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Journal of Chinese Society for Corrosion and protection  2015, Vol. 35 Issue (6): 535-542    DOI: 10.11902/1005.4537.2014.216
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Influence of Calcareous Deposit on Corrosion Behavior of Q235 Carbon Steel in f/2 Culture Medium with Amphora
Jiangwei WANG1,2,Jie ZHANG2(),Shougang CHEN1,Jizhou DUAN2,Baorong HOU2
1. College of Material Science and Engineering, Ocean University of China, Qingdao 266100, China
2. Key Laboratory of Marine Environmental Corrosion and Bio-fouling, Institute of Oceanology, Chinese Academy of Science, Qingdao 266071, China
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Abstract  

Calcareous deposit was formed on Q235 carbon steel surface in nature seawater by applying cathodic protection, afterwards, the corrosion test of the steel covered with and without calcareous deposit was carried out in f/2 culture medium containing Amphora. Then the morphology and chemical composition of corrosion products were characterized by means of XRD, SEM, FTIR and EIS. The result revealed that the calcareous deposit prepared by a current density of -30 µA/cm2 showed an even- and uniform-surface morphology composed of nice crystalline phase. The Amphora and its metabolite could adhere to the steel surface forming a biofilm, which could suppress the mass transfer of corrosive species from the medium to the steel surface to some extent, but not obviously that of the oxygen. Calcareous deposit was apt to combine with Amphora forming a composite film on the steel surface, which then could rather effectively suppress the migration of oxygen. The corrosion process of Q235 steel beneath the composite film can be described as the following three stages: as the corrosive media penetrated the composite film on to the steel surface, the steel is corroded leading to the formation of corrosion products, while, with which the combination of the existed biofilm, thus the composite film could act as barrier enabling the corrosion rate to be decreased to some extent; later as damages occurred within the composite film, thereby its protectiveness deteriorated, the corrosion rate of the steel increased again.
Key words:  Q235 carbon steel      calcareous deposit      amphora      dissolved oxygen      behavior of corrosion     
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Jiangwei WANG
Jie ZHANG
Shougang CHEN
Jizhou DUAN
Baorong HOU

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Jiangwei WANG,Jie ZHANG,Shougang CHEN,Jizhou DUAN,Baorong HOU. Influence of Calcareous Deposit on Corrosion Behavior of Q235 Carbon Steel in f/2 Culture Medium with Amphora. Journal of Chinese Society for Corrosion and protection, 2015, 35(6): 535-542.

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https://www.jcscp.org/EN/10.11902/1005.4537.2014.216     OR     https://www.jcscp.org/EN/Y2015/V35/I6/535

Fig.1  XRD spectra of the calcareous deposit formed in natural seawater after 72 h immersion at the current density of -60 µA/cm2 (a) and -30 µA/cm2 (b)
Fig.2  Surface images of calcareous deposit formed in seawater after immersion at -60 µA/cm2 (a) and-30 µA/cm2 (b) for 72 h and EDX results of areas I in Fig.2a (c) and II in Fig.2b (d)
Immerse time Rsol CPEf Rf CPEdl Rct
d Ω·cm2 Yf / Ω-1cm-2sn10-6 nf Ω·cm2 Ydl / Ω-1cm-2sn10-6 ndl Ω·cm2
1 11.7 160 0.86 198 470 0.8 5598
3 12.7 270 0.82 921 580 0.8 2295
5 11.4 340 0.67 1005 610 0.6 1654
9 12.5 460 0.53 1249 480 0.68 1890
12 12 500 0.57 1428 500 0.74 2140
15 9.9 2500 0.81 23 8700 0.8 1257
Table 1  Fitting electrochemical parameters of carbon steel with calcareous deposit after immersion in f/2 culture medium containing Amphora for different time
Immerse time Rsol CPEf Rf CPEdl Rct
d Ω·cm2 Yf / Ω-1cm-2sn10-6 nf Ω·cm2 Ydl / Ω-1cm-2sn10-6 ndl Ω·cm2
1 9.4 210 0.8 22 2100 0.53 3114
3 6.5 580 0.94 29 2400 0.63 2270
5 7.6 1000 0.89 36 3300 0.67 1585
9 6.4 1300 0.89 27 4000 0.69 1298
12 6.9 1600 0.89 23 4700 0.72 1013
15 6.3 2300 0.85 39 5100 0.79 988
Table 2  Fitting electrochemical parameters of carbon steel without calcareous deposit after immersion in f/2 culture medium containing Amphora for different time
Immerse time Rsol CPEf Rf CPEdl Rct
d Ω·cm2 Yf / Ω-1cm-2sn10-6 nf Ω·cm2 Ydl / Ω-1cm-2sn10-6 ndl Ω·cm2
1 19 150 0.98 211 3600 0.8 3023
3 19 64 0.96 212 3000 0.8 2243
5 18.8 61. 0.96 185 2800 0.64 2221
9 20 68 0.97 128 3000 0.72 2633
12 14 200 0.99 177 4300 0.9 2128
15 15.7 4000 0.98 201 4200 0.8 2116
Table 3  Fitting electrochemical parameters of carbon steel with calcareous deposit after immersion in filtrate of f/2 culture medium containing Amphora for different time
Fig.3  Nyquist (a1~d1) and Bode (a2~d2) plots of samples immersed for different time: (a) with calcareous deposit in f/2 culture medium containing Amphora, (b) without calcareous deposit in f/2 culture medium containing Amphora, (c) with calcareous deposit in the filtrate of f/2 culture medium containing Amphora, (d) without calcareous deposit in sterile culture medium
Fig.4  Equivalent circuit models (a~c) for fitting the impedance date of samples: (a) with calcareous deposit in f/2 culture medium containing Amphora or the filtrate of f/2 culture medium containing Amphora, (b) without calcareous deposit in f/2 culture medium containing Amphora, (c) without calcareous deposit in sterile culture medium
Immerse time Rsol CPEdl Rct
d Ω·cm2 Ydl / Ω-1cm-2·sn10-6 ndl Ω·cm2
1 6.4 620 0.8 1882
3 8.5 650 0.95 1904
5 5.5 690 0.94 1832
9 8.6 810 0.92 1662
12 7.8 1000 0.93 1364
15 7.7 1000 0.89 1555
Table 4  Fitting electrochemical parameters of carbon steel without calcareous deposit after immersion in sterile culture mediumfor different time
Fig.5  Time dependences of EOCP for carbon steel with and without calcareous deposit and dissolved oxygen tin f/2 culture medium containing Amphora under a 12:12 light-dark regime
Fig.6  FTIR patterns of the product films of samples with (a) and without (b) calcareous deposit after immersionin medium with Amphora for 3 d
Fig.7  SEM surface images of samples with (a) and without (b) calcareous deposit after immersion in medium with Amphora for 9 d
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