Egyptian Journal of Petroleum 28 (2019) 253–260

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Egyptian Journal of Petroleum

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Full Length Article

Preparation, characterization and evaluation of polybenzoxazine

thermoset/clay nanocomposites for metal coating
Salwa.M. El-Mesallamy
Department of Petrochemicals, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: A series of polybenzoxazine-clay nanocomposites with various organoclay contents (3, 5, 10, and 20 wt%)
Received 29 November 2018 were prepared by the one-shot procedure. from organo-montmorillonite (OMMT) and bifunctional
Revised 7 May 2019 benzoxazine, namely, bis-(3-dodecyel-3,4-dihydro-2H-1,3-benzoxazine) isopropane (B-dod). OMMTs
Accepted 19 May 2019
were prepared by modification of Na-MMT with different ammonium salts of amines such as tyramine
Available online 30 May 2019
(Tyr), amino lauric acid (ALA) and N,N-dimethyl stearyl amine (DMS). Transmission electron microscope
(TEM), X-ray diffraction (XRD) and infrared measurements (FTIR) were used to examine the structure and
Keywords:
modification of OMMTs. The morphology of polybenzoxazine nanocomposites (B-dod/Tyr-MMT, B-dod/
Polybenzoxazine
Nanocomposites
ALA-MMT, B-dod/DMS-MMT) was investigated by X-ray and TEM analyses. The X-ray analysis and
Organoclay TEM photos indicated that organoclay was exfoliated into polybenzoxazine matrix even at the highest
Mechanical properties organoclay loading (20%). Mechanical properties (viz, adhesion on metallic substrate, scratch hardness,
Metal coating tensile modulus, and elongation at break) of the prepared nanocomposites were measured. The tensile
properties of prepared samples were examined; as the content of modified clay was increased, the tensile
modulus increased; however, the elongation at break decreased. In addition, the optimum adhesion and
scratch hardness values of the prepared nanocomposites were increased more than the neat resin, also,
thermogravimetric analysis has the same manner. Therefore, the prepared nanocomposite materials
could be successfully used for metal coatings.
Ó 2019 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction response [21–23] Polybenzoxazine was utilized as sensors when

The structure and dynamics in clay nanocomposites
unequivocally impact on their macroscopic properties with the
goal that execution upgrades (thermomechanical, boundary, fire
retardant proficiency) are straightforwardly identified with the
scattering level of the filler and the quality of matrixes nanoparti-
cle interactions [1–8]. The previous quite a few years have seen
dynamic research on polybenzoxazines as cutting-edge thermoset
polymers, with noteworthy endeavors in fitting their properties for
the unique prerequisites of individual applications [9–12]. Until
now, some benzoxazine resins have been popularized by a few
organizations, including Huntsman [13]. Polybenzoxazine has
fascinating properties, including low volumetric shrinkage or
extension after curing [14], low water absorption, magnificent
protection from chemicals and UV light [15,16], high thermal prop-
erties [17] and simple handling [18]. These properties are credited
to the remarkable H-bonding structure found in these materials
[19,20]. They are polymerized by a thermally initiated ring opening
Peer review under responsibility of Egyptian Petroleum Research Institute.
E-mail address: s_mostafa@epri.sci.eg
prepared with carbon aerogel and graphene oxide nanoporous
material [24,25]. The hybridization of polybenzoxazine with
organoclay is an effective approach for acquiring superior
polybenzoxazine. Agag et al. prepared polybenzoxazine–clay
nanocomposites (OMMT) and mica [26–28]. As of late, polyben-
zoxazines have turned out to be expanding consideration in
corrosion insurance zone [29–31]. The corrosion protection
capacity of benzoxazine-cured epoxy covering (EPB) was addition-
ally explored on MS substrate [32]. Composites of maleimide-
containing polybenzoxazine/amine-capped aniline trimer were
prepared [33]. Corrosion resistance of the polybenzoxazine (poly
(BA-aptms)) coating was enhanced by consolidating epoxy into
the coatings network [34]. Polybenzoxazine coatings were pre-
pared from a phenol, para-phenylenediamine on 1050 aluminum
alloy by spin coating of solution [35]. Preparation of modified elas-
tic polybenzoxazine as matrix with polyaniline emeraldine salt as
filler was connected as a potential hostile to corrosion application
for carbon steel [36,37].
The current work represents the preparation of a series of
polybenzoxazine-clay hybrids with different organoclay and with
different loading wt% content. The morphology, mechanical and

https://doi.org/10.1016/j.ejpe.2019.05.003
1110-0621/Ó 2019 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
254 S.M. El-Mesallamy / Egyptian Journal of Petroleum 28 (2019) 253–260
thermal properties were investigated, to evaluated the polyben-
zoxazine nanocomposites in metal coating application.
2. Experimental
2.1. Materials
Bisphenol-A, dodecyl amine and Paraformaldehyde were
obtained from Kishida Co. Japan. ethyl acetate was obtained from
El-Naser Co. Egypt. Sodium montmorillonite (Na-MMT) with
cation exchange capacity (CEC) of ca. 119 mEq/100 g was supplied
from Kunimine Industry Co. Japan, under trade name Kunipia-F.
Aminolauric acid and N,N-dimethylstearyl amine was purchased
from Tokyo Kasei, Co. Japan. Tyramine hydrochloride from Aldrich
Chemical Co. All chemicals were used without further purification.
2.2. Preparation of organoclays
2.2.1. Preparation of tyramine-modified clay (Tyr-MMT)
Sodium montmorillonite (10 g) was dispersed into 300 mL of
hot water (about 80 °C) by using mechanical stirrer. Tyramine
hydrochloride (3.47 g, 20 mmol) dissolved in water (20 mL) was
added portion-wise into suspension montmorillonite under stir-
ring at 80 °C for 5 h. The precipitate was collected by filtration,
washed several times with hot water 80 °C until no white precipi-
tate of AgCl was formed by the addition of 0.1 N AgNO3 to the fil-
trate. Finally, the precipitate was dried under vacuum at 80 °C for
24 h to yield tyramine modified montmorillonite (Tyr-MMT). The
resulted organoclay was sieved to get particles less than 63 mm.
2.2.2. Preparation of 12-aminolauric acid-modified clay (ALA-MMT)
ALA-MMT was prepared by applying the same method as Tyr-
MMT using Na-MMT (15 g,), HCl (23.4 mmol, 2.43 g) and amino-
lauric acid (23.4 mmol, 5.03 g). The resulted organoclay was sieved
to get particles less than 63 mm.
2.2.3. Preparation of N,N-dimethylstearyl amine-modified clay (DMS-
MMT)
DMS-MMT was prepared from Na-MMT (10 g,), HCl
(1.19 m mol, 0.045 g) and N,N-dimethylstearyl amine (1.19 mmol,
0.353 g) in 30 mL dist. The resulted organoclay was sieved to get
particles less than 63 mm.
2.3. Preparation of polybenzoxazine – clay hybrids
In our previous work benzoxazine was prepared as described
elsewhere [19]. Into 100 mL flask, Tyr-MMT (0.66 g, 5%) was dis-
persed in dodecyl amine (40 mmol, 7.41 g) at 80 °C. Then,
bisphenol-A (20 mmol, 4.56 g) and paraformaldehyde (80 mmol,
2.42 g) were added. The mixture was heated for 2 h at 120 °C. After
cooling a yellow viscous material was obtained. The synthesized
monomer-clay was cast over glass plates after treating with
dichloro dimethylsilane. The cast film was heated at 120 °C for
4 h under vacuum to remove any entrapped air bubbles, followed
by thermal gradual treatment at 130, 150, 200, and 220 °C for 1 h
at each. The obtained hybrid films have wine color.
Similarly, polybenzoxazine-clay hybrids containing different
content of ALA-MMT and DMS-MMT were prepared.
2.4. Coating application on metal samples [38–43]
The monomers of (B-dod/OMMTs) were dissolved in ethyl acet-
ate and sprayed on steel metallic plates and left in air for 5 h to
evaporate the solvent. The coating samples were thermally cured
in an air oven at 100, 130,170, 200, and 220 °C for 1 h at each to
have uniform cured coating thickness of about 20–30 lm mea-
sured in accordance to method described in ASTM. D3359-07.
2.5. Characterization
FTIR was performed by Perkin Elmer-1430, in a wave number
range of 4000–400 cm 1. Differential scanning calorimetry (DSC)
was carried out using a Rigaku calorimeter Thermo Plus 2 DSC
8230 at a heating rate of 10 °C/min 1 under nitrogen atmosphere.
Thermogravimetric analysis (TGA) Shimadzu TGA-50H at a heating
rate of 10 deg min 1 from 50 to 800 °C under nitrogen atmosphere
and the sample weight was about 8–10 mg. The morphology of the
nanocomposite was examined by X-Ray diffraction. X-ray analysis
was carried out using a Rigaku di Vractometer, with Cu K radiation,
at a general voltage of 30 kV and a general current of 15 mA.
Scanning was in continuous steps at a speed of 5 deg min 1, and
2h range of 2°–20°. Transmission electron microscope (TEM) on a
JEOL JEM-2000EX (Tokyo, Japan) at an accelerating voltage of
100 kV. Mechanical properties (tensile) of the samples were tested
with an Instron mechanical tester [model DL-35/LR5K plus
(LLOYD)] at crosshead speed of 500 mm min 1. The I-shaped
specimen were prepared with 5 cm in length, 1 cm width, and
330–450 lm in thickness. For each datum point, five samples were
tested, and the average value was recorded. The mechanical prop-
erties of coating (viz, adhesion, scratch hardness, pencil hardness
and impact resistance) were measured according to the methods
described in ASTM D3359-95 (B), ASTM D3363, ASTM D2794-93,
and ASTM D522-93a, respectively.
3. Results and discussion
3.1. Preparation of benzoxazine-clay materials
The preparation of organoclays (OMMT) is shown in Scheme 1.
Characterizations of organoclays were investigated by TEM & XRD
in Figs. 1 and 2, respectively. The transmission electron microscope
has clarified the nanostructure of silicate in organoclay (Tyr-MMT,
ALA-MMT & DMS-MMT) as shown in Fig. 1a-c, respectively. The
silicate layers are separated into some thin lamellas. The XRD
diffraction Fig. 2 showed peaks of Na-MMT lattice structure due
to d-spacing was shifted to lower angels by the modification with
tyramine (Tyr), aminolauric acid (ALA) and N,N-dimethylstearyl
amine (DMS) as intercalating agent. The original d-spacing of Na-
MMT (1.24 nm) is increased to 1.52 or 1.83 or 1.97 nm with mod-
ification with Tyr, ALA, and DMS, respectively. This suggests that
the interlayer spacing is increased by increasing the length of the
intercalating agent.
The method which is used for the preparation of
polybenzoxazine-clay nanocomposites in this study is based on
the in-situ formation of benzoxazine monomers in presence of
organoclay shown in Scheme 2. Benzoxazine-clay materials were
prepared by the reaction of bisphenol-A, dodecyl amine and
paraformaldehyde in the presence of organoclay (Tyr-MMT). IR
Cl MMT
H3C H3 C H3C
R Cl Na-MMT N R
N (CH2)17 CH3 N R
H3C H3C
H3C (CH2)17CH3 (CH2 )17CH3
OMMT
R: -HDMS, (CH2)11COOH (ALA) (H2C)2 OH Tyr
Scheme 1. Preparations of organoclays.
 S.M. El-Mesallamy / Egyptian Journal of Petroleum 28 (2019) 253–260
Fig. 1. TEM of a) Tyr-MMT, b) ALA-MMT & c) DMS-MMT.
spectra, shows the absorption bands at 932 cm 1 (trisubstituted
benzene), 1206 cm 1 (cyclic ether linkage), 1331 cm 1 (CH2 of
benzoxazine ring), and 1491 cm 1 are attributed to benzoxazine
structure. The absorptions at 554 and 1024 cm 1 are due to Si-O in
the framework structure of MMT layers [27]. Table 1 summarized
the composition of benzoxazine-clay nanocomposites monomer.
The curing behavior of benzoxazine in the presence of organoclays
was studied by DSC. Fig. 3 show the DSC of the pristine
benzoxazine(B-dod), polybenzoxazine (B-dod)/5%Tyr-MMT and
polybenzoxazine (B-dod)/10%Tyr-MMT. The neat benzoxazine
monomer (B-dod) has an exotherm with the maximum at 255 °C
while for polybenzoxazine (B-dod)/5%Tyr-MMT and polybenzox-
azine (B-dod)/10%Tyr-MMT an exotherm maximum was observed
at 229 and 219 °C respectively. The shift of the curing exotherm to
lower temperature for both polybenzoxazine (B-dod)/5%Tyr-MMT
and polybenzoxazine (B-dod)/10%Tyr-MMT than the neat resin is
due to the catalytic effect of the acidic onium protons inside the clay
galleries on the ring-opening polymerization of benzoxazines [27].
The polymerization of benzoxazine-organoclay materials was
followed by DSC and FTIR analysis. DSC of cured (B-dod)/10%Tyr-
MMT, the disappearance of the exothermic peak due to the ring
255
opening polymerization suggests the completion polymerization
of the hybrid material. Further curing conformation of polybenzox-
azine (B-dod)/10%Tyr-MMT was by FTIR spectra. Fig. 4 shows the
decrease of the absorption bands at 920, 1492 cm 1 (trisubistuted
benzene), 1240 cm 1 (ether linkage) and 1330 cm 1 (CH2 of ben-
zoxazine ring). While the absorption for tetra-substituted mode
at 1491 cm 1 is increased. The absorption at 558 and 1034 cm 1
present in all stages is attributed to Si-O in MMT layers [27].
3.2. Morphology of polybenzoxazine-clay nanocomposites
TEM provided evidence of Tyr, ALA & DMS intercalation inside
the clay galleries. The TEM photographs for (B-dod)/5%Tyr-MMT,
(B-dod)/5%ALA-MMT and (B-dod)/5%DMS-MMT are shown in
Fig. 5a-c, respectively, the photographs showed very good clay
dispersion with uniform distribution of silicate layers, leading to
exfoliation morphology.
The increase and collapse of the interlayer spacing of the
lattice structure of the layered silicates is often monitored by
XRD. Fig. 6 shows Tyr-MMT, polybenzoxazine (B-dod)/3%Tyr-
MMT, polybenzoxazine (B-dod)/5%Tyr-MMT, polybenzoxazine
256 S.M. El-Mesallamy / Egyptian Journal of Petroleum 28 (2019) 253–260

(B-dod)/10%Tyr-MMT and polybenzoxazine (B-dod)/20%Tyr-MMT

and the XRD of ALA-MMT, polybenzoxazine (B-dod)/3%ALA-MMT,
polybenzoxazine(B-dod)/5%ALA-MMT, polybenzoxazine(B-do
b d)/10%ALA-MMT, polybenzoxazine (B-dod)/20%ALA-MMT. The
absence of reflections in the XRD patterns of the hybrids indicated
that the lattice structure of OMMT was collapsed due to the
polymerized of polybenzoxazine into the gallery of organoclay.
a
XRD of polybenzoxazine (B-dod)/DMS-MMT, polybenzoxazine
Relative intenisty

(B-dod)/3%DMS-MMT, polybenzoxazine (B-dod)/5%DMS-MMT,

polybenzoxazine (B-dod)/10%DMS-MMT, (B-dod)/20%DMS-MMT
c
confirmed the sheets of silicate were homogeneously dispersed
into the polybenzoxazine matrix. This suggests the disorder and
loss of structure registry of the MMT layers.

Na-MMT
3.3. Mechanical properties of polybenzoxazine-clay nanocomposites

The tensile properties of polybenzoxazine (B-dod)/Tyr-MMT,

(B-dod)/ALA-MMT and (B-dod)/DMS-MMT were examined, and
the results are summarized in Tables 2–4. For polybenzoxazine
(B-dod)/Tyr-MMT series, the tensile properties changed with the
incorporation of Tyr-MMT. As the content of clay modified
increase, the tensile modulus also increases, the neat resin
2 4 6 8 10
polybenzoxazine (B-dod) was 6.9 MPa while the polybenzoxazine
2 (B-dod)/3%Tyr-MMT and polybenzoxazine (B-dod)/5%Tyr-MMT
were 7.34 and 8.46 MPa. However, the elongation at break
Fig. 2. XRD of a) Na-MMT, b) Tyr-MMT, c) ALA-MMT & d) DMS-MMT. decreased with the increase of Tyr-MMT content. For polybenzoxazine

CH3
HO (CH2)2 NH3 MMT + HO OH + HCHO + CH3(CH2)10CH2NH2
CH3

CH2(CH2)10CH3
N
CH2(CH2)10CH3 CH3
N O O
+
CH3
MMT H3N (H2C)2 O N
H3C(H2C)10H2C

MMT

(CH2)10 CH3
OH OH
CH2
OH OH N

N
CH2 + H3C CH3 H3C CH3
(CH2)10CH3

(CH2)2NH2 MMT (CH2)2 NH3 MMT N

CH2
OH OH
(CH2)10 CH3

MMT

Tyr-MMT-B-dod Hybrid

Scheme 2. Preparation of polybenzoxazine (B-dod)/Tyr-MMT.

 S.M. El-Mesallamy / Egyptian Journal of Petroleum 28 (2019) 253–260 257

Table 1
Composition of benzoxazine ((B-dod))-MMT nanocomposites.

Code Composition Condition

Clay Bisphenol-A (mml, g) Dodecyl amine (mml, g) Paraformaldehyde (mml, g)
Type g, wt
B-dod 00 00 20, 4.56 40, 7.4 80, 2.4 Solventless
A Tyr-MMT 0.32, 3% 20, 4.56 40, 7.4 80, 2.4 Solventless
B Tyr-MMT 0.66, 5% 20, 4.56 40, 7.4 80, 2.4 Solventless
C Tyr-MMT 1.41, 10% 20, 4.56 40, 7.4 80, 2.4 Solventless
D Tyr-MMT 3.18, 20% 20, 4.56 40, 7.4 80, 2.4 Solventless
E ALA-MMT 0.32, 3% 20, 4.56 40, 7.4 80, 2.4 Solventless
F ALA-MMT 0.66, 5% 20, 4.56 40, 7.4 80, 2.4 Solventless
G ALA-MMT 1.41, 10% 20, 4.56 40, 7.4 80, 2.4 Solventless
H ALA-MMT 3.18, 20% 20, 4.56 40, 7.4 80, 2.4 Solventless
I DMS-MMT 0.35, 3% 20, 4.56 40, 7.4 80, 2.4 Solventless
J DMS-MMT 0.58, 5% 20, 4.56 40, 7.4 80, 2.4 Solventless
K DMS-MMT 1.22, 10% 20, 4.56 40, 7.4 80, 2.4 Solventless
L DMS-MMT 2.82, 20% 20, 4.56 40, 7.4 80, 2.4 Solventless

219 o C
b
c
229 o C
b *
Exo 255 C o

a *
Heat flow

T%

a *
*

0 100 200 300

Temperature / oC 2000 1700 1400 1100 800 500

Fig. 3. DSC of a) polybenzoxazine ((B-dod)/, b) polybenzoxazine (B-dod)/5%Tyr- cm-1
MMT & c) polybenzoxazine (B-dod)/10%Tyr-MMT.

Fig. 4. IR spectra of polybenzoxazine (B-dod)/10%Tyr-MMT a) before curing & b)

(B-dod)/DMS-MMT series the tensile decreased and the elongation
increased. There was a tendency for this type of clay modifier,
where the long aliphatic chain has high flexibility and low Tg.
While the series of Tyr-MMT aromatic manner have high Tg thus
have high modulus and low elongation. However, nanocomposite
specimens containing Tyr-MMT has higher values than those with
DMS-MMT and ALA-MMT. For instance, the nanocomposites with
10 wt% of Tyr-MMT, DMS-MMT and ALA-MMT are 60% 45% and
15% higher strength than those with the neat resin B-dod,
respectively.
3.3.1. Mechanical properties of coating samples
The result in Table 5. Show the coating adhesion with the metal
substrate was examined by the crosscut adhesion test. The coat-
ings show 100% adhesion to the metal substrates as they reached
5B. This result could be attributed to the presence of free hydroxyl
groups and long aliphatic chains of the benzoxazine skeleton. The
free hydroxyl group forms hydrogen bonds with metal surfaces
and enhances the adhesion properties. The cohesion strength of
after curing.
coating particles was evaluated with impact resistance test. The
polybenzoxazine resin has impact resistance 90 lb.cm. However,
the polybenzoxazine nanocomposites rise up to 120 lb.cm. Due
to the loading of clay contents. Furthermore, pencil and scratch
hardness tests supported the obtained results. These results could
be correlated to the highly cross-linked network structure leading
to higher hardness properties. The (B-dod)/10%Tyr-MMT coating
has the highest hardness properties as compared the other B-
dod/10%DMS-MMT and (B-dod)/10%ALA-MMT coatings. This
behavior could be attributed to the aromatic ring of tyramine mod-
ified clay. The coatings show the pencil hardness 3H, 4H, 5H, 6H for
B-dod, (B-dod)/10%ALA-MMT, (B-dod)/10%DMS-MMT and (B-
dod/10%Tyr-MMT, respectively. The best result was obtained by
polybenzoxazine/10%Tyr -MMT with the highest wt % content of
clay loading as well as the best modifier type of coatings. This
behavior reflects the excellent balance maintained between the
softer segments of long aliphatic chains of amine molecules and
258 S.M. El-Mesallamy / Egyptian Journal of Petroleum 28 (2019) 253–260

Fig. 5. TEM of a) B-dod/5%Tyr-MMT, b) B-dod/5%ALA-MMT c) B-dod/5% DMS-MMT.

Table 2
Tensile properties of polybenzoxazine (B-dod)/Tyr-MMT hybrid.

Code Clay content % E modules at Break (MPa) Elongation at Break %

B-dod 0 6.9 2
A 3 7.34 1.8
B 5 8.46 1.4
20Tyr-MMT C 10 11.23 1.1
D 20 12.23 0.56
Relative Intenisity

10%Tyr-MMT

Table 3
Tensile properties of polybenzoxazine (B-dod)/ALA-MMT hybrid.
5%Tyr-MMT
Code Clay content % E modules at Break (MPa) Elongation at Break %
B-dod 0 6.9 2
3%Tyr-MMT A 3 7.15 1.89
B 5 7.89 2.21
C 10 8.32 2.35
D 20 9.33 2.55
Tyr-MMT

Table 4
Tensile properties of polybenzoxazine (B-dod)/DMS-MMT hybrid.

Code Clay content % E modules at Break (MPa) Elongation at Break %

2 3 4 5 6 7 8 9 10
B-dod 0 6.9 2
A 3 7.12 2.2
2θ
B 5 7.98 2.4
C 10 10.11 2.5
Fig. 6. XRD of Tyr-MMT, polybenzoxazine (B-dod)/3%Tyr-MMT, 5% Tyr-MMT, 10%
D 20 11.3 3.15
Tyr-MMT & 20% Tyr-MMT.
 S.M. El-Mesallamy / Egyptian Journal of Petroleum 28 (2019) 253–260 259

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