Characterization of Protective Performance of Epoxy Reinforced With Nanometer-Sized Tio and Sio
Characterization of Protective Performance of Epoxy Reinforced With Nanometer-Sized Tio and Sio
Characterization of Protective Performance of Epoxy Reinforced With Nanometer-Sized Tio and Sio
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
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
3. Results
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. 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.
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
4. Discussion
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. 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
(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.
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