Corrosion of marine carbon steel by electrochemically treated ballast water

Corrosion of marine carbon steel by electrochemically treated ballast water

Yongxin Song, Kun Dang, Huafang Chi and Delin Guan, School of Marine Engineering, Dalian Maritime University, PRC

Laboratory weight-loss measurements, electrochemical tests and SEM techniques were used to study the corrosive behaviour of electrolysed ballast water on marine carbon steel. Experimental results showed that for the mass concentration of Total Residual Chlorine (TRC) being 7.5mg/l, 17mg/l and 28mg/l respectively, the corrosion rates within seven days were 1.25, 1.46 and 1.7 times those in natural seawater. The corrosion rates decreased as time progressed. The corrosion rate in the electrolysed seawater is controlled by the cathodic process which is mass transfer controlled. The SEM observation showed that the topographies of carbon steel corroded in electrolysed ballast water with mass concentration of TRC 7.5mg/l and 17mg/l were characterised by denudation and rupture. Both the weight-loss and electrochemical tests revealed that the chlorinated seawater accelerated the corrosion rate and that this is consistent with result of the SEM observation

LEAD AUTHORS BIOGRAPHY Yongxin Song, a lecturer at the School of Marine Engineering, Dalian Maritime University, completed a BSc and MSc in marine engineering, after which he worked as a teacher at the same university. He is now a doctoral candidate majoring in marine engineering. His main research interests are environment protection, ballast water treatment, metal corrosion and protection. He has published several technical papers and books, and has four patents granted.

INTRODUCTION
he introduction of invasive marine species into new environments by ships ballast water, hull fouling and by other means, has been identified as one of the four greatest threats to the worlds oceans.1 And according to the treatment guidelines and regulatory practices, ships entering many ports around the world will be required to undertake ballast water treatment to reduce, remove or kill organisms of concern before being allowed to discharge the water. Currently, there are lots of possible options2 for ballast

water treatment, such as filtration, ultraviolet irradiation, ozone, chlorination, heating, etc. Seawater electrolysis treatment is considered to be very promising and is being researched in several countries including China, South Korea and USA. According to a study by Lloyds Register, the majority of the systems provided (8 of the 27 reviewed) are based on electrolytic treatment (electrolysis or electrochlorination). Electrolytic technologies aimed at treating ballast water may be designed to generate chlorine, as in the classic seawater electrolysis, or other oxidative products. It is reported that this method is effective in killing almost all of species with the residual chlorine concentration below about 10mg/l.3 To date, three electrolysis treatment systems have been granted basic approval by the International Maritime Organization.4 Metal corrosion of ballast tanks, however, has to be seriously considered when utilising the seawater electrolyses method to treat ballast water. When electrolysing seawater, several kinds of oxidants, such as HClO, ClO-, Cl2 , OH - , [O] will be generated. While these oxidants are effective in killing the organisms, they are also corrosive to the metal of the pipeline and ballast tanks.

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Corrosion of marine carbon steel by electrochemically treated ballast water

Ventura5 studied the corrosion of stainless steel in flowing natural seawater with the residual chlorine concentration at about 0.1 to 0.2mg/l through continuous additions of sodium hypochlorite (NaClO). The study showed that residual chlorine of 0.1 to 0.2mg/l was able to reduce the corrosion rate. Gundersen6 studied the electrochemical properties of stainless steels in seawater with the residual chlorine concentration at 0.1 and 0.2mg/l through additions of sodium hypochlorite (NaClO) and showed that no corrosion occurred at a concentration of 0.2mg/l. Neville7 studied the corrosion of UNS S3276 superduplex stainless steel in high chlorine concentrations (up to 500mg/l). Eisnor8 evaluated the impact of secondary disinfectants (free chlorine, chloramines, chlorine dioxide and chlorite) on internal corrosion and water quality in old, unlined cast-iron water distribution system pipes. Results indicated that monochloramine and free chlorine increased the corrosion rate within distribution systems by an average rate of 5.9 and 3.3ml per year, respectively. Song9 studied the corrosive behaviour in ships ballast tanks of sodium hypochlorite-treated ballast water and found that the chlorinated seawater accelerated the metal corrosion rate to some degree. However, it has to be noted that in the studies mentioned, either the corrosive medium is a sodium hypochlorite (NaClO) solution or the metal is stainless steel. Thus, those studies do not simulate the scenarios of metal corrosion caused by seawater electrolysis treatment. Currently, there are very limited investigations into the corrosion of marine carbon steel in electrolysis treated ballast water with residual chlorine concentrations between 5 to 25mg/l. In this paper, the corrosive properties of ballast water treated by electrolysis on marine carbon steel Q235A were studied using laboratory weight-loss measurements and polarisation tests. Furthermore, the surface morphology of the metal species before and after corrosion was analysed by a scanning electron microscope (SEM). The aim of this study was to better understand the impact of corrosive behaviour on ships ballast tank metal when the seawater electrolysis method is employed as the ballast water treatment method. It is also hoped that the results will be helpful for the corrosion prevention of ballast tanks in the future and thus enable the utilisation of seawater electrolysis ballast water treatment technologies.

& D) of marine carbon steel, grade A steel is widely used in the construction of ballast tanks. In this paper, carbon steel of Q235A is chosen as the test specimen. The chemical composition of Q235A is shown in Table 1. Specimens were machined into 73430.37cm coupons for laboratory immersion tests. Some of the coupons were made into electrodes with a 131cm unsealed surface (other surfaces were sealed by epoxy resin) for electro-

Chemical elements (wt %) C Mn Si <0.21 ,0.6 <0.50 Mechanic properties 0.2/Mpa b/Mpa >235 >370

P <0.035 5 % >25

S <0.035

Table 1: Chemical composition and mechanical properties of the specimen

chemical measurements. The solutions were made by directly electrolysing the natural seawater. Different voltages were employed to generated three levels of Total Residual Chlorine (TRC): 7.5mg/l, 17mg/l and 28mg/l. The concentration of TRC was measured by means of the DPD spectrophotometric method. Immediately after the electrolysis, pH values were measured to determine the percentages of HOCl and OCl- . The volume of the solution generated is about 40 litres. All the experiments were conducted at T 298 1K.

Weight-loss measurement
Two different weight-loss measurements were carried out. One was to expose samples in ballast water that was chlorinated to different levels for identical periods of time (seven days). The aim was to study the impact of chlorine concentration on corrosion rates. The other was to expose samples in the same chlorinated ballast water for different times, for the purpose of studying the impact of exposure time on corrosion rates. Standard corrosion testing procedures were carried out to clean and weigh coupons before and after exposure, including the use of a high accuracy mass balance with 0.1mg precision. Since the TRC in the treated ballast water will decay with time, the solution has to be intermittently re-chlorinated in order to approximately maintain the TRC at the same concentration. In this paper, three kinds of solutions (I, II & III respectively) are employed. Table 2 shows the pH value and the decay of TRC of different solutions. It can be seen that within the first 24 hours (h), the
Solution II After 24h 15 Solution III After 24h 25

MATERIALS AND METHODS

Specimens and solutions
The vast majority of ships ballast tanks are constructed of carbon steel, which corrodes rapidly when exposed to oxygen and water. Among the different grades (A, B, C
Seawater After 24h 0

pH TRC(mg/l)

Initial 8.0 0

Initial 8.03 7.5

Solution I After 24h 4.5

Initial 8.12 17

Initial 8.35 28

Table 2: pH value and decay of TRC of different solutions

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residual chlorine decays slowly. So in this experiment, the corrosive solutions were re-chlorinated daily with new ones and the seawater was also refreshed daily.

Potentiodynamic polarisation curve measurement

Potentiodynamic polarisation experiments were conducted using a SI 1280 electrochemical measurement unit (Fig 1). The polarisation curves of the specimens in different chlorinated seawater were measured with a scanning rate of 0.5mv/s. The counter electrode was a platinum foil and the reference electrode was a saturated calomel electrode (SCE). The polarisation started from a cathodic potential about -65mv (vs open potential) and stopped at an anodic potential +50mv (vs open potential). The polishing and cleaning of electrodes were the same as specified in weightloss measurement.

Fig: 2: Corrosion rates for 7 days exposure in different chlorinated ballast water

estimate of a maximum level of corrosion, the following approach was adopted: 1. Extensive investigations10 have established that the average general corrosion rate of carbon steel in ballast tanks is at around 0.1,0.2mm/year (for single side of a tank). This represents the testing at 0mg/l in Table 3. As an approximation, this measured corrosion rate of 1.923103mg/mm2 .d is assumed to represent the base-line corrosion equivalent to an in-service corrosion of about 0.1,0.2mm/year. Based on this assumption, the corrosion rates at the other exposure conditions can then be recalculated from the base-line corrosion. The recalculated results are shown in Table 4 where it can be seen that the corrosion rate in chlorinated seawater will be 1.3,1.7 times of that in natural seawater.
17 2.8 28 3.32

2.

Fig. 1: Polarisation curve test rig

Corrosion potential (Ecorr ) measurement

A Ph-9C digital multimeter and saturated calomel reference electrode were employed to measure the corrosion potential with time in natural seawater and different chlorinated seawater.

Surface morphology analysis

The surface morphology of the metal specimens before and after corrosion was analysed by a Philips-XL-30 scanning electron microscope (SEM).

TRC (mg/l) 0 7.5 Corrosion rate 1.92 2.4 (103 mg/mm2 .d) (Note: 0mg/l represents natural seawater)

Table 3: Corrosion rates in different concentrations of TRC

RESULTS AND DISCUSSION

Corrosion rate evolution with TRC
Figure 2 shows the corrosion rates as a function of initial concentration of TRC. It can be seen that the rate increases with the increase of TRC concentration. To be precise the corrosion rates for the mass concentration of Total Residual Chlorine (TRC) being 7.5mg/l, 17mg/l and 28mg/l, respectively, are 1.25, 1.46 and 1.7 times of those occurring in natural seawater. However, the corrosion rates given in Fig 2 are higher. Such data are typical of short-term measurements made on clean bare steel plates. Corrosion rates based on long-term exposures (weight-loss) will be much lower. To give an

TRC (mg/l) Corrosion rate (mm/year)

0 0.1,0.2

7.5 0.13,0.26

17 0.15,0.3

28 0.17,0.34

Table 4: Recalculated corrosion rates

Corrosion rate evolution with time

Figure 3 shows the evolution of corrosion rates in the same chlorinated ballast water (17mg/l) with exposure time. It is clear that the corrosion rate decreases with exposure time. There is a very short period (,5 days) during which there is initially a very high corrosion rate followed by a steady decline.

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Fig 3: Evolution of corrosion rates with exposure time The usual interpretation from a theoretical perspective is that the early (,5 day) period is generally associated with activation control while the period immediately after is associated with concentration control. The latter involves the limited diffusion of oxidants through the corrosion product formation adjacent to the corroding surface. Fig 5: Open circuit potential in ballast water with different levels of chlorination chlorination will favour the anodic reaction and de-activate the cathodic reaction. (2) The chlorination will greatly lower the Open Circuit Potential (OCP). As can be seen from Fig 5, the OCP level in chlorinated seawater is much lower than that in natural seawater. As for the chlorinated seawater, the TRC will greatly lower the OCP immediately after immersion. Also, the higher the TRC concentration, the lower the OCP level. As time goes by, the OCP fluctuated and tended to be stable. After about 16 hours, the OCP for natural seawater is about -0.70v, while for 7.5mg/l, 17mg/l and 28 mg/l chlorinated ballast water it is about -0.731v, -0.74v and -0.75v, respectively. Since the ennoblement, ie, the increase of the opencircuit potential Ecorr is associated with the formation of a biofilm and the increase of exchange currency density of cathodic reactions.1113 In this experiment, the biofilm cannot be formed due to the existence of residual chlorine. Moreover, as mentioned above, the cathodic reactions will be de-activated with the increase of chlorine concentration, which will also lower the open-circuit potential. The greatly lowered open circuit potential may be explained by the synthetic impacts.

Electrochemical measurements
Figure 4 shows the Potentiodynamic polarisation curves for specimens in natural seawater, and 7.5 mg/l, 17 mg/l and 28 mg/l chlorinated seawater. Fig 5 is the result of Ecorr evolution with time. It can be seen that: (1) The corrosion rate increases with the increased concentration of chlorine. This is basically consistent with those of weight-loss experiments. Under the same over-potential, while the cathodic currency density decreases with the increased chlorine concentration, the anodic currency density is increased. This means the

Surface micrograph observation

Figure 6 (a-e) shows the SEM micrograph of metal specimens. It can be seen that: (1) Both the corrosion in natural seawater and chlorinated seawater are uniform, but the morphologies are different. (2) The corrosion in chlorinated seawater is more serious than that in natural seawater. Also, the extent of damage caused by corrosion is increased with the increase of TRC. Fig 4: Potentiodynamic polarisation curves for specimens in natural seawater, 7.5mg/l, 17mg/l and 28mg/l chlorinated seawater Corrosion in natural seawater morphologically has a lamella characteristic. However, in concentrations of 7.5mg/l and 17mg/l chlorinated seawater, the morphology were characterised by denudation and rupture, together with many bor-

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Fig 6: Surface micrograph after corrosion: (a) before corrosion (metallurgical); (b) in seawater; (c) in 7.5mg/l chlorinated seawater; (d) in 17mg/l chlorinated seawater; (e) in 28mg/l chlorinated

der lines separating the whole surface into many small areas. With the increase of chlorine concentration, the area became smaller. When the concentration is 28mg/l, the morphology was also of lamella characteristic, but the distance between lamellas was even shorter and the depth even deeper. As to the corrosion process, since the corrosion is processed from the boundaries to the grains, the coverage of corrosion products also appears from the boundaries to the grains. In the chlorinated seawater with higher chlorine concentration, the initial corrosion rate is higher at boundaries, generating more corrosion products and thus making the following corrosion more difficult. Therefore, the corrosion was shifted to the grains. However, in lower chlorinated seawater, the amount of corrosion product is small; the oxidants are more easily reached, thus sustaining the corrosion. From the perspective of metallurgical structure, this is due to the irregularity of structure. Relative to the ferrite,

the graphite and cementite in carbon steel is micro-cathode. Therefore, the ferrite will be corroded first, thus resulting in the lamella characterised morphology (Fig 6b). As the chlorine increases and time goes by, the corrosion will accelerate and progress. Big blocks will be locally corroded and break off from the body, thus making a morphology characterised as an ulcer (Figs 6c-d). When the concentration is 28mg/l, the corrosion is greatly accelerated; the body is thus corroded more deeply, resulting in thinner lamellas.

DISCUSSION
Explanation of corrosion process
When corrosion of metal in natural seawater takes place, the cathodic reaction is: O2 2H2 O 4e ! 4OH (1)

However, in chlorinated water, three more cathodic reac-

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tions can be involved in the cathodic processes. The reactions and their corresponding equilibrium formulate are: Cl2 2e ! 2Cl ( Cl2 ) E0 1:395 0:0295 log HClO ( Cl )2 H 2e ! H2 O Cl

(2) (3)

ClO and HClO are high enough, say several hundred mg/l, the cathodic current will fall with increased over-potential. This has already been observed by Neville.7

CONCLUSIONS
(1) Chlorinated seawater is more corrosive than natural seawater. The corrosion rate of carbon steel in sodium hypochlorite chlorinated seawater depends on the concentration of Total Residual Chlorine. The rates for specimens in chlorinated seawater with total chlorine of 7.5 mg/l, 17 mg/l and 28 mg/l are 2.4, 2.8 and 3.32 (103 g/cm2 day) respectively, ie, about 1.3,1.7 times of that in natural seawater. In general, the rates increased with the increase of concentrations of Total Residual Chlorine. A more accurate corrosion rate might be calculated if the period of corrosion time is extended to about six months. (2) The main cathodic electrode process in chlorinated seawater is the reduction of ClO iron. It takes place at a higher potential than for the reduction of oxygen, which will be more corrosive than the dissolved oxygen. (3) Chlorination will greatly lower the open-circuit potential, thus making carbon steel more vulnerable to corrosion. Specifically, while chlorination will promote the dissolution of metal, cathode reactions will be de-activated.

( HClO) E0 1:494 0:0295 pH 0:0295 log ( Cl ) ClO 2H 2e ! Cl H2 O E0 1:715 0:0591 pH 0:0295 log ( ClO ) ( Cl )

(4)

The relative rates of each reaction will depend on the pH of the solution and hence the relative concentrations of each species. According to Ives,14 at pH 8 to 9, the main oxidants presented in chlorinated seawater are ClO and HClO. Using a value of the equilibrium constant for the reaction: HClO OCl H
8 15

(5)

of 3.16 3 10 at T 298K, the ratio of thermodynamic activities, ClO /HClO at pH 8,8.3 is calculated as about 5:1. The dissolved oxygen will be improved a little by the presence of ClO, HClO to about 9.54mg/l,16 compared to 8.22mg/l in natural seawater at T 298K. Therefore, the ClO and HClO concentrations in the chlorinated seawater are not much higher than that of dissolved oxygen. As such, the recorded current could be representative of a composite cathodic reaction: ClO 2H 2e ! Cl H 2 O O2 2H2 O 4e ! 4OH

REFERENCES
1. Steve Raaymakers. 2002. Report for the GEF/UNDP/ IMO Global Ballast Water Management Programme (GloBallast). The Institute of Marine Engineering, Science & Technology Queens Golden Jubilee 2002 Marine Environment Award. London, October. 2. McCluskey DK, Holdo AE and Calay RK. 2005/6. A review of ballast water technologies. IMarEST Proceedings: Journal of Marine Design and Operations, Part B9, pp 2129. 3. Dangkun SP and Song Y. 2006. Fitted kinetic model of two algae in electrolyzed ships ballast water [J]. Journal of Harbin Engineering University, v27, n SUPPL. 2, Dec, pp216221. 4. http://docs.imo.org/ 5. Ventura G, Traverso E and Mollica A. 1989. Effect of NaClO biocide additions in natural seawater on stainless steel corrosion resistance. Corrosion (Houston), Vol 45, No 4, Apr, 1989, pp319325. 6. Gundersen R, Johansen B, Gartland PO, Fiksdal L, Vintermyr I, Tunold R and Hagen G. 1991. Source: Corrosion (Houston), Vol 47, No 10, Oct, pp800807. 7. Neville A, Hodgkiess T and Destriau X. 1998. Source: Corrosion Science, Vol 40, No 45, Apr-May, pp715730. 8. Eisnor JD and Gagnon GA. 2004. Impact of secondary disinfection on corrosion in a model water distribution system [J]. Journal of Water Supply: Research and Technology - AQUA, v53, n7, November, pp441452.

(6) (7) (8)

HClO H 2e ! H2 O Cl

The additional cathodic reactions (6) and (8), which are favoured in chlorinated seawater, might contribute to the lowered Ecorr . Since the ClO and HClO are more corrosive than O2, the corrosion rate of carbon steel in chlorinated seawater will be higher than that in natural seawater. Moreover, the rates will increase with the increase of TRC concentration.

Explanation of cathodic polarisation characteristics

As shown in Fig 4, the cathodic process in chlorinated seawater was de-activated compared with that of natural seawater. The possible reason might be the formation of scale. As is known, (OH ) will be produced by reactions (6), (7) and (8). With the increased concentrations of ClO and HClO, the local surface pH of carbon steel will be also increased during potentiostatic tests. Thus, scale, although little small in quantity, will be formed and possibly deposited on the surface. The amount of scale will increase with the concentrations of ClO and HClO (in seawater, the deposit will be less and invisible). If the concentrations of

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9. Song Y, Dang K, Chi H, Guan D. 2006. Corrosion behaviour of ships ballast tank in sodium hypochlorite treated ballast water [J]. Journal of Harbin Engineering University, v27, n SUPPL. 2, Dec, pp637641. 10. Wang G, Spencer J and Sun H. 2003. Assessment of corrosion risks to ageing ships using an experience database. Proceedings of the 22nd International Conference on Offshore Mechanics and Arctic Engineering, ASME, Paper OMAE 200337299. 11. Florian Mansfeld. The interaction of bacteria and metal surfaces [J]. Electrochimica acta 52(2007)76707680. 12. Fei Kuang, Jia Wang, Li Yan and Dun Zhang. 2007. Effects of sulfate-reducing bacteria on the corrosion behaviour of carbon steel. Electrochimica Acta, Vol 52, Issue 20, 10 June, pp60846088.

13. Wang Wei, Wang Jia and Xu Haibo. 2006. Influence of biofilms adsorption kinetics on the open-circuit- potential changes of passive metals in seawater [J]. Journal of Chinese Society for Corrosion and Protection, Vol 126, No 12, pp6569. 14. Ives MB, Lu YC and Luo JL. 1991. Cathodic reactions involved in metallic corrosion in chlorinated saline environments. Corrosion Science, Vol 32 No 1 pp91 102. 15. Applied Water Technology (1st edn). Campbell Petroleum Series. Oklahoma, June 1996. 16. Kun Dang and Yongxin Song. 2007. Electrolytic treatment of ships ballast water. IMarEST Proceedings: Journal of Marine Design and Operations, Part B12, pp915.

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