Characterization of Protective Performance of Epoxy Reinforced With Nanometer-Sized Tio and Sio

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Progress in Organic Coatings 62 (2008) 359–368

Characterization of protective performance of epoxy


reinforced with nanometer-sized TiO2 and SiO2
Hongwei Shi, Fuchun Liu, Lihong Yang, Enhou Han ∗
Environmental Corrosion Center, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
Received 31 May 2007; received in revised form 6 November 2007; accepted 19 November 2007

Abstract
Nano-TiO2 particles was uniformly dispersed and prepared into concentrated nano-paste. The effects of nano-TiO2 particles on the performance
of epoxy resin on 2024-T3 aluminum alloy were investigated. The effects of nano-SiO2 with ␥-glycidoxypropyltrimethoxy silane modification or
without modification on the performance of epoxy resin were also studied. It was found that the hardness of epoxy resin was improved by the
incorporation of 1 wt.% nano-TiO2 particles or nano-SiO2 . The results of electrochemical impedance spectrum (EIS) and salt spray test indicated
that the addition of nano-TiO2 /SiO2 significantly improved the corrosion resistance of epoxy resin. Fourier transform infrared spectra (FT-IR) proved
that the new absorptions at 1070 and 1090 cm−1 on silane-treated nano-SiO2 particles, which can evidence the ring structure of Si O Si. The
formation of layered ring structure of nano-SiO2 can be explained for the enhancement of the corrosion resistance and hardness of nano-SiO2 /epoxy
composite.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Electrochemical impedance spectrum; Nano-TiO2 ; Nano-SiO2 ; Glass transition temperature; Fourier transform infrared spectra

1. Introduction was improved by addition of 2% nano-Al2 O3 into epoxy


adhesive [6]. It is worth noting that most of the use of
Epoxy resin has been developed rapidly since invented, and nanoparticles was firstly treated with surface modification, and
are widely used in modern life [1–3]. The most important and then the nanocomposites were prepared by embedding or in
industrialized epoxy is bisphenol A, which is derived from situ polymerization. Bauer et al. [7] found that oligomeric
epichlorohydrin and consists of glycidol and hydroxyl groups siloxane structures presented on the surface of coated nanopar-
with ether bond on main chain. It is excellent in chemical resis- ticles by surface modification and covalent bond could form
tance, especially in acid and alkali resistance. Furthermore, it has between the surface-modified nanoparticles and the epoxy
high rigidity, heat and wear resistance [4,5]. It is widely used in resin, thus improving the thermal stability by shifting the
adhesive, electronic and coating industries due to the small vol- glass transition temperature. Zhang et al. [8] reported that
ume shrinkage in curing and outstanding electrical performance. ␥-glycidoxypropyltrimethoxy silane-modified nanosize silicon
The methylene in ether bond is prone to be photo-oxidized and dioxide could effectively improve the toughness and thermal
weak in photo-stability, so it is commonly used for primer matrix stability of cycloaliphatic epoxy resin. Zunjarrao et al. [9]
in coating industry. In aerospace industry, bisphenol A is com- compared the effect of nanometer- and micrometer-sized alu-
monly used as primer matrix on aluminum alloy 2024-T3 for minum particles on the fracture toughness and found that proper
protecting the surface of aircraft. silane treatment and improved particle dispersion resulted in
In the recent decade, some studies reported the modi- the enhancement of fracture toughness and the magnitude of
fied epoxy with nano-Al2 O3 , nano-SiO2 , nano-CaCO3 and increase of fracture toughness of epoxy was higher for addition
nano-TiO2 with improved properties [6–11]. For example, of 20–100 nm aluminum particles than that of 3–4.5 ␮m parti-
the adhesion between epoxy adhesive and steel substrate cles. In addition, nanoclay was also introduced into epoxy matrix
and endowed epoxy/clay composite significantly improved
physical and chemical properties [12,13]. It was found that the
∗ Corresponding author. Tel.: +86 24 23893841; fax: +86 24 23971525. toughness and stiffness were improved through the incorporation
E-mail address: ehhan@imr.ac.cn (E. Han). of nanoclay modified with silane [14].

0300-9440/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2007.11.003
360 H. Shi et al. / Progress in Organic Coatings 62 (2008) 359–368

Many new nanomaterial/epoxy composites have been substrates, respectively for mechanical measurement and accel-
reported in recent years and mechanical properties and thermal erated corrosion test. Panels for EIS experiment were 2024-T3
stability were found to be significantly enhanced by the addi- aluminum alloy with dimension of 50 mm × 50 mm. The sub-
tion of nanomaterials, however, little attention has been paid to strates were polished with 800 emery paper, then degreased with
the corrosion resistance of nanomaterial/epoxy composites. In TREP 44 cleaner solution for 5 min and deoxidized by chemi-
current work, the nano-TiO2 particles was firstly dispersed and cal solution (CrO3 0.36 kg, HNO3 0.773 kg, HF 40% 0.0878 kg,
prepared into nano-paste and then was incorporated into E20 water 8.78 kg). The coating films were coated by spreader bar
epoxy (bisphenol A) resin, and also nano-SiO2 was directly dis- and were dried at room temperature. The final thickness of
persed into or treated with surface modification, then dispersed the coated films was about 23 ± 3 ␮m for mechanical test and
into the epoxy resin. Four systems were studied: one without 30 ± 3 ␮m for corrosion test.
nanoparticles (varnish), one with nano-TiO2 particles, one with
nano-SiO2 particles and one with silane-treated nano-SiO2 par- 2.3. Characterization of DSC and FT-IR
ticles, respectively. The corrosion resistance of nano-TiO2 /SiO2
particles incorporated epoxy composites was investigated using Differential scanning calorimeter (DSC) was obtained using
electrochemical impedance spectra (EIS). In order to character- a NETZSCHSTA 449C Thermal Analysis System from −30
ize the performance change of epoxy resin with the addition of to 220 ◦ C at the heating rate of 10 ◦ C/min under nitro-
nanoparticles, the mechanical and thermal performance of the gen atmosphere. The data was analyzed by Perkin-Elmer 7
nanocomposites was also studied. FT-IR spectra were recorded Series Thermal Analysis System to obtain glass transition
for nano-SiO2 and silane-modified nano-SiO2 powder. temperature.
Fourier transform infrared (FT-IR) analysis was performed
2. Experimental on an IFS 55 spectrometer from Brucker with KBr pellets for
solid specimens.
2.1. Materials

E20 epoxy (bisphenol A) was used as matrix resin, supplied 2.4. Electrochemical test
by Shanghai Resin Factory. For blending epoxy resin and curing
agent, E20 was dissolved by additional xylene, butyl alcohol and All EIS measurements were carried out at room tem-
cyclohexanone with the same weight and the curing agent, 650# perature in 3.5% NaCl solution. Test system consisted of
polyamide resin, was prepared into solution with another 40% of a three-electrode cell, in which a saturated calomel elec-
xylene and butyl alcohol. The ratio of E20 epoxy to curing agent trode (SCE), a stainless steel electrode and a coated coupon
was 2.5:1. Nano-TiO2 particle has a round shape with diameter were used as reference, counter, and working electrodes,
from 20 to 40 nm. The nano-SiO2 particle is of round shape respectively. The exposed area of the coupons to the NaCl
with diameter approximately of 20 nm. The SEM photographs solution was 12.56 cm2 . Experiments were performed under
of nano-TiO2 and -SiO2 particles mixed in epoxy resin are shown the open circuit potential. EIS measurement instruments
in Fig. 1. The nano-sized powder was commercially purchased included an EG&G 273 Potentiostat/Galvanostat and an EG&G
from Zhejiang Yuda Chemical Co. Ltd. 5210 lock-in amplifier (0.5 Hz to 120 kHz) integrated with
a PC system. Impedance spectra of coupons in different
2.2. Preparation of substrates and coatings immersion times were recorded in 10−2 to 105 Hz fre-
quency range, with sinusoidal alternating potential signal of
Tinplates of 120 mm × 50 mm × 0.5 mm and 2024-T3 alu- 10 mV. The EIS data were analyzed with ZSimpwin soft-
minum alloy of 150 mm × 70 mm × 1.5 mm were used as ware.

Fig. 1. TEM micrographs of (a) nano-TiO2 without treatment, (b) nano-TiO2 in nano-paste, (c) nano-SiO2 without treatment, (d) silane-treated nano-SiO2 , dispersed
in epoxy resin.
H. Shi et al. / Progress in Organic Coatings 62 (2008) 359–368 361

2.5. Salt spray test

Salt spray exposure was performed according to ASTM


B117. The coated panels were exposed to a 5% NaCl solution
at 35 ± 2 ◦ C for 500 h. In this experiment, the AA 2024-T3 sub-
strates were coated with nanoparticles incorporated epoxy resin
(nano-TiO2 or -SiO2 /binder = 0.01). The panels were studied
under scratched (using X shape) condition.

3. Results

3.1. Preparation and characterization of epoxy/TiO2 and


epoxy/SiO2 nanocomposites

3.1.1. Preparation of nanocomposites


A practical problem often occurred in the preparation of
nanocomposites is the agglomeration of nanoparticles, so it is
of importance to uniformly disperse nanoparticles into organic
Fig. 2. Effect of TiO2 , treated SiO2 , and untreated SiO2 nanoparticles on the
matrix. In order to solve the problem of nano-TiO2 parti- DSC spectrum of E20 epoxy.
cles in epoxy coatings, nano-TiO2 paste was firstly prepared
[15]. The solvent, nano-TiO2 and dispersants were mixed, 3.1.3. DSC measurement
and then the mixture was ground to avoid the agglomeration Destreri et al. [16] reported that Tg (glass transition tem-
of nanoparticles. For nano-SiO2 , effects of direct dispersion perature) of high solid epoxy coatings is closely related to the
and silane surface modification followed by embedding were crosslinking degree: the higher crosslinking is, the higher Tg is.
compared. The detailed preparation process of surface mod- More compact structure of coatings can be obtained through
ification was as follows: 20 wt.% of nano-SiO2 was added improving crosslinking extent, which leads to better barrier
into KH560 (␥-glycidoxypropyltrimethoxy silane) solution performance against water permeation. A shift of the glass tran-
(KH560:water:ethanol = 2:49:49), then the mixture was heated sition temperature of about 20 K has been reported for 30 wt.%
at 80 ◦ C and stirred for 1 h, and eventually the mixture was nanoparticles incorporated epoxy system [7]. For low content
dried and ground to obtain the powder of nano-SiO2 . The pig- of nanoparticles, the glass transition temperature change of E20
ment/binder (P/B) used in the experiment was 1%. In the above epoxy/nanoparticle systems compared with epoxy resin is shown
process, firstly, the nano-TiO2 particles with diameter from 20 to in Fig. 2. The glass transition temperature results analyzed by
40 nm were dispersed in the solvent and dispersant to form nano- system software are given in Table 1. It is very interesting to
paste, which consists of high concentration of the nanoparticles, note that the second glass transition temperature appeared at
and then the nano-paste is incorporated into the coating forma- 89.4 and 91.01 ◦ C, respectively for nano-TiO2 and treated nano-
tion. The nano-TiO2 particles in the coating, shown in Fig. 1(b), SiO2 incorporated epoxy systems. The occurrence of the second
was found more separated than those directly dissolved in epoxy glass transition temperature could be attributed to the bonding
resin, shown in Fig. 1(a). This means the using of nano-paste is between epoxy resin and nanoparticles. For epoxy/nano-SiO2
an alternative way to promote the dispersing of nanoparticles in system, it was probably due to the interaction between epoxy
nanocomposites. The surface-treated nano-SiO2 particles with group on KH560 that linked with nano-SiO2 and epoxy resin.
diameter about 20 nm have bridge-linked structure, as seen in The effects of different nano-SiO2 contents on the second glass
Fig. 1(d), and were more also scattered than those untreated, transition temperature and the shift of the first glass temperature
shown in Fig. 1(c). will be further studied.

3.1.2. Mechanical property of incorporated epoxy varnish 3.2. Corrosion tests


For P/B = 0.01, the mechanical properties of nano-TiO2
and nano-SiO2 incorporated varnish were studied. The results 3.2.1. EIS measurements
showed that the varnish and nanoparticles incorporated varnish EIS measurement is based on the measuring of the impedance
are high in flexibility and impact resistance, and the values were spectrum over a period of immersion time to evaluate the bar-
1 mm and 120 kg cm, respectively. For hardness, it was 2H (pen-
cil hardness) for epoxy varnish. It was 3H for varnish with Table 1
nano-TiO2 , whereas it was 4H for varnish with nano-SiO2 . The Glass transition temperature of epoxy resin reinforced by 1 wt.% nanoparticles
improvement in hardness was probably due to the formation of
Tg (◦ C) Tg (◦ C)
a layered framework by the uniform and stagger distribution of
nanoparticles in coating film. The bridge-like layered framework Epoxy 23.078
structure of nano-SiO2 particles may contribute to the higher Epoxy + TiO2 24.26 89.4
Epoxy + treated SiO2 27.16 91.01
hardness of the nanocomposite than that of nano-TiO2 without Epoxy + untreated SiO2 27.337
linking.
362 H. Shi et al. / Progress in Organic Coatings 62 (2008) 359–368

rier effect and breakdown of coatings. The change of parameters explain the delamination and defect of coatings in present work,
in a simulated equivalent circuit is usually used to indicate the where C and R represent the diffusion capacitance and diffusion
change of structure and corrosion resistance of coatings. By cal- resistance, respectively. CPE is used to replace the capacitance
culating the change of values of the components in the simulated component in the equivalent circuit, so C, Cc and Cdl are substi-
equivalent circuit, the defect or delamination can be estimated tuted by Q, Qc and Qdl , respectively, in the fitting of impedance
quantitatively. The values of the parameter related with the high spectra in this work.
frequency part are Ccoat and Rcoat , which are considered to be
coating properties changed with the immersion time, and denote 3.2.1.1. EIS of epoxy resin and nano-TiO2 incorporated epoxy
coating capacitance and coating resistance, respectively. The resin. Fig. 4 presents the Bode diagram of epoxy varnish at
Ccoat value can be directly calculated by the following relation: different immersion times in 3.5% NaCl solution. With the
1 increasing immersion time, the modulus in low frequency (LF)
Ccoat = (1) range decreased steadily. Two apparent time constants were
2πfh Rcoat
apparently observed in the frequency–phase angle plot when
where fh is the frequency. Usually, the Ccoat increases with the immersed for 24 h, one in high frequency (HF) range related
immersion time in the initial period, and then remains approxi- with resistance and capacitance of polymer coating, the other
mately constant since the absorption of water becomes saturated in LF related with the reaction resistance and double-layer
even if the immersion time further increases. The Rcoat repre- capacitance. After immersed for 144 h, the modulus at 0.01 Hz
sents the coating resistance, and is inversely proportional to the decreased below 106 , and a horizontal line section appeared at
Ccoat . According to the equivalent circuits proposed by Zhang et middle frequency, which was the characteristic of delamination
al. [17], a series of equivalent circuits comprising Fig. 3(a) and of coating [18]. Taking into account the thickness of varnish,
(b), which represent corrosion process of an intact, water satu- the water was saturated in several hours and micro-cells were
rated epoxy coating on 2024-T3 alloy, are put forward, where formed on the substrate/coating interface. Delamination took
Rs denotes the solution resistance, Cc and Rc denote the electric place when more micro-cells grew up and linked together at this
capacitance and film resistance of the coating, respectively, Cdl time.
and Rct denote the double-layer capacitance and the charge trans- In order to verify the effect of nano-TiO2 on corrosion
fer resistance at the substrate/coating interface. With the increase resistance of epoxy varnish, impedance measurements were
of immersion time and accumulation of corrosion products at carried out for varnish in the presence of nano-TiO2 particles
metal/coating interface, a diffusion process was described in the on 2024-T3 aluminum alloy. For the system incorporated with
equivalent circuit as shown in Fig. 3(c), where Zw represents nano-TiO2 , it was clearly seen that only one apparent time con-
Warburg resistance. After long time of immersion in NaCl solu- stant was observed for 312 h of immersion as shown in Fig. 5.
tion, more time constants appear on the bode diagram, so a more By contrast with varnish, although the change trend of mod-
complex equivalent circuit as shown in Fig. 3(d) is introduced to ulus values at LF decreased with the immersion time, but the

Fig. 3. Equivalent electrical circuits.


H. Shi et al. / Progress in Organic Coatings 62 (2008) 359–368 363

Fig. 5. Bode plot of epoxy varnish with nano-TiO2 immersed in 3.5% NaCl
solution at different times.
Fig. 4. Bode plot of epoxy varnish immersed in 3.5% NaCl solution at different
times.

porated epoxy resin, the plot was characterized by a single


modulus values were much higher than those of varnish, sug- capacitive loop representative of resistance of coating as shown
gesting that the barrier effect of nano-TiO2 incorporated coating in Fig. 6(b).
was reinforced. It could be seen from Fig. 5 that the modu-
lus values at 0.01 Hz when immersed for 144 and 312 h were 3.2.1.2. EIS of varnish with untreated and treated nano-SiO2 .
approximately one order of magnitude higher than those of Figs. 7 and 8 present the Bode plots for epoxy varnish incorpo-
varnish. rated with non-treated and surface-treated nano-SiO2 immersed
The Nyquist plots obtained for varnish and nano-TiO2 incor- in 3.5% NaCl solution after different times. For epoxy varnish
porated varnish for different immersion times are given in with untreated nano-SiO2 , modification occurred steadily dur-
Fig. 6. For the epoxy varnish, water saturation was charac- ing the immersion period. With the increasing immersion time,
terized by two indistinct capacitance loops for 0 and 24 h the modulus value at LF part decreased, along with the slight
immersion, as shown in Fig. 6(a). However, with immersion decrease at HF part. After immersed for 192 h, the impedance
time up to 144 h, the results were quite different: two small modulus value decreased below 106 , indicating that the coat-
capacitance loops were observed, which indicated the break- ing film was defective and corrosion product had formed on
down of coating due to serious delamination and corrosion the substrate. It is clear that the time constants increased with
product accumulation. Additionally, a Warburg resistance, char- the immersion time from frequency–phase angle relationship in
acterized by a 45◦ slope after the second semi-circle, could the Bode plot. The equivalent circuit containing four time con-
be observed, indicating a diffusion process from substrate to stants was well fitted for the results of impedance plots after
coating caused by corrosion product. For the nano-TiO2 incor- immersion of 480 h. The increase of time constants showed the
364 H. Shi et al. / Progress in Organic Coatings 62 (2008) 359–368

Fig. 7. Bode plot of epoxy varnish with untreated nano-SiO2 immersed in 3.5%
Fig. 6. Nyquist plots for (a) epoxy varnish and (b) nano-TiO2 incorporated NaCl solution after different times.
varnish.

increase of delamination area and cross-sectional area of pores ded varnish are shown in Fig. 9. The coating resistance generally
[18]. With the increase of time, the delamination of coating film decreased with time. For treated nano-SiO2 coating, the coat-
grew up and corrosion product diffused from the substrate to ing resistance dropped at the first 24 h, and then a steady value
the electrolyte, characterized by the Warburg resistance at low above 108  was observed. For untreated nano-SiO2 coating,
frequency. however, the coating resistance steadily slowed down before
For varnish with treated nano-SiO2 , the magnitude of 480 h, and then maintained values approximately 103 order of
decrease of impedance value at LF was slight. In the immersion magnitude.
of 1128 h, the modulus value remained above 108 , two orders
higher than that of untreated nano-SiO2 at the end of immer- 3.2.2. Salt spray test
sion. Compared with varnish, the corrosion resistance of treated The corrosion resistance of incorporated epoxy was deter-
nano-SiO2 embedded epoxy was significantly improved. While mined by the rusts and blistering along the “X” marks on
for the epoxy varnish with untreated nano-SiO2 , the change 2024-T3 substrate. The aspects of epoxy resin, epoxy resin
trend of modulus value varied similarly with that of epoxy var- with nano-TiO2 , epoxy resin with untreated nano-SiO2 and with
nish, suggesting that the agglomeration of nano-SiO2 particles treated nano-SiO2 , after exposure in salt fog for 500 h, are shown
counteracted the barrier effect. An R (RC) circuit was still suc- in Fig. 10. After salt spray for 500 h, serious blistering appeared
cessfully fitted to simulate the components of equivalent circuit along the “X” marked for epoxy resin, with diameter of blis-
after 1128 h for treated nano-SiO2 incorporated varnish. ters more than 5 mm. However, no apparent blistering along the
The fitting results of the pore resistance as a function of marks was observed on the nano-TiO2 incorporated epoxy resin
immersion time for the untreated and treated nano-SiO2 embed- surface. Similar situation occurred in treated nano-SiO2 incorpo-
H. Shi et al. / Progress in Organic Coatings 62 (2008) 359–368 365

Fig. 9. Evolution of pore resistance of epoxy varnish incorporated with treated


and untreated nano-SiO2 immersed in 3.5% NaCl solution.

rated epoxy resin surface. However, small blisters with diameter


of 0.2–1 mm could be observed for untreated nano-SiO2 incor-
porated epoxy resin. The corrosion results coincided with the
impedance spectra, implying that the addition of nanoparti-
cles can effectively prevent the epoxy resin from blistering and
delamination.

4. Discussion

Results of salt spray test evidenced the better protective per-


formance of epoxy coatings with addition of nano-TiO2 and
Fig. 8. Bode plot for epoxy resin with surface-treated nano-SiO2 immersed in treated nano-SiO2 than the varnish and untreated nano-SiO2
3.5% NaCl solution after different times. incorporated epoxy coating. Comparison of EIS results shows
that the efficiency of the improvement of corrosion resistance
for embedding nano-SiO2 is higher than that of nano-TiO2 ,

Fig. 10. Aspects of (a) epoxy varnish, (b) varnish with nano-TiO2 , (c) varnish with untreated nano-SiO2 , (d) varnish with treated nano-SiO2 , after exposure in salt
spray for 500 h.
366 H. Shi et al. / Progress in Organic Coatings 62 (2008) 359–368

Fig. 12. Schematic illustration of the layered bridge structure of nano-SiO2 ,


crosslinked by KH560.

structure produced is shown in Fig. 12. In this work, the ground


Fig. 11. Crosslinking of nano-SiO2 particles by KH560. nanoparticles after surface treatment formed a macroscopical
structure as shown in Fig. 1(d). The crosslinking of nano-SiO2
particles corroborated the reactions described above on macro-
which is indicated by the higher coating resistance in LF part scale. Such a structure would contribute to the improved stiffness
in the immersion period. Considering the reinforced corrosion and toughness of dry coating film. For epoxy resin, the embed-
resistance for nano-SiO2 /epoxy resin, it could be explained ding of treated nano-SiO2 increases the resistance of the water
by the bonding between nano-SiO2 particles and silane. In and ion transportation. Meanwhile, the transport path is length-
this experiment, ␥-glycidoxypropyltrimethoxy silane, KH560 ened due to the framework structure. The deduced models for
[(OCH2 CH)CH2 OCH2 CH2 CH2 ]Si(OCH3 )3 , was used to mod- water and ion transportation in nano-SiO2 and -TiO2 epoxy
ify the surface of nano-SiO2 . Linking between nanoparticles and resin coatings are given as shown in Fig. 13. As the mod-
silane may originate from the reaction of the hydroxy bonds on els illustrated, the nano-SiO2 particles has formed a layered
the surface of nano-SiO2 particles with silane coupler. Thus, framework structure in the coating film as shown in Fig. 13(a).
silane surface treatment is appropriate for nano-SiO2 , which The probable reasons that such a structure brings to the corro-
is abundant in active hydroxyls [19]. If it was speculated that sion resistance of epoxy coating are ascribed to the following
there were X hydroxyls in one SiO2 particulate and all the OH aspects. First, the coating is more compact due to the framework
sites could theoretically react with the methoxy groups on silane of layer nano-SiO2 particles, thus the resistance for water and
molecules, X − 1 hydroxyls would be remained after the reac- Cl− transportation becomes stronger. Second, due to the length-
tion between the silanol which hydrolyzed by the silane and ened transport path, water and Cl− are more difficult to arrive
nano-SiO2 particle as reaction (1) showed. Then the remained at the coating/substrate interface. Accordingly, the bubble and
hydroxyls could continue to react with another silanol, forming delamination are difficult to occur to destroy the stable structure.
a structure with another silanol, X − 2 hydroxyls left. Further- Compared with nano-SiO2 , nano-TiO2 incorporated epoxy resin
more, due to the existence of the two hydroxyls on the product of should bear inferior anticorrosion performance due to the lower
reaction (2) or (3), the other nano-SiO2 particle would react with barrier effect and shorter path for water and Cl− transporta-
the product and form a more complex structure shown as (4). tion, as shown in Fig. 13(b). While for untreated nano-SiO2 , as
As a result, a slab of X silane molecules would cover the surface shown in Fig. 13(c), the transportation path is shorter due to the
of one nano-SiO2 particle and a network structure of nano-SiO2 agglomeration of nanoparticles comparing with treated nano-
particles could be formed through crosslinking through silane as SiO2 , which results the worse corrosion resistance as reflected
depicted in Fig. 11. A simulated three-dimensional framework in Fig. 9.

Fig. 13. Schematic models of the transportation of H2 O and Cl− in (a) silane-treated nano-SiO2 , (b) dispersed nano-TiO2 , and (c) untreated nano-SiO2 incorporated
coatings.
H. Shi et al. / Progress in Organic Coatings 62 (2008) 359–368 367

nano-SiO2 , it was two-order higher than that of untreated nano-


SiO2 at the end of immersion, above 108 . Meanwhile, the
hardness for nano-SiO2 and nano-TiO2 incorporated epoxy var-
nish was improved to, respectively 3H and 4H, tougher than that
of varnish (2H). Also, it was interesting to find that the sec-
ond glass transition temperatures at 89.4 and 91.01 ◦ C occurred
for nano-TiO2 and treated nano-SiO2 incorporated epoxy
resin.
The mechanism for the improvement of corrosion resis-
tance and mechanical performance of nano-SiO2 /epoxy resin
can be ascribed to the formation of a layered framework. Multi-
hydroxyls on nano-SiO2 particle promoted the construction of
Fig. 14. FT-IR spectra of nano-SiO2 and silane-treated nano-SiO2 . crosslinking structure, facilitated by silane coupler. The structure
of crosslinked nano-SiO2 particles in micro-scale contributed

(1)

(2)

(3)

(4)
Fig. 14 shows the IR absorption curves of nano-SiO2 and
silane-treated nano-SiO2 . The wide absorptions at peak of
to the compact nanocomposite coatings, which made water
3400 cm−1 indicated the abundance of OH on the surface of
and chloride ion hard to transport and reduced the trend for
nano-SiO2 powder. However, the corresponding peak shrank at
blistering and delamination so that the corrosion resistance
the silane-treated nano-SiO2 curve, representing the most of
was improved. The effect of this improvement was prefer-
hydroxyls were used up as the reaction (3) and (4) described
able, as well as in hardness, comparing with the nano-TiO2
above. The obvious wide absorption at peak of 1110 cm−1 on
particles.
nano-SiO2 curve showed the dissymmetry flexible vibration of
Si O Si. New absorptions at 1070 and 1090 cm−1 appeared at
treated nano-SiO2 IR curve comparing with that of nano-SiO2 Acknowledgment
powder, which is the characteristic of formation of ring structure
The authors gratefully acknowledge the financial support
with more than five Si O Si, indicating the layered frame-
from the National Natural Science Fundation of China (No.
work structure formed by reaction between SiO2 and KH560
50499334).
on molecular scale.

5. Conclusions References

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