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Modification of TiO2 nanotubes with

3-aminopropyl triethoxysilane and its
Cite this: DOI: 10.1039/c8nj00642c
performances in nanocomposite coatings†
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a
Hong Phan Duong, Chia-Hsiang Hung,b Hung Cuong Dao,c Minh Duc Led and
Chia-Yun Chen *b

Until now, mono-dispersion of nanofillers, such as TiO2 nanotubes, in a polymer matrix remained a
major challenge in the preparation of polymer nanocomposites. To improve the dispersion capability of
TiO2 nanofillers in the epoxy matrix, the surfaces of TiO2 nanotubes were successfully modified with
3-aminopropyl triethoxysilane (APTS) by a facile aqueous process. The weight loss of APTS-grafted TiO2
nanotubes could be attributed to three main contributions: dehydration of adsorbed water, physical
adsorption of APTS and thermal decomposition of APTS chains. In addition, transmission electron
microscopy (TEM) images of APTS-grafted TiO2 nanotubes further evidenced a tubular shape with no
destruction before and after grafting treatment. Furthermore, the APTS-grafted TiO2 nanotubes were used as
the white pigment for preparing the epoxy-based coatings. It was found that the amine group on nanotube
surfaces, which mediated as a curing agent, coordinated with the epoxy group through covalent bonding,
thus allowing improved composite formation between the nanotubes and the epoxy matrix. The effects of
APTS-grafted TiO2 nanotubes on the mechanical, thermal and corrosion resistances of epoxy coatings were
Received 5th February 2018, examined. From detailed mechanical characterizations, it was revealed that the performances of pull-off
Accepted 4th April 2018 adhesion, impact resistance and bending resistance of the APTS-grafted TiO2 nanotubes/epoxy coatings were
DOI: 10.1039/c8nj00642c greatly improved compared with the unmodified TiO2-based coating with the same 5% additive content. In
addition, the resulting thermal properties and corrosion resistances of the epoxy resin were significantly
rsc.li/njc improved due to the enhanced reinforcement of APTS-grafted TiO2 nanotubes within the epoxy matrix.

Introduction method,8 method involving anodizing of metal substrates9,10

and the Kasuga method11,12 have been investigated to synthesize
Titanium dioxide (TiO2) has been considered as one of the most TiO2 with controlled nanotubular features.13 It was found that
important oxide materials for wide applications in additives, nanoscale TiO2/epoxy composites exhibited enhanced stiffness,
coating, and the photodegradation of organic pollutants.1–5 toughness and scratch resistance compared to microscale TiO2/
Incorporation of TiO2 fillers with epoxy resins has been shown epoxy structures under similar filler ratios. Recently, Saeed et al.
to greatly improve the anticorrosion performance of epoxy have reported that the TiO2 tubular fillers as an inert lamellar
composites. To further strengthen the desired performances pigment could orientate themselves parallel to the substrate
of epoxy polymers, recent studies have demonstrated that TiO2 surfaces and improve the anti-corrosion behaviors by acting as
nanotubes with large surface areas and improved mechanical a barrier to water and oxygen from the environment.14
properties compared to bulk TiO2 additives are particularly Although TiO2 nanotubes exhibited many superior material
promising because TiO2 is inexpensive, harmless and chemically properties as additives, their practical features corresponding
stable. Many methods including replica method,6,7 template to device performance are strongly correlated with the proces-
sing challenges, which mainly arise from the poor management
a
The University of Danang, University of Science and Technology, of their morphologies and microstructures when filling into the
54 Nguyen Luong Bang, Vietnam polymeric matrix. This is because the electrostatic van der Waals’
b
Department of Materials Science and Engineering, National Cheng Kung forces between nanotubes strongly induce agglomerations due to
University, Tainan 701, Taiwan. E-mail: [email protected]
c
their large surface areas. More critically, the highly viscous polymer
The University of Danang, University of Education, 459 Ton DucThang, Vietnam
d
Institute of Occupational Safety and Health & Environmental Protection in Central
matrix might further hinder the uniform dispersion of TiO2-
of VietNam, 178 Trieu Nu Vuong, Vietnam nanotube additives.15 Therefore, the resulting composite behaviors
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c8nj00642c of TiO2 nanotubes/epoxy structures have been hampered by the

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involved dispersion methods, acting as decisive factors that have Detailed morphologies of the modified TiO2 nanotubes were
dominated the eventual material characteristics.16 To overcome characterized with transmission electron microscopy (TEM,
these issues, much effort has been directed towards minimizing JEOL JEM1010). The grafting of APTS on TiO2 nanotubes was
the additive agglomeration and to achieve dispersion stability of examined with attenuated total reflection Fourier transform
TiO2 nanotubes in the epoxy matrix through mechanical stirring. infrared spectroscopy (ATR-FTIR, Bruker Alpha-E FTIR, Germany)
One such method seemed to work reliably, but strongly relied on to identify the surface compositions of modified TiO2 nanotubes.
good surface modification of the TiO2-nanotube structures that Preparation of TiO2/epoxy coatings. Typical two-component
facilitated the sound contact of inorganic TiO2-nanotube additives epoxy resins modified with bisphenol A (D.E.R. 331, DOW) and
with the organic resin matrix.17 Coupling agents such as MPS, triethylene tetraamine (D.E.H. 24, DOW) as a curing agent were
APTS, n-PTMS and IPTMS were utilized that could supply the utilized. To prepare the nanocomposites, the first step was to
chemical linkages and assist the formation of well-dispersed uniformly disperse various contents of synthesized TiO2 nano-
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nanotubes within the polymer matrix. Nevertheless, despite these tubes within the epoxy matrix through ultrasonic oscillation
findings, a complete understanding of coating characteristics, (Sonics, VC-505). Subsequently, the formulated epoxy resin was
including mechanical, thermal and corrosion resistances, is mixed with the D.E.H. 24 curing agent. Mild steel (normal steel
lacking, which hinders practical utilization of such composites. SPCC JISG 3141) panels were sequentially polished with abrasive
Thus, in this study, we aimed to explore the feasibility of papers (400, 800, 1000 grades) and then degreased with acetone
applying 3-aminopropyl triethoxysilane as a grafting agent that prior to the spraying process. All epoxy-based nanocomposites
modified the TiO2 nanotubes for the preparation of nanocomposite were deposited onto the as-cleaned steel panels through a con-
coatings. Systematic characterizations to identify successful ventional spray process. Well-controlled composite films with
modifications of TiO2 nanofillers were performed. Moreover, uniform thickness of 30  5 mm were prepared for evaluating
the improved mechanical, thermal and corrosion resistances of their thermal, mechanical and corrosion properties. For evaluating
our designed nanocomposite coatings were identified with their thermal and mechanical properties, the as-prepared samples
standard examination analysis. of pure TiO2 nanotubes and modified TiO2 nanotubes with various
filler contents of 1, 3, 5, and 7 wt% APTS were used. TGA
measurements were performed for testing the thermal properties
Experimental details of composite coatings. In addition, the corresponding mechanical
Materials properties of films made with unmodified and modified nano-
tubes/epoxy nanocomposites were evaluated using the standard
All chemicals used during grafting treatments were obtained American Society for Testing Material (ASTM) method. The
from Aldrich. Titanium dioxide powder (P25) from Sigma-Aldrich measurements were carried out under a constant flow of nitrogen
had an average particle size of 21 nm.18 Well-defined TiO2 of 50 mL min 1, and the furnace temperature was raised from
nanotubes were synthesized by Kasuga’s hydrothermal method 30 1C to 700 1C at a constant heating rate of 10 1C min 1.
with a narrow range of diameters within 10–20 nm and lengths of Furthermore, ATR-FTIR spectroscopy was utilized to characterize
100–150 nm. APTS, which was used as a silane coupling agent and the changes in the molecular structures of the grafted polymers.
an epoxy curing agent, was also purchased from Sigma-Aldrich. Panels with a fixed dimension of 200 mm  70 mm  1 mm
D.E.R.331 (Dow, USA) liquid epoxy resin was a liquid reaction were utilized for all mechanical characterizations, including the
product of epichlorohydrin and bisphenol A with a molecular mass adhesion pull-off test, impact resistance, film hardness, and
of 182–192. Epoxy curing agent was also purchased from Dow, USA bending resistance following the ASTM D4541-02, D2794, D3363,
(D.E.H.24). Mild steel (Normal steel SPCC JISG 3141) panels were and D522 methods, respectively. The as-prepared panels were used
used as the base metal in these investigations. for the following measurements: (a) the adhesion pull-off test
(ASTM D4541-02) was determined by a hydraulic pull-off adhesion
Method and characterizations tester (Sheen, UK); (b) the impact resistance was tested by drop-
APTS-grafted TiO2 nanotube preparation. Grafted modification ping a 0.9 kg steel ball from various heights (Erichsen impact
of TiO2 nanotubes was carried out in the liquid phase. Generally, tester 304, ASTM D 2794); (c) film hardness was determined by
3 g of TiO2 nanotubes was dispersed in 100 mL toluene under using the Erichsen 293 pencil test (ASTM D 3363); (d) flexibility
ultrasonication for 10 min. Then, 200 wt% of the silane coupling (bending) resistance (ASTM D522) was measured by using a
agent (APTS) was added into the dispersed solutions and refluxed 10 mm cylindrical mandrel bending tester from Erichsen 266S.
in a three-necked round-bottom flask at 70 1C. After 8 h, the The panels were also used for conducting the salt spray test (Model
modified powders were washed three times with isopropyl alcohol SAM Y90) under the standard criteria ASTM B117.
and deionized water to remove excess organosilane.19–23 The
collected precipitates were dried in a low-pressure oven at
100 1C for 24 h. The thermal behavior of APTS grafted TiO2 Results and discussion
nanotubes was determined by thermo-gravimetric analysis
(TGA, Perkin Elmer STA 6000) and the as-prepared composites Schematic procedures for surface modification on nanotubes
were heated from room temperature to 700 1C with a heating through chemical treatment between TiO2 nanotubes with
rate of 10 1C min 1 under a dynamic flow of nitrogen gas. 3-aminopropyl triethoxysilane are presented in Fig. 1. In the

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Fig. 1 Schematic illustrations for the grafting processes of APTS on the

TiO2-nanotube surfaces.
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mixing process, the hydrolysis of APTS occurred, followed by

the condensation of hydrolyzed APTS with the OH groups of the Fig. 3 FTIR spectra of various TiO2 nanotubes: (a) unmodified TiO2
TiO2 nanotubes, as shown in scheme 2 of Fig. 1.20,24–26 It should nanotubes and (b) APTS-modified TiO2 nanotubes.
be noted that the modification processes were performed in a
non-aqueous phase, mostly toluene,17,27 which was critical for the
formation a monolayer graft by avoiding the hydrolysis of APTS Table 1 Summary of FTIR spectra in the investigation of the functional
molecules within the modification treatments. TEM investigations groups of APTS-grafted TiO2 nanotubes
of the as-prepared TiO2 nanotubes are presented in Fig. 2, showing Wavenumber
the uniform tubular shapes of APTS-modified TiO2 nanotubes.18 No. (cm 1) Peak assignment22
Both the nanotube lengths (80–150 nm) and diameter (10–20 nm) 1 945 Ti–O–Si stretching vibration
remained unchanged after APTS modification in the grafting 2 1076 Si–O asymmetric flexible vibration
process. The corresponding SEM images are presented in the ESI.† 3 1430, 1510 Main characteristic peaks of Si–O–C bonds
4 1620 N–H bending vibration of primary amines (–NH2)
Transmission FTIR spectra of TiO2 nanotubes with and without 5 1170 C–N bond
APTS modifications were compared, as shown in Fig. 3. We can 6 2830 Symmetrical stretching vibration C–H
clearly observe that the major peak is located below 700 cm 1, 7 2930 Asymmetrical stretching vibration C–H
which confirmed the presence of Ti–O–Ti groups.28 The broad
absorption band between 3400–3200 cm 1 and the low-intense
resulting weight loss dominantly occurred between 50 1C and
dip at 1640 cm 1 correspond to the stretching vibration of water
160 1C, arising from the elimination of the adsorbed water at
and the hydroxyl group (–OH) on the nanotubes surfaces,
large-area nanotube surfaces. When the temperature was higher
respectively.29,30 In addition, there is a series of explicit absorption
than 160 1C, the absorbed water could be completely removed and
dips at 945 cm 1 (Ti–O–Si stretching vibration), 1076 cm 1 (Si–O
the contributions of dehydroxylation were trivial compared with
asymmetric flexible vibration), 1170 cm 1 (C–N bond), 1430 cm 1
the weight loss resulting from the adsorbed APTS on APTS-grafted
and 1510 cm 1 (Si–O–C bonds), indicating that APTS molecules
TiO2 nanotube surfaces, as represented as curve (b) in Fig. 4.33 For
were grafted onto TiO2 nanotubes,31,32 as summarized in Table 1.
APTS-grafted TiO2 nanotubes, the physically adsorbed APTS was
Table 1 summarizes the assignments for the main FTIR bands of
the APTS-grafted TiO2 nanotubes. These experimental results
of ATR-FTIR spectra indicated that APTS chains have been
successfully grafted onto TiO2 nanotubes.
To evaluate the amount of grafted APTS on TiO2 surfaces,
TGA characterizations were investigated, as presented in Fig. 4.
Without APTS grafting, denoted as curve (a) in Fig. 4, the

Fig. 2 (a) Representative TEM image and (b) high magnification TEM image Fig. 4 TGA analysis of TiO2 nanotubes (curve (a)) and APTS-grafted TiO2
with measured lengths of as-prepared APTS-grafted TiO2 nanotubes. nanotubes (curve (b)).

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Fig. 5 Scheme of the epoxy-amine reaction for the graft polymerization

of NH2 groups on the APTS-grafted TiO2-nanotube surfaces with epoxy
resin. k1 and k2 corresponded to the non-catalyzed kinetic constants for
the addition of primary and secondary amines, respectively.
Fig. 7 TGA curves of (a) 5 wt% TiO2 nanotube/epoxy nanocomposite coatings;
(b) 5 wt% APTS-grafted TiO2 nanotube/epoxy nanocomposite coatings.
desorbed within 200 1C and 330 1C, which corresponds to the
boiling point (217 1C) of the APTS chains.34 These grafted APTS
molecules were then thermally decomposed at high temperature, band at around 3300–3600 cm 1 in the spectra could be
predominantly within the temperature range of 450 1C to 600 1C. ascribed to the –OH groups of the epoxy resin.39–42 These
The involved chemical grafting of silane chains is illustrated findings were supported by the observation of new peaks at
in Fig. 5. It can be clearly seen that the –NH2 groups on the 1040 cm 1, associated with the C–N stretching vibration.42 This
modified TiO2 nanotubes interacted with epoxy groups (–CO–) indicated that the C–O–C oxirane groups of D.E.H. 24 epoxy
of the epoxy D.E.H. 24, thus forming a strongly linked have been completely converted to the epoxy amine.
poly(APTS-grafted TiO2 nanotubes/bisphenol A). TGA analysis was carried out to study the effects of modified
Fig. 6 presents the ATR-FTIR spectra of TiO2 nanotubes/ TiO2 nanotubes on the thermal stability of the epoxy nano-
epoxy coatings.35–37 The peaks at 830, 920 and 1245 cm 1 were composites. The results are presented in Fig. 7, showing the
assigned to C–O–C, C–O and C–O–C stretching of the epoxy characteristic TGA plots of the epoxy matrix with nanofillers
oxirane and ether group, respectively. The ATR-FTIR spectrum containing 5 wt% of pure TiO2 nanotubes or 5 wt% of APTS-
recorded from APTS-grafted TiO2 nanotubes/ epoxy coatings grafted TiO2 nanotubes, respectively. The obtained results
was also presented.38 It was observed that the intensities of revealed that the thermal stability of 5 wt% APTS-grafted TiO2
the vibration band of the terminal epoxy groups (830, 920, nanotubes/epoxy nanocomposites was higher than that of the
1245 cm 1) decreased, indicating the partial ring-opening of 5 wt% TiO2 nanotubes/epoxy nanocomposites. This was because
the epoxy groups. In addition, the presence of an absorption the amine groups on the APTS-grafted TiO2 nanotubes behaved
as a curing agent, which could actively coordinate with the
epoxy group of the polymer chains via covalent bonding, as
shown in Fig. 5. Thus, the amine groups facilitated the separation
of nanofillers within the epoxy matrix and inhibited the possible
aggregation of TiO2 nanotubes. In addition, the summarized TGA
results of TiO2 nanotubes/epoxy nanocomposite coatings and
APTS-grafted TiO2 nanotubes/epoxy nanocomposite coatings
were shown in Table 2. It could be observed that nanocomposites
loaded with 1–5 wt% TiO2 nanotubes experienced 10% weight
loss in the temperature range of 333 1C and 337 1C. However, in
case of the APTS-grafted TiO2 nanotubes with similar loadings
from 1–5 wt%, the decomposition temperature significantly
increased up to the range of 340–343 1C. Also, the amount of
residual char at 600 1C was in the range of 12.5–16.7 wt% for the
nanocomposites with 1–5 wt% of unmodified TiO2 loading, but
this amount increased to 14.3–19.3 wt% for those with 1–5 wt%
of APTS-grafted TiO2 loading. Thus, it could be clearly inferred
Fig. 6 ATR-FTIR spectra of (a) TiO2 nanotube/epoxy coatings and (b) that the presence of the amine group on the TiO2 nanotubes
APTS-grafted TiO2 nanotube/epoxy coatings. through effective grafting treatment could substantially improve

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Table 2 Summarized TGA results of TiO2 nanotubes/epoxy nanocomposite coatings and APTS-grafted TiO2 nanotubes/epoxy nanocomposite coatings
with different contents

Nanocomposite Temp. of 10% weight loss Td (1C) Temp. of 80% weight loss Td (1C) Residual char at 600 1C (wt%)
1 wt% TiO2 nanotubes 333 434 12.5
3 wt% TiO2 nanotubes 337 483 15.5
5 wt% TiO2 nanotubes 336 487 16.7
7 wt%TiO2 nanotubes 343 618 20.5
1 wt% APTS-grafted TiO2 nanotubes 340 447 14.3
3 wt% APTS-grafted TiO2 nanotubes 341 450 16.6
5 wt% APTS-grafted TiO2 nanotubes 343 580 19.3
7 wt% APTS-grafted TiO2 nanotubes 343 605 20.4
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the thermal stability of the nanocomposites by raising the cross- when pure TiO2 nanotubes were used as nanofillers (Fig. 8(a)).
linking densities, as illustrated in Fig. 5. However, it should be However, such undesired blisters could not be found near
noted that with the same amount of nanofiller loading (7 wt%), scribes at interfaces of grafted nanofiller/epoxy coatings and
the thermal stability of the unmodified and modified TiO2 the underlying steel substrates, as evidenced in Fig. 8(b). This
nanotubes/epoxy nanocomposites at 600 1C is fairly similar. This test demonstrated that the modified TiO2 nanotubes could
finding can be understood by considering the thermodynamics: positively improve their anti-corrosion behaviors for practical
the agglomeration of nanofillers become the dominant needs. Good dispersion of the grafted TiO2 nanotubes gave rise
phenomenon during both with or without grafting treatment to the strengthened chemical junctions within the polymer
due to the substantial addition of TiO2 nanofillers. matrix, thus inhibiting the possible diffusion of cracks or
The mechanical properties of unmodified and modified- defects in such strongly bonded nanocomposites. Based on
TiO2 nanotubes/epoxy nanocomposite coatings were evaluated the findings from the detailed salt-spray test, Fig. 9 illustrates
using the American Society for Testing Materials (ASTM) standard the anticorrosion mechanism in the APTS-grafted TiO2/epoxy
test method.16,43 The resulting data are summarized in Table 3. nanocomposite coatings.45,46 The presence of the APTS-grafted
First, the evaluation of the adhesion pull-off test (ASTM D4541-02)
indicated that the pull-off strength of the APTS-grafted TiO2
nanotubes/epoxy nanocomposite coatings was better than that of
the unmodified TiO2 nanotubes/epoxy nanocomposite coatings.
Next, from the impact resistance test (ASTM D2794), represented
with the drop heights, we found that the grafted TiO2 nanotubes/
epoxy coating still demonstrated improved impact resistance
compared to the pure TiO2 nanotubes /epoxy-based coating.
Furthermore, the film hardness by the pencil test (ASTM D3363)
of the grafted TiO2 nanotubes/epoxy coatings was slightly lower
compared to that of the TiO2 nanotube/ epoxy coatings. These
results indicated that the epoxy resin became more flexible
because the surface of the TiO2 nanotube was thoroughly
covered with APTS chains, leading to the reduced initial hardness
of TiO2 nanotubes.44 Finally, the flexibility test (ASTM D522)
evidenced that the flexibility performances of these composite
coatings were comparable because of no visible cracks were
created during flexibility explorations. Fig. 8 Salt-spray corrosion test after 500 h exposure: (a) epoxy/5 wt%
The salt spray test results are presented in Fig. 8. After 500 h TiO2 nanotube based coatings, (b) epoxy/5 wt% APTS-grafted TiO2 nano-
of exposure, numerous blisters appeared near the scratches tube based coatings.

Table 3 Mechanical-resistance performance of nanocomposite coated panels (200 mm  70 mm  1 mm)

Samples Flexibility Hardness (N) Adhesion (MPa) Impact (cm)

1 wt% TiO2 nanotubes Pass 3 2 40
1 wt% APTS-grafted TiO2 nanotubes Pass 3 2 40
3 wt% TiO2 nanotubes Pass 4 2 40
3 wt% APTS-grafted TiO2 nanotubes Pass 3 2.5 50
5 wt% TiO2 nanotubes Pass 5 3 55
5 wt% APTS-grafted TiO2 nanotubes Pass 4 3.5 75
7 wt% TiO2 nanotubes Pass 6 4 65
7 wt% APTS-grafted TiO2 nanotubes Pass 6 4 65

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