMO system in the present work has
conductivity. The high conductivity in the aHMS−MO coating outstanding thermal insulation capability at a very low coating
was due to the conducting MO fillers with ∼20 times higher thickness (∼65 μm), i.e., at a low dry film thickness (DFT).
thermal conductivity than the HMS filler. However, when 3.3. Corrosion Protection Performance of Coatings.
modified MO, i.e., sMO, was used, the conductivity decreased The influence of HMS and MO fillers on the corrosion
with a low crystallinity index of the matrix,36 as in aHMS− protection performance of epoxy coatings at varying
sMO and sHMS−sMO (Figure S8b). The decrease in the immersion times in a 3.5 wt % NaCl solution was investigated
crystallinity of the matrix was further corroborated by the using EIS measurements. Figure S10 depicts the Nyquist plots
electrochemical impedance measurement. The equivalent of the various coating systems. Figure S10a shows that at the
series resistance (Rs), which has a significant contribution beginning of immersion (0 h), the impedance value of bare
from the electronic conductivity of the matrix phase, decreases epoxy was around 108 Ω·cm2 and that of composite coatings
with the addition of fillers. Figure S9a shows that as the was approximately 1010 Ω·cm2. Initially, only one time constant
crystallinity of the epoxy in the composite coating decreased, was detected; however, as the immersion time reaches 360 h,
the equivalent series resistance (obtained from the EIS the coatings exhibit two-time constants, which can be
analysis, discussed later) increased, indicating that the coating attributed to the electrolyte diffusion through the coating as
becomes increasingly electrically insulating, given that the the immersion time increased, i.e., the corrosion protection
electrolyte resistance and overall filler loadings remained efficacy of the coatings decreases. After 360 h of immersion
constant. The increase in equivalent series resistance (Rs) (Figure S10b) in the 3.5 wt % NaCl solution, the impedance
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Figure 10. (a) |Z|0.01 vs time of exposure of coating systems. (b) Protection efficiency vs time of exposure plot of coating systems when exposed to a
3.5 wt % NaCl solution.

value of epoxy was reduced to 106 Ω.cm2, but the impedance wt % NaCl solution. After 720 h of immersion, the initial
values of aHMS−MO, aHMS−sMO, and sHMS−sMO were 2 protection efficiency of the aHMS−sMO and sHMS−sMO has
× 109, 5 × 109, and 9 × 109 Ω·cm2, respectively. An increase in been enhanced to 99.94 and 99.99%, respectively. According to
immersion duration to 720 h (Figure S10c) resulted in a these findings, the corrosion resistance of the epoxy composite
further decline in the corrosion performance of the bare coating has enhanced greatly with aHMS−sMO and sHMS−
coating. For bare epoxy, aHMS−MO, aHMS−sMO, and sMO fillers. This is predominantly due to the presence of well-
epoxy−sHMS−sMO systems, the impedance values are 4 × distributed fillers on the coating matrix, which produced a
105, 8 × 108, 2 × 109, and 8 × 109 Ω·cm2, respectively, after tortuous and longer diffusion path for corrosive species.22,51
720 h. From the EIS analysis, the impedance value at low Especially, the sHMS−sMO coating provided the best
frequency, |Z|0.01Hz, of the coated samples was calculated and corrosion resistance, which was due to the hydrophobic
plotted against the time of exposure, as shown in Figure 10a. properties of the coating, as shown in Table 1. The
As the immersion duration increased, the barrier characteristic comparatively high hydrophobic character of the sHMS−
of the bare epoxy coating noticeably declined more than sMO (CA = 96.4°) coating system, compared to that of
composite coatings. For bare epoxy coating, the impedance aHMS−sMO (CA = 94.5°) and aHMS−MO (CA = 75.34°)
value decreased by around 3 orders of magnitude, i.e., from coating systems, prevented wetting of the coating surface with
1.08 × 108 to 4.41 × 105 Ω·cm2. The initial |Z|0.01 Hz values for the aqueous corrosive media and therefore delaying their
composite coating systems aHMS−MO, aHMS−sMO, and penetration into the coating layer. This increased the time for
sHMS−sMO were 1.62 × 1010, 3.22 × 1010, and 5.14 × 1010 corrosive species diffusion and hence the barrier characteristics
Ω·cm2, respectively, which were reduced to 3.17 × 108 Ω·cm2, of the coating. Figure S12 depicts the possible mechanism for
6.18 × 108 cm2, and 4.51 × 109 Ω·cm2 after 720 h of corrosion protection of the sHMS−sMO composite coating.
immersion. There was a 2-order decrease in the impedance The hills and valleys on the surface of the hydrophobic coating
value for aHMS−MO and aHMS−sMO coatings but just one trap air within them, which prevents the journey of corrosion
order decrease in the impedance value for the sHMS−sMO media toward the metal substrate.52 The water absorption
system. eq 350,51 was used to calculate the corrosion protection property of the coatings was also measured (by performing test
efficiency (PE) of the coatings based on the impedance values based on the ASTM D570 standard), as shown in Figure S13.
From Figure S13, it is clear that with the addition of fillers, the
l
o 1 1 |
]o water absorption property of the composite coatings decreased
o [R
o pepoxy
Rp o
o
PE = 100m }
composite
drastically. After 240 h of immersion in the water, the quantity
o
o 1 o
o
o Rp o of absorbed water decreased by 79% in the sHMS−sMO
n epoxy ~ (3)
coating compared to bare epoxy. This confirms that the used
where Rpepoxy is the coating resistance of epoxy and Rpcomposite is the fillers variable length scale and uniform distribution in the
d d

matrix can drastically improve the barrier performance of the

coating resistance for the HMS−MO composite coating. The composite coatings. This result corroborates the corrosion
coating resistance was found out by fitting the EIS data using resistance results discussed in the previous section. The
the equivalent circuit model shown in Figure S11a,b. Figure adhesion strength of the coatings was also measured by
S11a depicts the equivalent circuit for EIS data with a one-time performing a pull-off adhesion test based on the ASTM D4541
constant, whereas Figure S11b depicts the equivalent circuit for standard, Figure S14. It was clear from Figure S14 that the
two-time constant behavior. The circuit parameters were adhesion strength has improved in aHMS−sMO and sHMS−
solution resistance (Rs), coating resistance (Rp), constant sMO coatings. The improved adhesion of the composite
phase element of coating (CPEc), constant phase element of coating is in line with the increase in corrosion performance
the double layer (CPEdl), and charge-transfer resistance (Rct), and the barrier properties (Figures 10 and S13).
as depicted in the diagram. The coating resistance vs time of
exposure for the coatings is depicted in Figure S11c. The PE
versus time plot in Figure 10b clearly showed that the 4. CONCLUSIONS
composite coatings outperform bare epoxy coatings. The initial Unique epoxy composite coating systems for thin thermal
protection efficiency of the aHMS−MO system was 98.38%, shielding coating applications were successfully demonstrated.
which increased to 99.89% after 720 h of immersion in the 3.5 Using silica-modified HMS and stearic acid-modified MO
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nanoparticles in the composite coating, a two-way heat S11); schematic of the mechanism of corrosion
shielding mechanism was achieved with high IR reflection protection of the composite coating system (Figure
and low thermal conductivity. Due to the simultaneous S12); percentage water absorption values of various
functioning of the two-way heat shielding mechanism, the coatings when immersed in the water (ASTM D570)
thin epoxy−sHMS−sMO composite coatings with a thickness (Figure S13); and adhesion strength (pull-off adhesion)
of only 65 μm demonstrated exceptional thermal shielding test results for various coatings (Figure S14) (PDF)
performance. A temperature reduction of up to 31 °C (15 cm
away from the substrate) and 21 °C (at the bottom surface of
the panel) was obtained in these coatings applied to a 1 mm
thick mild steel substrate. For thermal insulation coatings,
■ AUTHOR INFORMATION
Corresponding Author
Smrutiranjan Parida − Indian Institute of Technology
increasing the IR reflection may be an essential route, but for
Bombay, Mumbai, Maharashtra 400076, India;
applications requiring a coating with low DFT, tuning the
orcid.org/0000-0002-6987-7244; Email: paridasm@
formulation to achieve low thermal conductivity also plays a
iitb.ac.in
crucial role, as demonstrated in this study. The work also
demonstrated that with a combination of the hydrophobicity Authors
and composite effect of the filler, the corrosion resistance of S. S. Ananthapadmanabhan − Indian Institute of Technology
the coatings can be exceptional. Due to the superior barrier Bombay, Mumbai, Maharashtra 400076, India;
performance, the composite coating, sHMS−sMO, effectively orcid.org/0000-0002-6359-8412
inhibited electrolyte diffusion during the long-term exposure Tapan Kumar Rout − Tata Steel Ltd., Jamshedpur,
(ca. 720 h in 3.5 wt % NaCl solution) test, showing an Jharkhand 831001, India
exceptional corrosion protection efficiency of approximately Sudin Chatterjee − Tata Steel Ltd., Jamshedpur, Jharkhand
99%. The novel hydrophobic thin thermal insulating epoxy 831001, India
composite coating developed in this study with high corrosion Titas Dasgupta − Indian Institute of Technology Bombay,
protection performance presents a very attractive solution for Mumbai, Maharashtra 400076, India; orcid.org/0000-
application on the exterior surfaces of large warehouses, 0002-8261-9784
roofing, and facilities that require thermal management and
Complete contact information is available at:
sustainability.
https://pubs.acs.org/10.1021/acsami.3c11712

■
*
ASSOCIATED CONTENT
sı Supporting Information
Funding
TATA Steel, Jamshedpur (Grant number Spons/MT/SP-1/
The Supporting Information is available free of charge at 2018) and the Industrial Research and Consultancy Centre
https://pubs.acs.org/doi/10.1021/acsami.3c11712. (IRCC), IIT Bombay, have provided financial support for this
research work.
Schematic of the coating preparation and application
procedure (Figure S1); surface (a and c) and cross- Notes
sectional (b and d) morphologies of aHMS−MO (a and The authors declare no competing financial interest.
b) and sHMS−sMO (c and d) coatings (Figure S2);
particle size distribution of (a) MO and (b) sMO
obtained from TEM analysis (Figure S3); schematic of
■ ACKNOWLEDGMENTS
The authors would like to thank the Department of
the surface modification of MO to prepare sMO giving it Metallurgical Engineering and Materials Science at IIT
its hydrophobic nature (Figure S4); time vs apparent Bombay and the Sophisticated Analytical Instrument Facility
temperature (a) of the coating at the bottom surface of (SAIF) at IIT Bombay for their experimental and instrumental
the coated panel, time vs apparent temperature (b) of support.
the coating at 15 cm below the coated panel (Figure
S5); schematic of thermal conduction through the
coating (a) bare epoxy and (b) coating with only HMS
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