Progress in Organic Coatings 146 (2020) 105715

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Progress in Organic Coatings

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

Corrosion-inhibiting, self-healing, mechanical-resistant, chemically and UV T

stable PDMAS/TiO2 epoxy hybrid nanocomposite coating for steel
petroleum tanker trucks
A.M. Fadla,*, M.I. Abdoua, M.A. Hamzab, S.A. Sadeekc
a
Egyptian Petroleum Research Institute (EPRI), Nasr City, Cairo, Egypt
b
Chemistry Department, Faculty of Science, Ain-Shams University, Abbassia, Cairo, Egypt
c
Chemistry Department, Faculty of Science, Zagazig University, Zagazig, Egypt

A R T I C LE I N FO A B S T R A C T

Keywords: Nanocomposite coatings play a strategic role in the treatment of metal surfaces in the petroleum sector, espe-
PDMAS/TiO2 nanocomposite cially steel oil transportation trucks, by providing novel materials exhibiting superior stability to various severe
Epoxy coating conditions. To confirm this concept, TiO2 nanoparticles (TNPs) were fabricated by a simple template-free sol-gel
Anti-corrosion performance method and blended with poly-dimethylamino siloxane (PDMAS) to fabricate PDMAS/TiO2 nanocomposite
Self-healing
acting as a multifunctional modifier for polyamine-cured epoxy coating. TNPs were characterized by TEM, XRD
Mechanical properties
UV resistance
and DLS measurements. FTIR characteristic spectra were employed to affirm the formation of hybrid nano-
composite coating. The anti-corrosion performance of surface-modified PDMAS/TiO2 epoxy coated films versus
unmodified conventional epoxy was investigated by salt spray accelerated corrosion test. Surface morphology
combination (SEM/EDX) analysis and weight loss study confirmed that NT/PDMAS-E coated film manifested the
best corrosion mitigation properties with a detected self-healing effect. The mechanical resistance characteristics
of the coatings were studied by adhesion (pull-off and cross-cut), abrasion and bend coating strategies to em-
phasize their class strength and workability. The chemical durability was checked by water and solvent im-
mersion tests. Finally, UV resistance test was performed to show the effect of fluorescent UV radiation on the
checked epoxy coated films. The thermophysical and electrical properties were also investigated to offer the
thermal and electrical conductivities of investigated coatings with increasing the loading level (%) by weight of
the nanocomposite modifier via the coating layer. The obtained results illustrated the superior anti-corrosion,
mechanical, chemical, electrical, thermal and UV resistance characteristics of the PDMAS/TiO2 epoxy hybrid
nanocomposite coating.

1. Introduction
Tanker trucks are vehicles used to transport crude oil and other
forms of petroleum from the oil fields to petroleum refinery plants and
from these plants to fuel stations when other transportation means such
as pipelines, tanker ships, and rail cars are not available or illogical to
be used [1,2]. Therefore, the protection of these trucks from corrosion
due to weather, ultraviolet radiation, the impact of chemicals and water
is a foregone conclusion to preserve the integrity of the truck body and
prevent the leakage of petroleum materials during transport. Nowa-
days, epoxy coatings have been widely employed for corrosion miti-
gation as they provide physical barrier films offering their outstanding
chemical stability, in addition to their high cross-linking densities, and
robust adhesion affinity to various surfaces [3,4]. Unfortunately, the
hydrophobic nature of the epoxy coatings may cause their damage ei-
ther by surface wear or by abrasion which lead to the formation of
localized cracks and pinholes that appear over coating surface, and
their depth and width increase by increasing exposure time to ag-
gressive media that lead to the coating damage [5,6]. In addition to
that, these defects provide facile conductive pathways for the corrosive
species where they could quickly move underneath the coating layer to
the metal surface leading to localized corrosion [7–9]. Several in-
vestigations have incorporated nanoparticles with the epoxy to form
coatings exhibiting a higher degree of protection of the traditional
epoxy coatings [10]. Because of their high surface properties, these
nanoparticles could block the cavities, porosities, and pathways
through the coating providing a suitable barrier against the corrosive
media to diffuse into the coating matrix [10–16].

⁎
Corresponding author.
E-mail address: fadl8693@yahoo.com (A.M. Fadl).

https://doi.org/10.1016/j.porgcoat.2020.105715
Received 17 January 2020; Received in revised form 13 March 2020; Accepted 20 April 2020
Available online 26 May 2020
0300-9440/ © 2020 Elsevier B.V. All rights reserved.
A.M. Fadl, et al.
Due to its availability, low cost, non-toxicity, chemical stability, and
UV resistance, TiO2 nanoparticles were incorporated with epoxy na-
nocomposites. It was found that TiO2/epoxy nanocomposites could
improve the anticorrosion behavior, the glass transition temperature
(Tg), and dielectric properties of the epoxy resin [17]. Shi et al. [18]
studied the enhanced protecting performance of TiO2/glycidoxypropyl
trimethoxy-silane epoxy nanocomposite layer on Al alloy surfaces
where they displayed an excellent barrier film, improved hardness and
enhanced Tg upon comparing to the untreated epoxy. Also, the dis-
persion of TiO2 nanoparticles has a higher influence than their micro-
size counterparts in enhancing the coating characteristics such as
hardness, friction resistances, abrasion, swelling, and reduction of
water permeability [19,20]. Besides, Ghosal and Ahmad [21] studied
the in-situ growth TiO2 from titanium isopropoxide (TIP) in a matrix of
polyamide (PA) and DGEBA, where TIP acts as bridging agent, con-
densation agent and inorganic modifier for epoxy. The results showed
the remarkable reinforcement of corrosion mitigation, abrasion re-
sistance properties, and scratch hardness of the hybrid coatings [21].
The influence of TiO2/silane composite on enhancing the mechanical,
thermal and corrosion inhibition performance of bisphenol-A based
phthalonitrile resins had been studied [22]. Incorporating micro/na-
nocapsules in coating matrix provides release of repairing agent rapidly
after triggering due to crack propagation in coatings and gifts the self-
healing to the coatings [23]. Several epoxy monomers have been easily
encapsulated using various methods [24]. However, the encapsulation
of suitable hardeners remains an issue. Xiuxiu Liu et al. [25] prepared a
smart self-healing coating consisted of an epoxy resin (diglycidyl ether
of bisphenol A) as matrix and microcapsules filled with the same
polymer as curing agent. Capsules were synthesized by interfacial
polymerization of epoxy droplets with ethylenediamine (EDA). These
microcapsules exhibited high shell strength while they could rupture
under external force, releasing the healing agent to the damaged area.
Thermally healable poly(siloxane-urethane) elastomers (PDMS-DA-PU
and PDMS/PCL-DA-PU) with Diels–Alder (DA) bonds were prepared
and showed good self-healing and remoldable behaviors via DA and
retro-DA reactions, which was confirmed by UV–vis and 1H NMR [26].
Recently, many research articles shed light on the utilization of self-
healing materials in epoxy coatings [27–35]. Dual components of a self-
healing epoxy system comprising an epoxy resin and its amine based
curing agent were encapsulated in a polyacrylonitrile (PAN) shell via a
coaxial electrospinning technique [27]. Utilization of core-shell nano-
fibers showed a compromising potential for the development of self-
healing nanofibers with the minimum drawbacks and limitations [28].
The microcapsules (MCs) containing alkyd resin based on coconut oil
with different concentrations: 5, 10, and 15 % were added into a
commercial epoxy coating to investigate its healing performance for
steel surface applications [32]. EIS results indicated when the MCs
concentration was equal to 10 %, the amount of the released healing
agent (alkyd resin based on coconut oil) was adequate to satisfactorily
heal the cracks. Some researchers focused on inhibitor and polymeric
healing agents encapsulated in organic and inorganic containers for the
self-healing epoxy coating. The different organic and inorganic con-
tainers such as micro/nano polymer capsules, cellulose nanofibers,
halloysite nanotubes, titanium dioxide nanocontainers, mesoporous
silica, hollow glass fibers, and core–shell nanofibers have been utilized
as reservoirs to store the self-healing agents [28–35].
Recently, polysiloxane coatings (silicon-oxygen backbone based
polymers), are intensively used in industrial protective and main-
tenance coatings which are featured by their high stability against
chemicals, abrasion, high temperatures, and extreme UV exposure
when compared with the traditional carbon-carbon backbone based
organic polymers and Polysiloxanes are used as silicon-based defoamers
[36–38]. Therefore, The novelty of this work is obvious in the pre-
paration of PDMAS/TiO2 nanocomposite as a novel multi-functional
modifier for epoxy coating applied on the carbon steel surface of pet-
roleum tanker trucks in which it offers the all required properties for
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Progress in Organic Coatings 146 (2020) 105715
such application such as corrosion mitigation, self-healing, mechanical-
resistance, chemical and UV immovability in addition to exhibiting
superior electrical and thermal resistances. And this performance is not
found before to be achieved by another utilized modifier and also this
modifier offers excellent cost implication compared to the conventional
utilized commercial modifiers to achieve the investigated properties
required for such application.
2. Experimental procedure
2.1. Materials
Titanium tetra isopropoxide (TTIP) was delivered from Sigma
Aldrich Company. Epoxy vehicle (D. E. R 671-X75) was obtained from
Dow Chemical's Company, Ancamine 1734 as a hardener, was obtained
from Anchor Chemicals Agency. Polydimethyl aminosiloxane (PDMAS)
was obtained from El-Fanar Company for Chemicals. Other chemicals
utilized in this investigation were received and employed without any
further purification.
2.2. Carbon steel preparation and composition
The C-steel panels used for salt spray experiment were prepared
with dimensions 10cm × 15 cm × 2 mm. The dimensions of steel spe-
cimens used for cross-cut and pull-off adhesion, bend and chemical
durability coating tests were 0.8 mm × 10cm × 15 cm. And those uti-
lized for abrasion test were with 100 mm square rounded corners and
with ¼ inch (6.3 mm) hole centrally located on each coupon.
Sandblasting was used for obtaining 50 μm roughness. Thereafter,
washing the roughened steel specimens with acetone and subsequently,
distilled water for coating implementation was done. The chemical
composition of C-steel coupons was analyzed as: C 0.160 %, Ni 0.063 %,
Cr 0.5 %, P 0.020 %, S 0.001 %, Mn 1.650 %, Al 0.043 %, Si 0.450 %, Fe
Balance.
2.3. Synthesis of TiO2 nanoparticles
A simple template-free sol-gel method was employed to synthesize
TiO2 nanoparticles (TNPs), as reported in our previous work [39] and
illustrated in Scheme 1. Briefly, 50 mL of TTIP were dissolved in 500 mL
of isopropanol with continuous stirring for 1 h. An appropriate amount
of distilled water was added drop by drop to this precursor solution to
hydrolyze it to Titanium hydroxide sol. Titanium hydroxide gel was
subjected to filtration and washing using isopropanol and distilled
water after aging of 2 days. As a final point, Ti(OH)4 gel was dried at
Scheme 1. A schematic diagram for the template-free sol-gel method for the
synthesis of TiO2.
A.M. Fadl, et al.
80 °C for 24 h, and calcined at 550 °C for 4 h to obtain TNPs.
2.4. Physicochemical characterizations
XRD patterns were done using Panalytical X′pert PRO MPD X-ray
Diffractometer with Cu Kα radiation (λ: 0.15418 nm, 2θ range 5˚–80˚,
scanning mode: continuous, scan step size: 0.04˚ and scan step time:
0.5 s). The average crystalline size of TNPs was estimated by the
Scherrer equation, eq. 1:
kλ
D=
β cosθ (1)
where D is the average crystalline size (nm), λ is the wavelength of the
X-rays (λ=0.115406 nm), k is the shape factor of the particles
(k = 0.9), β is the full width at half maximum of the peak (FWHM), and
θ is the diffraction angle (in radians). High-resolution transmission
electron microscope (HRTEM) images were captured using JEOL JEM
2100 electron microscope operating at an accelerating voltage of
200 kV. Dynamic light scattering (DLS) technique was utilized to esti-
mate particle size distribution and the zeta potential of the as-synthe-
sized TNPs particles using Malvern Zetasizer Nano ZS. FTIR analysis
was performed using Thermo Fisher Nicolet IS-10-FTIR spectro-
photometer (400–4000 cm−1).
2.5. Fabrication of PDMAS/TiO2 epoxy nanocomposite coating
Fabricated TNPs were mixed with polydimethyl aminosiloxane
(PDMAS) as 80:20 by ratio. After that, isopropanol, nonylphenol
ethoxylate, and dioctyl phthalate (DOP) were incorporated with a ro-
bust stirring for 20 min by ultrasonication device for obtaining PDMAS/
TiO2 nanocomposite paste as a multifunctional modifier. The nano-
composite paste was added to epoxy resin with different percentages
(0.5, 1, 1.5, 2 and 2.5 %), and xylene was incorporated to obtain
homogeneous admixtures. Five modified epoxy nanocomposite coatings
(NT/PDMAS-A, NT/PDMAS-B, NT/PDMAS-C, NT/PDMAS-D and NT/
PDMAS-E), against another conventional epoxy (blank) were obtained.
Ancamine 1734 as a hardener (curing agent) was employed to form
epoxy/polyamine adduct, and the two parts were mixed as 1.65:1 by
weight (epoxy: hardener). The formed cured coating film on the steel
surface was measured (80 ± 5 μm, DFT).
2.6. The anti-corrosion behavior
2.6.1. SEM/EDX morphology combination with respect to salt spray trial
SEM and EDX morphological surveys were employed to offer the
anti-corrosion performance of the tested coatings after lineal exposure
to salt spray aggressive vapor with humidity of 95 %, test solution of 5
% NaCl at 35 °C for 500 h according to ASTM B117-03. Sheen salt spray
chamber was used for performing the test. SEM and EDX techniques
were carried out by QUANTA FEG 250 scanning electron microscope.
The self-healing properties of the modified PDMAS/TiO2 epoxy nano-
composite coated layers were also studied and discussed through sur-
veying the coating films after exposure to the accelerated corrosive
vapor.
2.6.2. Weight loss technique
Based on the salt spray fog exposure, a weight-loss strategy was
carried to confirm the anti-corrosion performance of the employed
coated panels. 0.0001 g accuracy electronic balance was employed to
weigh the coated films before and after 500 h direct exposure to the
corrosive fog with removing the rust by 1 M HCl, washing with water
and acetone, then air-drying was carried out. The corrosion mitigation
performance of the coated films was illustrated by the weight loss
calculations. Weight loss per unit area per unit time (ΔW, g cm−2 h−1),
corrosion rate (CR, mm/y) and protection efficiency (PE%) were cal-
culated using eqs. (1) and (2) [40]:
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Progress in Organic Coatings 146 (2020) 105715
(ΔW ) X 87.6
C. R =
a. d. t (2)
W 0 − W1
PE = %
W0 (3)
where W0 is the weight loss of unmodified coating, W1 is the weight loss
of modified PDMAS/TiO2 nanocomposite coating specimen in mg, d is
the density of steel equal 7.85 g/cm3, a is the surface area in cm2 and t
is the time of exposure in hours.
2.7. Mechanical performance
Sheen cross-hatch cutter was used for measuring adhesion force of
the coating films (ASTM D 3359-17) [41]. Tensile tester (0−25 N/
mm2) was utilized to pull-off adhesion testing (ISO4624:2002) [42].
Conical mandrel apparatus was employed for bend property measuring
(ASTM D 522-93a) [43]. Taber Abraser apparatus was utilized for
abrasion resistance testing (ASTM D 4060-95) [44].
2.8. Chemical cure durability and UV immovability tests
Cure (solvent) and water resistance tests (API 5L2 4th edition, July
2002) were implemented to evaluate the chemical cure durability of
the investigated coatings [45]. UV immovability trial (ASTM D4587-
11, G151-19, and G154) was carried out for UV coating resistance
testing [46–48].
2.9. Thermophysical and electrical properties of the investigated
nanocomposite coatings
The themophysical properties of the investigated nanocomposite
coatings (thermal Conductivity, thermal Diffusivity and specific heat
capacity) were simultaneously measured at room temperature by LFA
467 HyperFlash® – Light Flash Apparatus [49]. The LFA 457 has an
operating range of −125 °C to 1100 °C and can be adapted to run down
to −150 °C. The samples were cut into quadrate shape with
1 cm × 1 cm and about 0.8 mm in thickness and then coated with
graphite by spraying. A Mettler-ToledoTM delta range balance was used
to measure the mass of the samples. The sample sizes were measured
using a caliper square. A two-electrode system (Meggar; MIT1525, 15
KV) was used for electrical resistance properties of the employed na-
nocomposite coatings and the tested coated films were cut with the
dimensions of 1 cm × 1 cm × 1 mm.
3. Results and discussion
3.1. Coating formulation overview
The suggested formed cross-linking network of PDMAS/TiO2 epoxy
nanocomposite coating is illustrated in Scheme 2. DGEBA-epoxy type
was anticipated for holding the checked coating components (coating
vehicle). Novel PDMAS/TiO2 nanocomposite particles were designed as
an epoxy varnish modifier for petroleum transportation trucks to offer
several required functions (corrosion mitigation, self-healing, mechan-
ical resistance, chemical stability and UV immovability) at the same
time. Isobutanol was employed for complete dispersion of PDMAS with
TNPs and the formation of homogeneous lotion for the epoxy treatment
in addition to increasing the polarity of the coating medium [50].
Isobutanol was selected for epoxy coating formulations to control the
application viscosity because it had strong solvating power. This be-
cause it had moderate Hansen solubility parameters such as δD (London
dispersion forces) and δH (hydrogen bonding forces) interactions and it
had strong δP (polar force) [51]. PDMAS was annexed as a coating
leveling agent (defoamer) in which performed as surfactant for the
coating film [50] and self-healing encapsulation material for epoxy as it
could chemically react with the un-reacted remnant epoxy and support
A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Scheme 2. The formation of three-dimensional networks of polyamine cured PDMAS/TiO2 epoxy hybrid nanocomposite coating.

the cross-linking density in the scratched steel area. The viscosity of the
coating lotion was controlled using xylene in which it had a strong δD
(London dispersion forces) [51]. The silicon-oxygen backbone pre-
sented in PDMAS made it more resistant to the effects of UV radiation
than the carbon-carbon backbone of organic polymers, thereby en-
hancing the UV resistance of epoxy. Epoxy-PDMAS hybrid composite
generated by chemically poly-condensation could create weather and
corrosion-resistant properties. The coating emulsions were treated with
nonylphenol ethoxylate to improve the induction period and decrease
the foam appearance during the stirring process. Dioctyl Phthalate
(DOP) plasticizer was added to enhance the epoxy layer elasticity. DOP
increased the flow and thermoplasticity of a polymer by decreasing the
elastic modulus of the finished product without altering the funda-
mental chemical character of the plasticized material [52]. The curing
Fig. 1. XRD patterns of the synthesized TiO2 nanoparticles.
agent utilized for the various investigated epoxy emulsions was Anca-
mine 1734 for constructing three-dimensional networks with epoxy and
formation of chemically inert cured-epoxy layer [49]. 53.85, 55.10, 62.21, 62.65, 68.91, 70.36 and 75.08 confirming the
Anatase phase structure (A; tetragonal), while the further peaks located
3.2. XRD analysis of TNPs at 2θ = 27.41, 36.11, 39.21, 41.21, 44.05, 54.30, 56.61 and 64.06
confirming the presence of the rutile phase (R; tetragonal). Thus, Eq. 2&
XRD measurements were executed to examine both the nature and 3 are utilized to calculate the percentages of both Anatase and Rutile
size of crystalline phases of the synthesized TiO2 nanoparticles. The phases [39,53]:
analysis of the XRD pattern shown in Fig. 1 had revealed the presence of
A% = [0.79 IA / (IR + 0.79IA)] x 100 (4)
different peaks located at 2θ = 25.30, 36.96, 37.76, 38.55, 48.05,

4
A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Table 1
The crystalline parameters of the synthesized TiO2 nanoparticles.
Crystalline phase Phase% D (nm) Space group Cell parameters Reference Card No.

a (Å) b (Å) c (Å) α( ) o

B( ) o
γ( ) o

Anatase 65 31.9 I41/amd 3.782 3.782 9.515 90 90 90 04-001-7641

Rutile 35 58.9 P42/mnm 4.953 4.593 2.986 90 90 90 04-005-7381

Fig. 2. TEM images of a) Dispersed TiO2 nanoparticles and b) Lamellar-shaped TiO2 nanocrystallites.

R% = [IR / (IR + 0.79IA)] x 100 (5) potential (Zpot) distribution value of TNPs was recognized at −31.4.
The recognized value of Zpot reflected about the steric stabilization of
IA, peak intensity of Anatase at 25.3° and IR, the peak intensity of the
dispersed TNPs. The agglomeration and deposition of TNPs could be
Rutile phase at 27.4°. The calculations tabulated in Table 1 revealed
forbidden in the solvent suspension. This gave an idea about fully-dis-
that the tetragonal Anatase is the dominant phase (65 %) in the syn-
persion and the non-agglomeration of TNPs via the coating binder.
thesized TiO2 sample with an average crystalline size of 31.9 nm, be-
sides the presence of tetragonal Rutil phase (35 %) with an average
crystalline size of 58.9 nm. 3.4. FTIR analysis

3.3. TEM morphology and DLS analysis of TNPs
As shown in Fig. 2, the nano-surface morphology of the checked
titania was visually displayed by the TEM micrographs [39]. Fig. 2a
demonstrated the non-agglomeration of TNPs and manifested a white
bar of 50 nm-length in which represented the size reference for the TEM
micrographs. Furthermore, Fig. 2b affirmed the nano-dimensions and
the flaky nature (lamellar shape) of these grains. Fig. 3 offered the re-
levance between particle size and the distribution intensity of TNPs in
which 100 % of these particles located in the nano-size scale. Zeta-
Fig. 3. Particle size distribution (PSD) of the synthesized TiO2 nanoparticles.
Fig. 4(a, b) displayed the FTIR spectra of the cured neat epoxy and
modified PDMAS/TiO2 epoxy nanocomposite coating layers. A broad
band assigned to OeH stretching of cured epoxy was appeared at
3458 cm−1 [40,54]. According to Fig. 4(a, b), the disappearance of
bands at 3329 and 3144 cm−1 characteristic to NeH stretching of pri-
mary amine of the hardener and PDMAS molecules, was appointed to
the chemical bonding of these amino-groups to form DGEBA-PA and
DGEBA-PA-PDMAS phases. The detected bands at 2966–2896 cm−1
were assigned to asymmetric and symmetric stretching vibrations of
eCH2– group [55,56]. The band that appeared at 1120 cm−1 was at-
tributed to CeN stretching affirming Polyamine-epoxide poly-
condensation reaction [57]. According to Fig. 4b, the stretching bands
appeared at 434, 485, and 829 cm−1, were appointed to TieO bond.
Also, the stretching band appeared at 692 cm−1 was characteristic to
OeTieO bond and the signalizing bands at 1180 and 1040 cm−1 were
attributed to the TieOeC bond. The stretching peaks observed at 1246
and 753 cm−1 were due to SieOeSi bond, 1279 and 917 cm−1 were
owing to SieCH3 and Sie(CH3)2 bonds, respectively affirmed the
modification of epoxy with the PDMAS. The shifts in eOH from
3424 cm−1 (epoxy and PDMAS) to 3423 cm−1 (PDMAS/epoxy-TiO2
comp) and epoxide bands from 910 to 917 cm−1 (PDMAS/epoxy–TiO2
comp), signalizing the condensation reactions of TNPs with PDMAS/
epoxy composite [21]. Besides, the formed OeTieO linkage affirmed
the connection between inorganic and organic phases to form the novel
nanocomposite. The appeared signals at 1456 and 1458 cm−1 were
assigned to eC]Ce of aromatic rings of cured epoxy films. The bands
appeared at 1295–1182 cm−1 range, were characteristic to the

5
A.M. Fadl, et al.
Fig. 4. FT-IR spectra of a) Cured unmodified epoxy and b) Cured modified PDMAS/TiO2 epoxy nanocomposite coating.
aliphatic chains [55]. The band appeared at 1180 cm−1 was appointed
to CeOeC (ester group) of cross-linked epoxy. The absence of 971, 917
and 775 cm−1 bands in the spectra revealed the complete cross-linking
of the terminal oxirane groups of epoxy [58]. As shown in Fig. 4b, the
disappearance of band characteristic to secondary OeH groups of cured
conventional epoxy at 972 cm−1 was assigned to the consistency of
OeTieO interconnection [21].
3.5. The anti-corrosion performance of unmodified and modified PDMAS/
TiO2 epoxy nanocomposite coating films using SEM/EDX combination
survey and weight loss method
The anti-corrosion behavior of the applied investigated coated pa-
nels was studied using the SEM/EDX combination morphology ex-
amination, as offered in Fig. 5. The drawbacks appeared over the
coating surface such as pinholes, microcracks, and rusting could be
evaluated using salt spray quick corrosion experiment. This test was
performed to measure the corrosion inhibiting performance for pro-
tective modifiers after the exposure to severe media [59]. The peak
intensity of Fe (arrow detected) gave an idea about the inhibiting layer
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Progress in Organic Coatings 146 (2020) 105715
formed on the carbon steel surface. The chemical structures of the
patterned coating layers on the steel surface was affirmed by EDX
elemental survey to illustrate the treatment of coating with PDMAS/
TiO2 nanocomposite molecules with different mass ratios versus un-
treated epoxy. Fig. 5a showed the SEM/EDX combination survey of the
untreated epoxy coating after the direct exposure to the corrosive fog
for 500 h. The untreated epoxy layer had succumbed to a harsh che-
mical fail because of the dispersal rusting and microcracks on the
coating surface due to increasing the pathways of aggressive species to
diffuse under the coating film thereby, consolidating the corrosion
process. Fig. 5b displays the SEM/EDX combination survey of NT/
PDMAS-A coating layer (treated with 0.5 % of nanocomposite by wt)
after exposure to the same interval. A modification in the inhibiting
performance of the coating and a reduction in the intensity of iron (Fe)
peak were detected owing to blocking the active sites through the
coating film by nanocomposite molecules. When the concentration of
the PDMAS/TiO2 nanocomposite particles was increased by wt via the
coating film in the case of NT/PDMAS-B (modified with 1 % by wt of
nanocomposite), and NT/PDMAS-C (modified with 1.5 % by wt of na-
nocomposite) coated films it was recognized that the anti-corrosion
A.M. Fadl, et al.
Fig. 5. The surface morphology investigation of blank epoxy against surface-modified PDMAS/TiO2 epoxy nanocomposite coated films.
behavior on C-steel substrate was improved than for NT/PDMAS-A
coating as displayed in Fig. 5c and d, respectively. But, a little rusting,
some microcracks, and roughness were observed over the coating sur-
face and absence of cracks close to the coating/steel interface. Fur-
thermore, SEM images displayed the appearance of white the sodium
chloride crystals spread and precipitated over the coated panel after
prolonged exposition period. The outstanding anti-corrosion behavior
was recognized for NT/PDMAS-D (modified with 2 % by wt of nano-
composite), and NT/PDMAS-E (modified with 2.5 % by wt of nano-
composite) coated films as shown in Fig. 5e and f. The EDX analysis
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Progress in Organic Coatings 146 (2020) 105715
quantitatively displayed the decrease in the Fe peak intensity from
55.53 (for the blank unmodified epoxy) to 8.2 % (for NT/PDMAS-A
coating), as illustrated in Table 2. Furthermore, the disappearance of Fe
peaks with enhancing the mass ratio (%) of PDMAS/TiO2 nano-
composite by weight via the coating layers reflected the enhancement in
the protective behavior of these coatings with the modification process.
Also, the increase in the Ti and Si intensities (%) with raising the
concentration of nanocomposite molecules confirmed the modification
process. Furthermore, EDX analysis illustrated the presence of Na+ and
Cl− species spread over the surface of coated films that reflected the
A.M. Fadl, et al.
Fig. 5. (continued)
exposure to 5 % NaCl solution as an aggressive medium.
The ability of PDMAS/TiO2 nanocomposite molecules to enhance
the corrosion inhibiting behavior could be attributed to their complete
dispersion through the epoxy binder, which blocked the paths of cor-
rosive fog species through the coating film. This led to establishing of
TieOeC, OeTieO, and TieO linkages in addition to SieOeSi and SieO
interconnections (inorganic phases) with epoxy and formation of cross-
linked hybrid networks of PA-PDMAS-TiO2 and PA-DGEBPA-TiO2 nano-
phases as illustrated in Scheme 1. These linkages supported the for-
mation of an effective barrier due to the increase in chemical bonding
density with epoxy. Also, TNPs absorbed more epoxy molecules on their
surfaces to enhance the film density and prohibit the breakthrough of
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Progress in Organic Coatings 146 (2020) 105715
the corrosive NaCl vapors via the zigzag ways of the coating film,
thereby decreasing the steel corrosion propagation process [60–62].
The predicted corrosion mitigation mechanisms were shown in Fig. 6(a,
b). The synergistic corrosion mitigation behavior of the surface-mod-
ified PDMAS/TiO2 epoxy nanocomposite coating on the steel petroleum
transmission truck surface was discussed based on the molecular
structures offered in Table 3. Fig. 6b offered the inhibitive mechanism
of the modified coating versus the deterioration in coating properties
for unmodified epoxy illustrated in Fig. 6a. The corrosion inhibiting
action could be discussed according to the following aspects: I). The
distinguished inhibitive behavior observed by the aromatic rings π-
electrons adsorption (organic moieties), as shown in Fig. 7a and
A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Table 2 agglomeration of TNPs and supported the inter-coat adhesion, thereby

EDX analysis of the investigated unmodified and modified PDMAS/TiO2 epoxy increasing the surface safeguard [21]. The layer swelling, cracking and
nanocomposite coated layers after direct exposure to salt spray fog with 5% blistering were prohibited due to the formation of barrier layer in-
NaCl for 500 h. hibited the aggressive ions transportation via the coating layer path-
Coating code Net Intensity (%) of elements (Counts) ways, thereby reinforcing the interface surface interactions and film
stiffness [64] as offered in Fig. 7b. Furthermore, the hydrophobicity of
Fe Ti Si Na Cl coating was reinforced then, the wettability of the corrosive medium via
Blank epoxy coating 55.53 – – 7.22 34.86
the epoxy layer was reduced. IV). Also, the enhancement in adhesion
NT/PDMAS-A 8.2 1.37 0.12 11.82 23.52 property depended on the H-bonding established among DGEBPA-
NT/PDMAS-B – 1.55 0.14 5.63 5.63 PDMAS system polar sites and the vacant orbitals of C-steel substrate, as
NT/PDMAS-C – 1.78 0.15 312.24 494.21 offered in Fig. 7b. For neat epoxy coating, H2O molecules could
NT/PDMAS-D – 1.93 0.19 10.35 10.34
transfuse to epoxy/steel interface through voids or pores spread over
NT/PDMAS-E – 2.72 0.23 6.89 5.35
the coating film [65]. Also, H2O molecules of salt spray fog induced the
electrochemical reactions under the coating film in case of neat epoxy
participation of the lone pair of electrons on oxygen atoms of PDMAS and caused in the formation of OH− anions through cathodic reactions
on the steel surface. The donating positions of epoxy resin set up an that could react with Na+ cations of the medium. Furthermore, NaOH
adherent plastic film with the C-steel vacant orbitals. The reinforcement ions were established as a strongly alkaline medium, which led to epoxy
in the adhesion property of the established layer for the surface-mod- layer delamination owing to pH enhancing beneath the coating layer
ified PDMAS/TiO2 epoxy nanocomposite coating was due to enhancing [66–68]. So, the TieOeC, TieOe and eOeTieOe nano-linkages sup-
the chemical bonding density (donor/acceptor interactions), as offered ported by SieOeSi and SieO linkages created perfect cross-bonded
mechanism displayed in Fig. 7b. The established cured film reduced the networks of the epoxyeTiO2 and epoxyeTiO2- OSi(CH3)2 hybrid nano-
aggressive species transport to the C-steel surface [63,64]. II) The polar linkages and prevented the coating layer failure in case of modified
moieties of surface-modified PDMAS/TiO2 epoxy nanocomposite coating [69]. The corrosion mitigation performance was also affirmed
coating induced durable electrostatic attractions between the C-steel by studying the weight loss method to investigate corrosion rate (CR)
effective sites and the coating layer. III) The established barrier film by and protection efficiency (PE) of surface-modified coatings against neat
surface-modified PDMAS/TiO2 epoxy nanocomposite coating could be epoxy after the forthright exposure to the corrosive fog for 500 h (21
assigned to the dispersion of titania nanoparticles which responsible for days) period. Blank neat epoxy coated layer offered the highest weight
forming OeTieO, TieO and TieOeC clusters and SieOeSi and SieO loss value at 468.3 mg and CR of 0.2090 mm/y as illustrated in Table 4.
linkages with epoxy vehicle, worked as internal bridges which cause a This could be attributed to the spreading of pores through the cured
decrease in total free volumes, reduced segmental motions and there- coating layer, thereby enhancing the generation of corrosion products
after reinforced stiffness. This performance prohibited the in which offered the highest weight loss value with removing them

Fig. 6. The predicted protective mechanism employed by a) Blank conventional epoxy, b) Modified PDMAS/TiO2 epoxy nanocomposite coating.

9
A.M. Fadl, et al.
Table 3
Molecular structures of the investigated molecules and their 3D models.
Molecular structure
[70]. The measured weight loss value decreased for NT/PDMAS-A
coated layer compared to the neat epoxy layer and was recorded at
153.7 mg. A decrease in the CR was also observed at 0.0686 mm/y and
an increase in the PE was calculated at 67.1 %. The outstanding anti-
corrosion results were observed in case of NT/PDMAS-E in which the
weight loss attained the minimum estimation at 1.5 mg, CR fulfilled the
least record at 0.0006 mm/y and the PE displayed the highest estima-
tion at 99.7 %. The superior inhibitive performance of the surface-
modified PDMAS/TiO2 hybrid epoxy nanocomposite film could be as-
signed to the recently discussed mechanisms. Spreading of titania na-
noparticles with the SieOeSi and SieO linkages via the epoxy matrix
was responsible for occupying the coating holidays, causing filling of
the free volumes and supporting the effective barrier formation [71].
So, the corrosion mitigation performance depended on the synergy
between the coating composition and the surface hardness [72]. The
reduction in CR and enhancing in PE (%) of the coating layer with an
increase in the mass ratio (%) by weight of the PDMAS/TiO2 nano-
composite molecules via the coating surface were illustrated in Figs. 8
and 9.
3.6. Self-healing behavior of PDMAS/TiO2 epoxy nanocomposite coating
The self-healing encapsulation effect of PDMAS/TiO2
10
Progress in Organic Coatings 146 (2020) 105715
3D model
nanocomposite molecules via the epoxy coating was obviously illu-
strated by surveying the cutting area established over the cured coated
steel panels after performing the salt spray accelerated corrosion test.
These panels were exposed directly to corrosive vapor (5% NaCl soln)
for 500 h at 35 °C. Fig. 10a showed a complete electrolytic degradation
via the cutting area (high percent of rust), for blank conventional epoxy
coating and illustrated as the following equations:
2Fe + O2 + 4H+ 2Fe2+ + 2H2O (6)
−
4Fe + 8Cl 4FeCl2 + 8e' (7)
4H2O + 2O2 + 8Na+ + 8e' 8NaOH (8)
FeCI2 + 2NaOH Fe(OH)2 + 2NaCl (9)
4Fe(OH)2 + O2 2Fe2O3.H2O + 2H2O (10)
As shown in Fig. 10b, it could be observed that the surface-modified
PDMAS/TiO2 epoxy nanocomposite coating displayed superior anti-
corrosion performance, and the scratched area was protected by the
self-healing mechanism [73]. Also, it was observed that the healing
effect was enhanced by raising the mass ratio (%) by weight of the
nanocomposite molecules as active nanocapsules. Furthermore, the
effect of weight fraction and size of these capsules on the anti-corrosion
A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Fig. 7. The highly cross-linking density of the investigated epoxy coatings a) Blank conventional epoxy, b) Modified PDMAS/TiO2 epoxy nanocomposite coating.

behavior through the self-healing performance could be discussed [74].
The self-healing mechanism can be discussed according to different
presumptions: i) Uniform distribution of the PDMAS/TiO2 nanocapsules
through the coating matrix is made through the conventional epoxy to
establish the epoxy nanocomposite sol; ii) Equality in the fill content of
each nanocapsule is observed due to the well-dispersion by their polar
terminals and the growth in the inorganic TieOeC, TieOe and
eOeTieOenano-linkages supported by SieOeSi and SieO linkages is
occured; iii) Neglecting the shell of nanocapsules is considered in which
the nanocomposite molecules are dispersed directly without shelling via
the epoxy vehicle; iv) poly-condensation is progressed by PDMAS with
the remnant non-reacted epoxy molecules to form epoxyeTiO2eCH2N
(CH2)3OSi(CH3)2 hybrid nanophases in which fill and inhibit the
scratched area (self-repair) in addition to filling the micro-cracks via the
coating layer [75]. The discussed mechanics of self-healing effect of the
investigated epoxy nanocomposite coating were compared to some
mentioned discussions in the published literature [76]. Epoxy-en-
capsulated TiO2 nanotubes and amine-immobilized mesoporous silica
were added into epoxy applied on the steel surface. Scanning Electron
Microscopy (SEM) analysis was employed to monitor the self-healing of
the scratch effect of the investigated modified epoxy. The results con-
firmed that the epoxy pre-polymer was slowly released into the crack.
The released epoxy pre-polymer came into contact with the amine
immobilized in mesoporous silica and cross-linked to heal the scratch.
The PDMAS/TiO2 nanocapsules with a diameter (d) are randomly dis-
persed in the epoxy resin. The number of nanocapsules that are rup-
tured (n), after planar scratching is:
n=N X P (11)
where; N = total no. of dispersed nanocapsules in epoxy;
P = probability that rupturing of nanocapsules can occur.
The probability nanocapsules to be dispersed through epoxy is:
Ad ρAd
P = =
M /ρ M (12)
where; A = scratch plane area = H X L; d = nanocapsules diameter;

Table 4
Weight loss data of unmodified epoxy and modified PDMAS/TiO2 epoxy nanocomposite coating films before and after 500 h exposure in salt spray cabinet using 5%
NaCl soln.
Coating code Initial weight before exposure (mg) Final weight after exposure (mg) Weight loss (mg) CR (mm/y) PE (%)

Blank epoxy coating 86289.6 85821.3 468.3 0.2090 –

NT/PDMAS-A 81563.8 81410.1 153.7 0.0686 67.1
NT/PDMAS-B 83876.3 83833.8 42.5 0.0189 90.9
NT/PDMAS-C 86123.5 86085.5 38.0 0.0169 91.9
NT/PDMAS-D 84673.1 84660.7 12.4 0.0055 97.3
NT/PDMAS-E 86716.7 86715.2 1.5 0.0006 99.7

CR = Corrosion Rate.
PE = Protection Efficiency.

11
A.M. Fadl, et al.
Fig. 8. The effect of concentration of PDMAS/TiO2 nanocomposite (by weight
via the epoxy coating film) on the corrosion rate values.
Fig. 9. The protection efficiency enhancement of the investigated modified
epoxy nanocomposite coatings against conventional epoxy.
Fig. 10. Self-healing mechanism of PDMAS/TiO2 epoxy hybrid nanocomposite coating against electrolytic deterioration of unmodified conventional epoxy.
12
Progress in Organic Coatings 146 (2020) 105715
M = coating mass; ρ = coating density; H = coating thickness;
L = scratch length.
The total number of dispersed nanocapsules in epoxy can be mea-
sured as:
ØM
N =
m (13)
where Ø = weight fraction of nanocapsules in epoxy and m = the mass
of one nanocapsule.
The influence of particle size, shape, distribution and concentration
of TiO2 nanoparticles (TNPs) on self-healing effect of the epoxy coating
can be described in the following: i) The well-dispersed TNPs with tiny
size absorbed more epoxy molecules on their surfaces to enhance the
film density formed over the scratched area and prohibit the break-
through of the corrosive NaCl vapors to the steel surface, thereby in-
creasing the self-healing effect with polyamine cured epoxy by the
formation of PA-DGEBPA-TiO2 nano-phases and decreasing the steel
corrosion propagation process. The lamellar-shape of well-dispersed
TNPs enhances the self-healing effect by formation overlapping plates
of DGEBPA-TiO2- CH2N(CH2)3OSi(CH3)2 nano-phases in which ar-
ranged via coating layer parallel to the steel surface and forbid the
transmission path of aggressive species thereby enhancing the corrosion
mitigation. The increase in the concentration of TiO2 nanoparticles will
enhance the self-healing effect by increasing the inorganic TieOeC,
TieOe and eOeTieOenano-linkages and generate cross-linked net-
works of the epoxyeTiO2- CH2N(CH2)3OSi(CH3)2 hybrid nanocompo-
site phases and protect the scratched area.
Based on the discussed presumptions, the synergistic autonomous
self-healing mechanism of the PDMAS/TiO2 nanocapsules and epoxy
(DGEPA) cured by polyamine (PA) could be attributed to the combined
effect of the extra cross-linking density (poly-condensation) produced
A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Table 5
Mechanical performance properties of unmodified epoxy and modified PDMAS/TiO2 epoxy nanocomposite coating films.
Coating code Pull-off adhesion (MPa) Adhesion cross-cut Bend (total elongation) Abrasion resistance (weight loss(mg)/500cycle/CS-17 wheel/1000 g, wt)

Blank epoxy coating 4.8 3B 21 87

NT/PDMAS-A 5.6 4B 27 42
NT/PDMAS-B 5.9 5B 54 25
NT/PDMAS-C 6.5 5B 88 21
NT/PDMAS-D 7 5B 115 13
NT/PDMAS-E 7 5B 132 9

Fig. 11. Adhesion cross-cut test of a) Blank conventional epoxy and b) PDMAS/TiO2 epoxy hybrid nanocomposite coating.

Fig. 12. The predicted adhesion mechanism of modified PDMAS/TiO2 epoxy hybrid nanocomposite coated film against unmodified conventional epoxy.

by PDMAS-DGEPA-TiO2 in which perform as the interconnected bridges (CH2)3OSi(CH3)2 hybrid nanocomposite phases in which promote the
of the resin matrix. So, the growth in the inorganic TieOeC, TieOe contact of fracture surfaces and inhibit the scratched area. The self-
and eOeTieOenano-linkages supported by SieOeSi and SieO lin- healing effect prevents the migration of the solvent (ions and water) in
kages could generate cross-linked networks of the epoxyeTiO2-CH2N the vicinity of coating and causes the passivation of the steel substrate.

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A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Fig. 13. Bend flexibility test of the investigated epoxy coated films.

Table 6 PDMAS/TiO2 epoxy nanocomposite coated film was shown in Fig. 12.
Cure (solvent) durability and water immersion tests. The bend flexibility property of the employed coating films was offered
Coating code Cure durability Water resistance
in Fig. 13. The conventional epoxy coating film offered whole layer
degradation displayed the maximum crack volume at a bend property
Blank epoxy coating Appearance of blistering, wrinkling, Few softening value of 21 as illustrated in Table 5. The cracking size decreased with
softening and loss of adhesion boosting the mass ratio (%) by weight of the nanocomposite molecules
NT/PDMAS-A Appearance of wrinkling, softening and Pass
loss of adhesion
and NT/PDMAS-E coating offered perfect coating surface without
NT/PDMAS-B Pass Pass cracking and achieved the highest bend value at 132. The abrasion
NT/PDMAS-C Pass Pass resistance of the checked unmodified and surface-modified nano-
NT/PDMAS-D Pass Pass composite coatings was illustrated in Table 5. Measuring the weight
NT/PDMAS-E Pass Pass
loss in the coating layer as a function of the abrasion resistance property
was discussed. The neat unmodified epoxy illustrated the elevated mass
loss value after the abrasion process at 87 mg/500cycle/CS-17 wheel/
3.7. Mechanical properties
1000 g, wt. Furthermore, a decrease in the weight loss value and an
improvement in the abrasion durability of the coating layer were ob-
The mechanical properties of the surface-modified PDMAS/TiO2
served with increasing the mass percent of the NT/PDMAS molecules
epoxy nanocomposite coating films against unmodified neat epoxy
via the epoxy layer and achieved the outstanding performance for NT/
were studied by measuring the adhesion (pull-off and cross-cut), bend
PDMAS-E coating. The prominent behavior in the adhesion property
and abrasion characters and the results were depicted in Table 5. The
could be attributed to enhancing the interface surface interaction be-
neat epoxy exhibited the least adhesion characters at 4.8 MPa for pull-
tween PDMAS/TiO2 nanocomposite linkages (SieOeSi, SieO eOe-
off and class 3B for cross-cut adhesion, as displayed in Fig. 11a. With
TieOe, TieOe and TieOeC), and epoxy resin matrix. This perfor-
increasing the concentration of nanocomposite molecules via the epoxy
mance decreased the free layer spaces, reinforced cross-linking density
vehicle, there was an enhancement in the adhesion characters in which
and promoted the adhesion strength [77]. The increase in bend prop-
achieved the highest values at 7 MPa and 5B degree, as displayed in
erty and the decrease in film abrasion for the modified PDMAS/TiO2
Fig. 11b. The predicted adhesion mechanism offered by the modified

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A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Fig. 14. Photographic images of a) Conventional unmodified epoxy and b) PDMAS/TiO2 epoxy hybrid nanocomposite coating film after immersion in isopropanol
solvent for 4 h.

Fig. 15. Mechanism offers the chemical durability of a) Conventional unmodified epoxy and b) PDMAS/TiO2 epoxy hybrid nanocomposite coating film.

epoxy nanocomposite coating could be assigned to the full spreading of
PDMAS molecules and TNPs in which lead to increasing in the interface
surface interactions, thereby contributing in filling the holidays via the
coating film and working as bridges that connect the epoxy matrix
molecules. This performance causes a depression in the free volumes
and an increase in the cross-linking density of the formed cured epoxy
film, thereby diminishing segmental chain motions, enhancing tough-
ness and generating less abraded epoxy film [40]. Furthermore, the
reinforcement in abrasion resistance and toughness of coating film
could be assigned to the π–π interactions produced by the aromatic
rings in epoxy presented in the proximity of the coating surface [78].
The mechanical properties of the investigated PDMAS/TiO2 epoxy na-
nocomposite coated films were re-tested after the direct exposure to the
salt spray fog for 500 h and offering the hybrid synergistic self-healing
effect. It was found the measured cross-cut and pull-off adhesions; bend
and abrasion resistance of the modified nanocomposite coatings
achieved accepted criteria from the application point of view and of-
fered the same results before performing the test. The observed data
were similar to the tabulated results in Table 5.

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A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Fig. 16. Photographic images for a) Conventional unmodified epoxy and b) PDMAS/TiO2 hybrid epoxy nanocomposite coating film after direct exposure to UV
radiation via solar box.

Fig. 17. Mechanism offers the UV resistance of a) Conventional unmodified epoxy and b) PDMAS/TiO2 epoxy hybrid nanocomposite coating film.

3.8. Chemical resistance
Solvent and water resistance tests for NT/PDMAS-A, NT/PDMAS-B,
NT/PDMAS-C, NT/PDMAS-D, NT/PDMAS-E against conventional un-
modified coated layers were performed. NT/PDMAS-B, NT/PDMAS-C,
NT/PDMAS-D, NT/PDMAS-E cured coated films offered ideal chemical
durability against chemical failure in the case of conventional epoxy
and NT/PDMAS-A coatings as illustrated in Table 6. All the investigated
coated films offered a preferable water immersion resistance against a
few softening in case of neat epoxy. Solvent durability passed coated
films displayed perfect adhesion (5B), no softening, no wrinkling, and
no blistering detected after 30 min from 4 h recovery duration and
against complete failure generated in case of conventional epoxy and
NT/PDMAS-A coatings as shown in the photographic images in
Fig. 14(a, b). The reinforcement in chemical immovability may be re-
ferred to the interface interactions occurred through the coating film

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A.M. Fadl, et al. Progress in Organic Coatings 146 (2020) 105715

Table 7
Thermophysical and electrical properties of unmodified epoxy and modified PDMAS/TiO2 epoxy nanocomposite coating films.
Coating code Thermal conductivity (λ, W Thermal diffusivity (α, m2 Polymeric coating density Specific heat capacity (Cp, J Electrical resistivity (P,
m−1 K−1) S−1) x 10-6 (ρ, kg/m3) Kg−1 K−1) Ω.m) x 105

Blank epoxy coating 0.102 0.0345 1230 2403.6 1.23

NT/PDMAS-A 0.057 0.0167 2150 1587.5 2.15
NT/PDMAS-B 0.034 0.0118 2330 1236.6 2.93
NT/PDMAS-C 0.031 0.0113 2864 957.8 3.65
NT/PDMAS-D 0.014 0.0057 2890 849.9 3.89
NT/PDMAS-E 0.005 0.0051 2940 333.4 4.34

period at irradiance 10 to evaluate the effect of ultraviolet radiation on

the employed investigated coatings applied on the C-steel surface of
petroleum transmission trucks, as shown in Fig. 16. The modified na-
nocomposite coated films offered effective UV resistance and achieved
the maximum performance for film displayed rust grade: 10, blistering
degree: few and adhesion class of 5B in addition to glossy loss at 60°
from 22.31° to 21.92° The unmodified epoxy and NT/PDMAS-A coated
panels demonstrated full degradation as rust grade: 7, loss of adhesion:
3B, and glossy loss at 60° from 22.31° to 13.73° due to the penetration
of the ultraviolet rays the coating through the open active channels and
absorption of these rays by the epoxy vehicle as the mechanism shown
in Fig. 17a. The positive UV resistance results for the modified nano-
composite coatings may be assigned to the full spreading of titania
Fig. 18. Experimental values of the thermal conductivity of PDMAS/TiO2
nanoparticles with PDMAS molecules which fill pinholes over coating
epoxy hybrid nanocomposite coatings against neat epoxy.
layer and form TieO, OeTieO, TieOeC, SieOeSi and SieO linkages
as interconnected coating bridges in addition to establishing a shield of
the overlapping plates (blocking barrier). These linkages decrease the
total free spaces and preventing the UV rays penetration to the steel
surface. Also, the arrangement of PDMAS molecules and TiO2 nano-
particles through the coating reinforced the interface interactions be-
tween epoxy and these molecules, thereby improving the film stiffness,
enhancing the inter-coat adhesion strength and blocking the open
channels of the film as illustrated in Fig. 17b. Acceptance glossy be-
havior of the modified nanocomposite coated films was because
TieOeC, TieO, OeTieO, SieOeSi and SieO linkages absorbed the UV
irradiation and converted it into heat and liberated to the external at-
mosphere [64,82].

3.10. Thermophysical and electrical properties of the nanocomposite

Fig. 19. The electrical resistivity values of the investigated coatings with in-
creasing the concentration of nanocomposite modifier via the coating film.
owing to complete dispersion of PDMAS/TiO2 nanocomposite linkages
(eOeTieOe, TieOeC, SieOeSi and SieO) as bridges, thereby redu-
cing the free spaces in epoxy coating structure and enhancing the cross-
linking intensity. After that, the modified PDMAS/TiO2 epoxy nano-
composite coating resists the influence of organic solvents as shown in
the chemical resistance mechanisms illustrated in Fig. 15b. Further-
more, the substantial adhesion of epoxy on the surface of steel depends
on the donor-acceptor chemical interactions among the epoxy polar
groups and steel active sites, as shown in Fig. 7b. Chemical failure could
be produced due to the diffusion of H+ and OH− species of water and
isopropanol solvent through the free spaces in the epoxy/steel interface,
thereby generating electrolytic chemical degradation [79–81] as shown
in Fig. 15a. The interface H2O molecules could readily break the che-
mical bonds owing to the establishment of robust H-bonding [79].
Then, PDMAS/TiO2 nanocomposite linkages blocked the pores
spreading over the surface of the paint and prevented the transmittance
pathway of H2O and aggressive ions to the coating/steel interface.
3.9. UV resistance
UV resistance test was performed at 340 nm wavelength for 80 h
coatings
The thermophysical properties (thermal Conductivity, thermal dif-
fusivity and specific heat capacity) of the surface-modified epoxy na-
nocomposite coatings against the neat epoxy were investigated and
depicted in Table 7. A decrease in the thermal Conductivity (λ) values
was observed with increasing with increasing the concentration of
PDMAS/TiO2 nanocomposite modifier in epoxy and achieved the
lowest value at 0.005 W m−1 K−1, as shown in Fig. 18. In addition, the
thermal diffusivity (α) values were also measured and recorded the
lowest value for NT/PDMAS-E coating (modified with 2.5 % nano-
composite), at 0.0051 × 10-6 m2 S−1. As illustrated in Table 7, the
measured specific heat capacities (Cp) of the investigated nano-
composite coatings offered a decrease in their values with increasing
the loading level (%) by weight of the nanocomposite modifier through
the coating film and it was calculated from the following equation
[83,84]:
λ
Cp =
αρ (14)
The least measured Cp value was recorded for NT/PDMAS-E at 333.4 J
Kg−1 K−1. The published literature confirmed that the thermal con-
ductivity and thermal diffusivity values of the polymeric coatings were
increased with increasing the conductive materials and decreased with
decreasing the size of the filled particles [83–85]. The obtained results

17
A.M. Fadl, et al.
confirmed the thermal stability of PDMAS/TiO2 epoxy nanocomposite
coating and this could be attributed to the combined thermal resistivity
effect of the epoxy resin and PDMAS/TiO2 nanocomposite molecules.
The well-dispersed titania nanoparticles with PDMAS molecules could
form TieO, OeTieO, TieOeC, SieOeSi and SieO linkages as inter-
connected coating bridges in addition to establishing a shield of the
overlapping plates (blocking barrier). These linkages support the
thermal stability of the epoxy coating. The electrical resistivity (P) of
the epoxy coating was also increased with increasing the mass ratio (%)
by weight of the nanocomposite modifier through the coating layer as
illustrated in Table 7. Blank unmodified epoxy offered the least elec-
trical resistivity value at 1.23 × 105 Ω.m. An improvement in the
electrical resistivity values was observed with the modification process
as shown in Fig.19. The enhancement in electrical resistance properties
of the epoxy nanocomposite coatings could be assigned to the growth in
the inorganic TieOeC, TieOe and eOeTieOenano-linkages sup-
ported by SieOeSi and SieO linkages in which produced cross-linked
networks of the epoxy-TiO2-PA and epoxyeTiO2-CH2N(CH2)3OSi(CH3)2
hybrid nanocomposite phases. On the other hand, with increasing the
content of TiO2 NPs in epoxy coating, the storage modulus decreases
gradually [49]. The presented work affirmed the role of transition
metal-organic hybrid nano-linkages as TieOeC, TieOe and eOe-
TieOe in enhancing the whole polymeric coating properties for
widespread applications [86] and giving idea about the epoxy nan-
composites as a product [87]. Furthermore, the proposed work offered
a new strategy by using the nanocomposites with polymeric epoxy
coating to obtain multifunctional nanocomposite protective coating
with electrical insulation characteristics for various applications
[88,89].
4. Conclusions
PDMAS/TiO2 nanocomposite was prepared as a multi-functional
modifier for epoxy coating to offer several required application prop-
erties such as corrosion mitigation, self-healing, mechanical-resistance,
chemical and UV immovability for steel petroleum transmission trucks.
The anti-corrosion performance and self-healing behavior of surface-
modified PDMAS/TiO2 epoxy nanocomposite coated films were in-
vestigated using accelerated corrosion salt spray cabinet. The SEM/EDX
morphology analysis displayed a drastic chemical failure in case of
unmodified epoxy. With increasing the mass ratio (%) by weight of the
nanocomposite modifier via the coating layer, an improvement in the
protective behavior and a reduction in the intensity of Fe peak were
recognized and achieved the maximum behavior for NT/PDMAS-E
coating at 2.5 % loading level. The mechanical properties were en-
hanced with the modification process of the coating and offered an
outstanding behavior for NT/PDMAS-E coating. The prominent che-
mical immovability characteristics of the modified coated films against
complete degradation in case of blank neat epoxy were observed for
NT/PDMAS-E by performing cure (solvent) and water resistance tests.
UV resistance properties of the modified epoxy nanocomposite coated
films offered positive results and recorded the best performance for NT/
PDMAS-E coating contra the full-deterioration of the unmodified epoxy
coating. The investigated epoxy nanocomposite coatings offered ex-
cellent thermal and electrical stabilities with increasing the content of
PDMAS/TiO2 nanocomposite via the coating layer.
Author public statement
The novelty of this work is obvious in the preparation of PDMAS/
TiO2 nanocomposite as a novel multi-functional modifier for epoxy
coating applied on the carbon steel surface of petroleum tanker trucks
in which it offers the all required properties for such application such as
corrosion mitigation, self-healing, mechanical-resistance, chemical and
UV immovability in addition to exhibiting superior electrical and
thermal resistances. And this performance is not found before to be
18
Progress in Organic Coatings 146 (2020) 105715
achieved by another utilized modifier and also this modifier offers ex-
cellent cost implication compared to the conventional utilized com-
mercial modifiers to achieve the investigated properties required for
such application.
Declaration of Competing Interest
The authors declare that they have no conflict of interest.
Acknowledgments
Authors offer the names of appreciation to each of the Egyptian
Petroleum Research Institute (EPRI), Ain Shams University, and
Zagazig University for full support in producing this integrated applied
work from the perspective of applied scientific research for the petro-
leum and industry sectors.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.porgcoat.2020.
105715.
References
[1] Refined Fuel Trucks - Westmor Industries Fuel Delivery Equipment, (2017)
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