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Eects of Nano Pigments on the Corrosion Resistance of Alkyd Coating

Hongwei SHI, Fuchun LIU, Enhou HAN and Yinghua WEI
Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
[Manuscript received January 12, 2007, in revised form April 3, 2007]

Alkyd coatings embedded with nano-TiO2 and nano-ZnO pigments were prepared. The eects of nano pigments on anticorrosion performance of alkyd coatings were investigated using electrochemical impedance spectrum (EIS). For the sake of comparison, the corrosion protection of alkyd coatings with conventional TiO2 and ZnO was also studied. It was found that nano-TiO2 pigment improved the corrosion resistance as well as the hardness of alkyd coatings. The optimal amount of nano-TiO2 in a colored coating for corrosion resistance was 1%. The viscosities of alkyd coatings with nanometer TiO2 and ZnO and conventional TiO2 and ZnO pigments were measured and the relation between viscosity and anticorrosion performance was discussed. KEY WORDS: Electrochemical impedance spectrum (EIS); Alkyd coating; Nano-TiO2 ;
Nano-ZnO; Corrosion resistance

1. Introduction Many nano-composite coatings were reported to exhibit better performance in comparison with the traditional coatings[19] . For instance, the addition of nano-SiO2 into acrylic-based polyurethane coatings apparently improved the microhardness, macrohardness and abrasion resistance[2] . Colloid SiO2 is another kind of nanometer SiO2 , which was also used to improve hardness, wear resistance and scratch resistance of coatings. Soloukhin et al.[3] found that elastic modulus and hardness of methacrylate coating on polycarbonate substrate were improved via addition of colloid SiO2 . Literatures also reported the improved performances of epoxy/nanoSiO2 composites[4,5] . Nano-Al2 O3 , nano-ZrO2 and nano-CaCO3 particles were found to have similar effects as nano-SiO2 [69] . In recent years, nano-TiO2 and nano-ZnO have been paid much attention since their application improved the optical property and endowed other special function to coatings[1015] . It was found that nano-ZnO could reinforce the UV shielding ability of acrylic latex paint[10] . Nano-TiO2 , especially in rutile type, has the similar UV shielding ability as nano-ZnO[13,14] . Anatase TiO2 is characterized by outstanding photocatalytic feature and has been used in antifouling and self-cleaning coatings[15] . These properties changes for the nano-composite coatings were attributed to the modication of coating structures. It is reasonable to suppose that the diusion behavior of corrosive specimens in the nanocomposite coatings may be much dierent from that in the conventional coatings. However, most studies on nano-composite coatings were focused on mechanical or optical properties rather than anticorrosion performance. Our group recently began to investigate the eects of nano pigments on anticorrosion property of coatings. In previous work, it was found that less amount of nano-ZnO (P/B , pigment/binder=0.3) was required, less than conventional ZnO (P/B =1) when the best corrosion resistance was obtained and
Prof., Ph.D., to whom correspondence should be addressed, E-mail: ehhan@imr.ac.cn.

the former was better in anticorrosion property[16] . In this work, nano-TiO2 and nano-ZnO were selected and incorporated into alkyd coatings to obtain corresponding nano-composite coatings. The protective performances of the nano-composite coatings to the metal substrate exposed to 3.5% NaCl solution were investigated. To compare the eects between the nano and conventional pigments in coatings on anticorrosion properties, alkyd coatings lled with the microsize TiO2 and ZnO particles were studied for corrosion test. The optimal amount of nano-TiO2 in a colored coating was determined. In addition, the viscosities and mechanical properties of the nano-composite coatings were measured and discussed in this work. 2. Experimental 2.1 Materials The alkyd resin was middle oil length resin with solid content of 53%57%, T-4 (25 C) viscosity of 100200 s and acid value less than 13. Other chemicals in alkyd coating formation including conventional titanium dioxide, conventional zinc oxide, coupling agent, dryer, leveling agent, solvent naphtha, French chalk, barium sulphate, white spirit, etc, were industrial grade products and used as purchased. Figure 1 shows the TEM (transmission electron microscopy) micrographs of nano-TiO2 , nano-ZnO, conventional TiO2 and conventional ZnO dispersed in alkyd resin, respectively. Nano-TiO2 pigment, which is rutile titanium dioxide, has an acicular structure with average length around 60 nm and aspect ratio around 4:1, while micron TiO2 is of round shape with diameter of 100300 nm. Nano-ZnO pigment is of irregular triangle and claviform shape with particle size less than 50 nm. For micron ZnO, the particles are of claviform shape, with uneven size distribution in micron grade. 2.2 Preparation of the nano-composite coatings Tinplates of 120 mm50 mm0.5 mm and A3 steel plates of 150 mm70 mm2 mm were used as substrate, respectively for mechanical measurement and accelerated corrosion test. Panels for electroch-

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Fig.1 TEM micrographs of dispersed: (a) nano-TiO2 , (b) conventional TiO2 , (c) nano-ZnO and (d) conventional ZnO in alkyd varnish

emical impedance spectrum (EIS) experiment were fabricated into 50 mm50 mm sheets. Substrates were polished with 800 emery paper, then degreased with acetone and washed by ethanol. The coating lms were coated by spreader bar and were dried at room temperature. The nal thickness of coated lms was about 20 m for mechanical test and 30 m for corrosion test. In order to solve the dispersion problem of nano pigments in alkyd coatings, nano-oxide concentrated slurry was rstly prepared[17] . The solvent, nano pigments and dispersants were mixed, and then the mixture was ground to avoid the agglomeration of nanoparticles. The preparation of nano-composite coatings was as follows. The nano pigment incorporated varnish and colored coatings were mixed and dispersed for 15 min, then ground for 8 h to obtain the proper neness. In this work, P/B (pigment/binder) is 0.02. When colored coating was applied, the formation is composed of alkyd resin (64.6 g), conventional TiO2 (13 g), French chalk (7 g), conventional ZnO (0.8 g), kaoline (8 g), atting agent (1.2 g), white spirit (7.9 g) and cobalt dryer (3 g). A series of amounts of nano-TiO2 (0.5%, 1% and 2%) was incorporated into colored alkyd coating to determine the optimal content. 2.3 Electrochemical test All EIS measurements were done at room temperature in 3.5% NaCl solution. Test system consisted of a three-electrode cell, where a saturated calomel electrode (SCE), a stainless steel electrode and a coated coupon were used as reference, counter, and working electrodes, respectively. The working area of cell was 12.56 cm2 . Experimental tests were performed under the open circuit potential. EIS measurement instruments included an EG&G 273 Potentiostat/Galvanostat and an EG&G 5210 lock-in amplier (0.5 Hz-120 kHz) integrated with a PC system. Impedance spectra of coupon in dierent immersion times were recorded in the frequency range of 101 105 Hz with initial time delay of 100 s and sinusoidal alternating potential signal of 20 mV. The EIS data were analyzed by Z -view 2.2 software.

2.4 Corrosion test Salt spray exposure was carried out according to ASTM B117. The coated panels were exposed to a 5% NaCl solution at 352 C for 96 h. For this experiment, the A3 steel plates were coated with varnish and pigmented varnish (P/B =0.02). The panels were studied under scratched (using X shape) condition. 2.5 Viscosity measurement A DV-III ULTRA programmable rheometer from Brookeld Company, USA, was used to measure the viscosity of varnish and pigmented varnish as a function of rate of shear. 3. Results and Discussion 3.1 Corrosion analysis of alkyd coatings with TiO2 and ZnO pigments 3.1.1 EIS of varnish The Bode plots of EIS obtained at dierent exposure times of the specimen coated with varnish immersed in 3.5% NaCl solution are shown in Fig.2. It can be seen that the impedance values of varnish remained relatively high until immersed for 648 h, which indicates that after the specimen was cured at room temperature, it was hard for electrolyte to penetrate through the coating lm.

Fig.2 Bode plots of alkyd varnish immersed in 3.5% NaCl solution at dierent immersion times

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Qc

Qc

Rs

Rs Rpo
Rpo

Qdl

Rct

Fig.3 Equivalent electrical circuit in the initial stage of immersion

Fig.4 Equivalent electrical circuit in the middle and the end stage of immersion

Fig.5 Evolution of pore resistance (a) and coating capacitance (b) vs immersion time for alkyd varnish

The interpretation of impedance spectra was performed after numerical tting using the equivalent circuits presented in Figs.3 and 4. The equivalent circuits are composed of the solution resistance Rs , the pore resistance Rpo due to penetration of electrolyte, and the capacitance of the coating Qc . Analysis of impedance spectra according to the equivalent circuit of Figs.3 and 4 rendered the parameters Rpo and Qc to be changed as a function of time as shown in Fig.5. The Rpo value showed a sharp decrease during the rst 12 h and then a sharp increase. After 144 h of immersion, Rpo slowly decreased with time, which can be explained by the dissolution of corrosion product from substrate to the NaCl solution. The decrease in Rpo during the initial stage of immersion can be attributed to the uptake of saturated electrolyte in coated lm. Contrasting to the above decrease in Rpo , Qc increased during the initial immersion stage. The following sharp increase in Qc can be ascribed to the blocking of transmission channels by the corrosion product.

Fig.6 Bode plots for alkyd varnish containing conventional TiO2 (a) and nano-TiO2 (b) immersed in 3.5% NaCl solution after dierent times

Correspondingly, electrolyte penetrated into larger area of interface of substrate/coating, characterised by the increase in Qc in the end stage. Qc was approximately 4109 F after 312 h of immersion, twice more than that in the initial stage. 3.1.2 EIS of varnish with pigments Figure 6(a) and (b) show the Bode plots of conventional and nanometer TiO2 pigmented alkyd coatings of P/B =0.02 after dierent immersion times in 3.5% NaCl solution. The impedance value of the low frequency varied with the coatings. As shown in Fig.6(a), alkyd coating containing conventional TiO2 exhibited relatively high resistance during the initial stage of immersion, with impedance value in low frequency reaching approximately 109 orders of magnitude. The impedance value decreased with time. However, the impedance of the prewashed cold rolled steel coated with conventional TiO2 showed still high impedance value (above 106 cm2 ) after 648 h of immersion. Such high

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Fig.7 Bode plots for alkyd varnish containing conventional ZnO (a) and nanometer ZnO (b) immersed in 3.5% NaCl solution after dierent times

Fig.8 Bode plots for alkyd varnish and pigmented alkyd varnish immersed in 3.5% NaCl solution after 2164 h

impedance value shows good barrier eect of conventional TiO2 pigmented alkyd coatings. Two time constants were present in the Bode plot of 648 h, which can be ascribed to the formation of Fe oxide or hydrate during immersion. In the case of nano-TiO2 pigmented alkyd coatings, higher impedance values were reected in low frequencies in Bode plot until the immersion time was up to 648 h, showing that nano-TiO2 as pigment performed excellent barrier eect for alkyd coating. Additionally, it is evident that the impedance value in low frequency of nano-TiO2 pigmented coatings uctuated with immersion time, which was probably due to the dissolution of old corrosion product and regeneration of the new and thicker corrosion product in electrolyte. The above results can be also observed in Bode plot of conventional TiO2 pigmented alkyd coating. Figure 7(a) and (b) show the Bode plots of conventional and nanometer ZnO pigmented alkyd coatings for P/B =0.02 after dierent immersion times. Conventional ZnO pigmented alkyd lm maintained the relatively high impedance values, i.e., approximately 107 108 cm2 . The impedance value of nano-ZnO pigmented coating decreased with immersion time, but the value was much lower than that of conventional ZnO pigmented coatings. It is worthy to note that the dierence of impedance value in low frequency is evident for nano-ZnO compared with other pigments. No apparent impedance rise in the latter stage of immersion can be observed. The reason was that the

coated lm was delaminated from the substrate and the corrosion product could not eectively block the saturated area with immersion time. After 2164 h of immersion, the Bode plots for alkyd varnish and pigments added varnish are shown in Fig.8. It is clear that the low frequency impedance of nano-TiO2 pigmented coating is the highest among all coatings, indicating that the nano-TiO2 particles can eectively block the pores formed in coating lm. The excellent anticorrosion protection is attributed to the size and shape of nano-TiO2 , which has the smallest size and largest aspect ratio. For the small particles, free space between the particles and resin is far lesser than that of larger particles. Thus electrolyte is harder to penetrate through the pores in coating lm with addition of nano pigment[18] . In addition, due to longer diusion path around the nano-TiO2 in the lm, the water and ions need more time to arrive at the substrate. In contrast, the impedance value in low frequency of coating lm pigmented with conventional TiO2 is below 1106 cm2 , which indicates the coated lm is poor for protection at this time. As for the conventional ZnO pigmented coating, the impedance value is similarly lower than 106 cm2 as conventional TiO2 . At this time, the severe rusting can be observed on the substrate. Indeed, the lm was already delaminated from the substrate and was thinner than the original one. Similar state can be observed for substrate coated with varnish. Whereas for the coating pigmented with nano-ZnO, the impedance value decreased to 103 cm2 , suggesting that the nano-ZnO pigmented lm was seriously corroded. The coated lm thoroughly shelled o from the substrate. Fitting values of the coating pore resistance and capacitance as a function of the exposure time for the pigmented alkyd coatings are shown in Fig.9. The pore resistance, which reects the resistance of coating lm to electrolyte penetration, generally deceases with time (Fig.9(a)). Clear dierence is evident when the four samples are compared. For nano-TiO2 pigmented coating, Rpo value gradually decreased with the exposure time, but the coating maintained the highest Rpo values. Furthermore, unlike the other three coatings, no sharp decrease was found in the end stage of the immersion and the ultimate Rpo value was still above 107 . For the conventional TiO2 and ZnO, a similar trend of decrease in Rpo with time was

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Fig.9 Evolution of pore resistance (a) and capacitance (b) of alkyd coatings loaded with dierent pigments during the immersion in 3.5% NaCl solution

Fig.10 Aspects of alkyd varnish (a), conventional TiO2 pigmented varnish (b), nano-TiO2 pigmented varnish (c), nano-ZnO pigmented varnish (d), and conventional ZnO pigmented varnish (e) after exposure in salt fog for 96 h

Fig.11 Typical Nyquist plots of EIS of alkyd coating containing dierent nano-TiO2 content: (a) 0, (b) 0.5%, (c) 1%, (d) 2% at dierent times immersed in 3.5% NaCl solution

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Fig.12 Evolution of pore resistance (a) and capacitance (b) of alkyd coating loading with dierent content nanoTiO2 pigments during the immersion in 3.5% NaCl solution

observed, and a rapid decrease after 648 h was apparent. For nano-ZnO pigmented alkyd coating, the Rpo values were sharply increased at the start, but were obviously lower than the other three after 648 h. The change of the capacitance of the coating (Qc ) related to water uptake is shown in Fig.9(b). In the end stage, Qc of alkyd coating containing nano-ZnO exhibited the highest value, showing that the coated lm was delaminated from substrate. The following were coatings containing conventional TiO2 and conventional ZnO, with the nano-TiO2 pigmented coating showing the smallest value of Qc . From the results of Qc and Rpo , it can be concluded that the nano-TiO2 pigmented alkyd coating exhibits the best protective property. 3.1.3 Corrosion test The corrosion resistance of pigmented coatings was determined by the rusts and blistering along the X marks. The aspects of alkyd varnish and pigmented varnish after exposure in salt fog for 96 h are shown in Fig.10. As can be seen in the gure, no apparent rust and blistering along the scribes were observed on the nano-TiO2 pigmented coating surface. The similar situation along X mark occurred on alkyd varnish surface, however, large area of small rusts could be observed in the other part of surface. For conventional TiO2 pigmented coating, small blisters with diameter of 0.010.3 mm could be observed along X mark. In the cases of nano-ZnO and conventional ZnO pigmented coating, water saturated zone with width of 0.75 cm was found along the X marks. 3.1.4 EIS of colored coating containing nanoTiO2 In order to investigate the eect of nanoTiO2 content on the corrosion resistance of alkyd coatings, the EIS plots of alkyd colored coatings with a series of nano-TiO2 contents (wt pct) from 0 to 2% were compared. Typical Nyquist impedance plots after dierent immersion times for alky coatings with dierent contents of nano-TiO2 are shown in Fig.11(a)(d), respectively for 0, 0.5%, 1%, and 2%. For colored coating without nano-TiO2 , EIS spectra show apparent two time constants after 48 h of immersion in Fig.11(a), which is related to the corrosion activity due to the Fe dissolution and O reduction. For coating with 0.5% nano-TiO2 , lower impedance modulus values were reected in Nyquist diagram than the previous one. After 48 h of immersion, a 45 slope is obtained after the semi-circle,

as shown in Fig.11(b), which is the characteristic of Warburg resistance, indicating that a possible diusional progress occurred and corrosion product had clogged the path of water transportation. For coating with 1% nano-TiO2 , from 0 to 1032 h, only one semi-circle is observed with the values of radius bigger than 107 cm2 . The above results suggest that the coating was compact in structure with improved anticorrosion performance. With the content of nanoTiO2 increased to 2%, it is evident that, although semi-circle is as well presented in Nyquist plot, the radius of the semi-circle is much smaller and the radius of the second one is below 5106 cm2 , showing the decrease in barrier eect of coating. It is possible that the agglomeration of nano-TiO2 particles occurred with addition of 2% content. When nanoTiO2 content was more than 2%, the resistance value decreased fast in short time and more serious agglomeration could occur. Figure 12 shows the tting values of coating pore resistance and capacitance as a function of immersion time for the colored coatings. The pore resistance values similarly decreased with time. As shown in Fig.12(a), the coating containing 1% nano-TiO2 exhibited the highest pore resistance among the four coatings in the immersion time. For 0.5% nanoTiO2 , the coating showed the lowest resistance value. Whereas for 2% nano-TiO2 , Rpo value uctuated at rst immersion stage and was a little more than that of without nano-TiO2 in the end stage of immersion. As far as the pore resistances of nano-TiO2 pigmented are concerned, the above results show that the optimal content of nano-TiO2 is 1%. If the content of nanoTiO2 was insucient (less than 1%), nano particles could not fully play the barrier eect and the corrosion resistance was partly counteracted by the uptake of water that reected by the increase in Qc . Excessive dosage (more than 1%) would cause agglomeration. Thus, it can be concluded that a critical amount of nano pigment exists in nano-composite coatings. As shown in Fig.12(b), the capacitance (Qc ) values of nano-TiO2 pigmented colored coating gradually increased with time, which are higher values than the coating without nano-TiO2 , indicating that the addition of hydrophilic nanoparticle could result in more uptake of the electrolyte solution in coating lm. In the latter immersion stage, it can be seen that the capacitance of the coating containing 2% nano-TiO2

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Fig.13 Viscosity of alkyd varnish

of coatings[20] . In general, the change of thixotropy companies with the change of pigment state. A benecial attempt to observe the change of nano pigment state is to measure the viscosity related to thixotropy using rheoviscometer. Figures 13 and 14 show the viscosity curve of varnish and varnish added with 2% (in wt pct) conventional TiO2 and ZnO, nano-TiO2 and nano-ZnO, respectively, as a function of rate of shear. As shown in Fig.13, the viscosity of varnish is very low and decreases with the rate of shear, indicating that the alkyd resin is non-Newtonian uid. Addition of nano-ZnO caused the increase in viscosity and presented coating as non-Newtonian uid. Other pigmented coatings show the characteristic of Newtonian uid. Corresponding to results as shown in Fig.8, nonNewtonian coating, i.e. nano-ZnO pigmented coating, showed the poor corrosion resistance in the long immersion time. On the contrary, Newtonian coatings, i.e. conventional ZnO and TiO2 and nano-TiO2 pigmented coatings presented the relatively higher resistance. Additionally, it seems that low-viscosity coatings represent higher corrosion resistance. It is presumed that high viscosity will reduce the extent of curing, which results in low crosslinking density, so electrolyte is prone to penetrate through coating lm and the corrosion resistance could be lowered. The further study is being carried out to investigate the viscosity on anticorrosion performance of organic coatings. 4. Conclusions

Fig.14 Viscosity of pigmented alkyd varnish

was higher than those of the other three ones. It can be inferred that if agglomeration occurs, transmission of water will transfer from zigzag path to big pore, and thus the capacitance of coating is enhanced. Furthermore, with the addition of more nano-TiO2 particles, the area of absorbed points is increased, which results in the increase in absorbed electrolyte, and thus the capacitance of coatings increases. From the capacitance point of view, it can be also concluded that the amount of nano pigment is critical to corrosion resistance of nano-composite coatings. 3.2 Mechanical property of pigmented alkyd varnish For P/B =0.02, the mechanical properties of pigmented varnish were studied. The results show that the coatings with addition of all the four pigments were high in exibility and impact resistance due to the characteristic of alkyd resin. The values of exibility and impact resistance were 1 mm and 120 kgcm, respectively. The hardness of the nano-TiO2 added coating is the highest, with value of HB (pencil hardness), whereas it is B for others. The improvement in hardness is probably due to the formation of a spacial framework by the uniform and stagger distribution of nano-TiO2 particles in coating lm, and the hardness of nano-TiO2 in essence. Also, as shown in Fig.1(a), nanoparticles of TiO2 have higher aspect ratio, which could result in the higher strength[19] . 3.3 Viscosity of pigmented alkyd varnish Thixotropy is the reection of the microstructure

(1) For P/B (pigment/binder)=0.02, Nano-TiO2 pigmented alkyd varnish exhibits the best corrosion resistance among the four nanometer and conventional ZnO and TiO2 pigmented coatings. The order of anticorrosion performance of the four coatings was as follows: nano-TiO2 >conventional TiO2 >conventional ZnO>nano-ZnO. Additionally, in terms of the mechanical property, nano-TiO2 pigmented varnish is the highest in hardness than others. Small size eect and high aspect ratio of nano-TiO2 are the probable reasons to inhibit the corrosion and reinforce the barrier eect of coating lm. (2) The experiment on amount of nano-TiO2 in a formation evidences that 1% is the optimal amount for alkyd colored coating. Excessive incorporation of nano-pigment could cause agglomeration. Also, it shows that the critical amount is a crucial factor to improve the anticorrosion performance of nanocomposite coatings. (3) Except for nano-ZnO pigmented alkyd varnish, conventional ZnO and TiO2 and nano-TiO2 pigmented coatings behaved as Newtonian uid. Viscosity of pigmented alkyd varnish probably has relation with corrosion resistance when the coating is cured. Due to high viscosity, the extent of curing is reduced, which results in low crosslinking density, so that electrolyte is prone to penetrate through coating lm and the corrosion resistance could be lowered.
Acknowledgement The authors are grateful for the nancial support from the National Natural Science Foundation of China (No. 50499334).

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