Corrosion Science 48 (2006) 39073923 www.elsevier.

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Monitoring corrosion rates and localised corrosion in low conductivity water

L.R. Hilbert
*
Department of Manufacturing Engineering and Management, Technical University of Denmark, Building 204, DK-2800 Lyngby, Denmark Received 18 November 2004; accepted 16 March 2006 Available online 15 May 2006

Abstract Monitoring of low corrosion rates and localised corrosion in a media with low conductivity is a challenge. In municipal district heating, quality control may be improved by implementing on-line corrosion monitoring if a suitable technique can be identied to measure both uniform and localised corrosion. Electrochemical techniques (LPR, EIS, crevice corrosion current) as well as direct measurement techniques (high-sensitive electrical resistance, weight loss) have been applied in operating plants. Changes in the corrosion processes are best monitored in non-aggressive, low conductivity media with sensitive electrical resistance technique and crevice corrosion current measurements. 2006 Elsevier Ltd. All rights reserved.
Keywords: A. Mild steel; B. EIS; B. Corrosion monitoring; B. District heating

1. Introduction Internal corrosion control of the district heating transmission and distribution net is primarily obtained by control of the water quality. Uniform corrosion of carbon steel is thus mitigated by low oxygen concentration and conductivity, and high pH. In spite of high water quality internal corrosion failures can occurprimarily localised corrosion under deposits or in crevices due to oxygen ingress, local changes in water composition or microbially inuenced corrosion. On-line monitoring of water quality parameters,
*

Tel.: +45 45 25 21 93; fax: +45 45 93 62 13. E-mail address: LRH@ipl.dtu.dk

0010-938X/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2006.03.004

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e.g., conductivity, is carried out in some systems, but most water quality parameters are only obtained by periodical analysis. This may be adequate to control uniform corrosion, but will not reveal the variations that occur and the resulting risk of localised corrosion. If the risk of corrosion is detected at an early stage, then it may be possible to correct the problem and avoid a failure. However, monitoring low corrosion rates and localised corrosion in a media with low conductivity is a major challenge, and suitable techniques must be identied to measure both uniform and localised corrosion. The aim of this paper is to evaluate the reliability and applicability of corrosion monitoring techniques for carbon steel piping in the specic water chemistry in Danish district heating systems [13]. This work is part of a Nordic research project on quality control in district heating systems, where monitoring techniques were tested in district heating (Denmark, Finland), district cooling (Sweden), and geothermal waters (Iceland, Norway). 1.1. Limiting corrosion in district heating Theoretically, in deaerated pure water at pH values 9.810 iron is in a FeFe3O4 equilibrium, where the hydrogen ion reduction reaction can accelerate the formation of a thin, protective layer of magnetite [4]. In the pH range of passivity, however, the risk of formation of oxygen concentration cells is large if oxygen ingress should occur. The electrochemical potential in the aerated zones will increase and stabilise the passive areas on which the cathodic reaction can take place, while the anodic reaction will proceed with a high rate in the low potential non-aerated zones, e.g., in crevices. The rate of localised corrosion is enhanced with increasing conductivity as the range of the corrosion element is increased, hence a larger area of, e.g., the pipe can act as cathode and crevices can be activated as anodes. Furthermore, the amount of corrosive species is increased for higher conductivity media. If a general pH decrease occurs in deaerated water, then passivity may be lost and the uniform corrosion rate increases. Mercer and Lumbard [5] have shown that in water, with the complete absence of halide or other aggressive ions, dissolved oxygen promotes the formation of a protective passive layer and the corrosion rate is very low and stable. In triple distilled water at neutral pH and 50 C, carbon steel was exposed to 80 ppb oxygen, air saturated and oxygen saturated conditions. Uniform darkening of probes and low corrosion rates occur in the 80 ppb dissolved oxygen condition. The most severe corrosion attacks occur in air saturated water by localised corrosion. In the oxygen saturated water steel is passivated. Giving corrosion rates as thickness reduction, 80 ppb oxygen results in rates of 1530 lm y1, while the passive state (oxygen saturated) gives 220 lm y1. Mercer and Lumbard also show that the risk of localised corrosion is present if aggressive ions in even small concentrations enter the system [5]. In district heating water, passivation is facilitated by the water chemistry, so uniform corrosion rates of 23 lm y1 are obtained. There is a risk of localised corrosion as described above if aggressive ions like chlorides should enter the system and if oxygen concentration cells are formed. The Danish District Heating Association [6] has consequently specied the criteria for the quality of water for Danish district heating systems to obtain acceptable corrosion resistance of carbon steel, copper alloys and stainless steels. The system water is categorised into four qualities: untreated, softened, partially desalted or desalted. For the last three qualities, the pH should be 9.8 0.2 and the oxygen concentration below 20 ppb. In desalted water, the conductivity must be <25 lS cm1. The make-up water is categor-

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ised into three qualities: potable water, softened water and desalted water. The best quality is desalted (conductivity <10 lS cm1), adjusted to a pH of 9.8 0.2 and deaerated (<100 ppb). 1.2. Considerations when implementing corrosion monitoring in district heating systems On-line, real-time corrosion monitoring of uniform corrosion rates in water distribution systems like cooling water is typically obtained with linear polarisation resistance (LPR), electrical resistance (ER), or o-line by use of weight loss coupons [79]. For district heating systems corrosion monitoring with non-destructive, on-line, real-time techniques would be ideal, and both low uniform corrosion rates as well as localised corrosion risk should be assessed. ER measurements are widely used as an electrical analogue to weight loss and can be applied without any restrictions of the type of media. With traditional ER technique, the change in absolute resistance is taken as a measure of the accumulated corrosion rate over a long time period. During the last decade, ER probes and instrumentation with better resolution on the metal thickness and better temperature compensation have been developed, increasing the sensitivity and shortening the response time. With sensitive techniques [10,11] corrosion rates of few lm y1 can be measured in a few hours. ER is not recommended for localised corrosion as the eect of complex geometry changes on electrical resistance is not trivial and in any case the average rate will be overestimated. 1.2.1. Electrochemical techniques in low conductivity media The combined resistance measured with LPR is the sum of the solution resistance Rs and the polarisation resistance Rp. In case of large Rs (low conductivity), there is a risk of underestimation of the corrosion rate if IR compensation is not applied, which is the main reason why the use of electrochemical techniques in low conductivity media is not recommended [8,12]. However, if corrosion rate is also very low (large Rp values), then it could be argued that the error will be small. The Rs in district heating water with a conductivity of 25 lS cm1 is actually less than 1/10 of the Rp for the uniform rates of 2 3 lm y1, in which case the error would be less and LPR possibly applied [13]. In the LPR technique, the corrosion current is approximated by a linear correlation to the slope of the potentialcurrent (Ei) response in the vicinity of the corrosion potential. Corrosion rate is calculated using the correlation factor B, which is a function of Tafel slopes and corrosion controlling mechanism. LPR data from real corroding systems often deviate from linearity by curvature and asymmetry in the Ei response. The slope R is therefore determined as the tangent at the corrosion potential, but this may be dicult if the linear part of the curve is small or if the corrosion potential is unstable. The LPR technique is commercially claimed to give instant monitoring of variations in corrosion rates in aqueous systems like cooling water. Automated systems often scan with a high rate to give data within minutes and give no option to evaluate the appearance of the curve, and therefore no option to examine, if hysteresis dominates the Ei response. This hysteresis is a result of time dependent current contributions that add to the faradaic current. Potential hysteresis is observed for too high scan rates in systems with large interfacial capacitances, large polarisation resistances, pseudocapacitances or mass transport limitations [12]. To avoid hysteresis the scan rate must be adjusted to the time constant of the corrosion cell. In cells with large capacitative or diusional eects very low scan

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rates should therefore be applied to avoid overestimating the corrosion rate [12], opposite to the error expected in low conductivity water. Electrochemical impedance spectroscopy (EIS) is very useful to support the analysis of the reliability of LPR data. The Rs value can be measured and in addition possible eects of diusion identied. For diusion controlled systems, measuring at very low frequencies is necessary to obtain the low frequency plateau for the polarisation resistance, which is the sum of charge transfer resistance and diusion resistance [12]. The disadvantage is therefore that an EIS measurement with adequately low frequencies could take days and the system may then change invalidating the measurement. 1.2.2. Monitoring localised corrosion Localised corrosion occurs stochastically and is, therefore, also dicult to monitor on separate probes. For weight loss coupons visual inspection gives further clarication of the corrosion mode, but the response time is large. LPR is based on averaging corrosion rate over a known surface area, so if the actual corroding area is smaller, the localised corrosion rate will be underestimated. For on-line monitoring, a number of systems exists either based on galvanic probes of copper and steel, e.g., or on generating a geometry to favour localised corrosion and measuring the resulting current between the expected anode and cathode areas. Lei et al. [14] used an articial occluded cell for monitoring the propagation rate of localised corrosion based on monitoring the current owing between an anode and a cathode. No or low current indicates a low driving force for crevice corrosion, while an increasing current indicates localised corrosion. An alternative method for evaluating the risk of localised corrosion is the application of electrochemical noise (EN), where analysis of the potential and current noise pattern can indicate whether pitting or uniform corrosion is occurring. EN is increasingly being applied for industrial corrosion monitoring and has been tested in parts of the overall project [15], but since only few data exist from the Danish systems EN, will not be discussed further in this paper. 2. Experimental procedures Corrosion probes were made from carbon steel or iron. ER probes were made of 0.1 mm thick iron foil of 99.9% Fe and with a rectangular design of the dimensions 200 2 mm. High-sensitive ER Metricorr equipment [11] produced continuous data. For rectangular standard weight loss coupons, the material used was carbon steel sheet and the dimension was 100 13 1 mm. Weight loss was based on periodical removal of probes after a minimum of 6 months exposure. Rod shaped carbon steel was the base material for the electrochemical tests. A probe with three close spaced cylindrical (40 B7 mm) steel electrodes, each with an area of 9.2 cm2, was used. Periodical measurements were conducted with a Gamry FAS 1 potentiostat. LPR measurements were conducted either with 10 mV amplitude and 0.05 mV s1 scan rate or with 5 mV amplitude and 0.005 mV s1 scan rate, the latter based on previous laboratory tests [13]. For analysis, a straight line tangent was tted to the curve going in the anodic direction at the corrosion potential. The empirical B value determined from a range of laboratory tests was 15 mV for steel in district heating water [15], and this value has been applied for calculating corrosion rates from polarisation resistance values. EIS included 5 points per decade, amplitude of 10 mV and a frequency range of 100 kHz to

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minimum 100 lHz. Laboratory data showed that acquisition of an acceptable EIS measurement in this media took up to 3 days [16]. Crevice corrosion risk was measured on a probe [17,18] in which the anode was a cylindrical plate with an area of 1.77 cm2 made of Armco iron. The anode is the central part of the probe and is electrically isolated from the rest of the system and mounted under a glass lter, allowing a certain transport of ions but still limiting diusion. The galvanic current measured continuously between the iron electrode and the rest of the system (in principle the entire pipe) with a zero resistance ammeter (ZRA) is a measure of the crevice corrosion current on the iron electrode. A laboratory trial of 21/2 months duration to simulate district heating conditions has been conducted in a prototype unit of 30 l volume [15]. Probes and techniques were similar in laboratory and eld trial. The prototype unit was lled with N2-purged water of pH 9.82 (adjusted with 1 M NaOH) and conductivity of 23.2 lS cm1. The water was kept at 60 C and recirculated, and after 11/2 months corrosion monitoring was initiated. At this point pH was almost unchanged (9.77), but the conductivity had increased to 87.9 lS cm1, due to the release of metal ions from corrosion of the inner surfaces of the unit or slow dissolution of the corrosion scale on these surfaces. Monitoring by ER, crevice cell, EIS and LPR was carried out for one month (start day 0) on the unchanged system. Followed by 1 h of oxygenation on day 27 to provoke corrosion. Bypass units similar to the prototype unit have been mounted on the return stream in ve Danish district heating plants. In addition, two bypass units were mounted on the central cooling and central heating systems of a large pharmaceutical plant to study the eect in water of lower quality. The bypass unit was permanently mounted on the system, while monitoring was conducted with instruments that were moved around to dierent locations. The unit and probes were exposed to the media for a minimum of one month prior to measurements. Values of corrosion rates and water chemistry parameters (oxygen, pH, conductivity, temperature) were measured simultaneously for a minimum of 3 weeks for each system. The unit and the specic analytical techniques have been described in detail elsewhere [1,17]. 3. Results 3.1. Laboratory trial in prototype The laboratory unit experiment is a simulation of the performance of techniques in non-corrosive media (simulated district heating water) as well as how the techniques react to forced ingress of oxygen for 1 h. The data shows the corrosion rate (Fig. 1) after 11/2 months of initial exposure as well as the following month (day 028). The ER technique responded with a very low corrosion rate (30.3 lm y1) until the oxygenation event, where the measured corrosion rate increased to 35 lm y1. During the following day, the ER rate increased continuously to maximum 1200 lm y1. The crevice corrosion cell indicated zero current until oxygenation. For the 1 h oxygen ingress, crevice corrosion current increased to 7 lA and continued to increase to maximum 22 lA for the following 5 h and then decreased steadily. The combination of techniques shows that severe localised corrosion attacks were initiated, and that they continue after oxygen has been shut o. The measured extreme ER rate of 1200 lm y1 does not relate to uniform corrosion, and the continued increase of ER corrosion rate is a result of the changed geometry, as

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(one hour oxygenation)

1200 1000 800

30 25 20 15 10 5 0
A

my-1

600 400 200 0 26 26.5 27 Time - days 27.5 28

Fig. 1. Laboratory trial in deaerated articial district heating water. Data given are corrosion rate measured by ER (lm y1) and crevice corrosion current (lA) during the last two days of the experiment, including 1 h oxygenation on day 27.

corrosion attacks penetrate the thin foil. This was documented on retrieval of the ER probe, where severe localised attacks from the oxygenation were found. Both techniques responded quickly to the change of media, and an eect could be seen hours after the oxygenation had been turned o. To evaluate the use of LPR for this application, LPR as well as EIS for supporting mechanistic analysis was conducted. Based on ER data the corrosion rate decreases from 3 to 0.3 lm y1 from day 020, so the values are low, but changing even within few days. The LPR data in Fig. 2 during day 026 are stable, but quite asymmetrical in terms of anodic and cathodic current. Estimated Rp is around 18 kX cm2, indicating higher corrosion rates (10 lm y1) than ER. The measurement at day 27 gives a quite symmetrical straight curve giving Rp values of 1500 X cm2 (115 lm y1).

0.04
day 27

Potential V vs Fe

0.02 0 -0.02 -0.04 -0.06 -0.08 -1.E-06

days 0 to 25

-3.E-06

1.E-06

3.E-06

Current Acm-2
Fig. 2. Laboratory trial in deaerated articial district heating water. LPR curves showing only slightly changing response from day 0 to 25 and the dramatic change in corrosion potential and slope on day 27.

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The EIS responses were also initially unchanged (Figs. 3 and 4), except for a small decrease in solution resistance to approximately 1800 X cm2. A full equivalent circuit was not tted to the data set as the number of points at low frequencies was so few that this part would disappear in the tting procedure. Going for lower frequencies would increase the measurement time to more than two days. Corrosion rates were therefore estimated by tting the low frequency data to a large semicircle (typical values: R  400 kX cm2, C  45 mF cm2) indicating very low corrosion rates (0.4 lm y1) in the same range as the ER data. The large capacitance values are interpreted as an interfacial capacitance, probably incorporating diusion phenomena or surface layers. After oxygenation (day 27), the response changed to a small depressed semicircle (Nyquist plot). Estimation of polarisation resistances from day 27 gives 1900 X cm2 giving a corrosion rate of 92 lm y1, but this response is unstable as the system is changing. This Rp value is almost

12000
Days 0 to 25

-Zimag Ohmcm2

8000

4000
Day 27

0
0 4000 8000 12000

Zreal Ohmcm2
Fig. 3. Laboratory trial in deaerated articial district heating water. EIS Nyquist plot showing only slightly changing response from day 0 to 25 and the dramatic change on day 27.

10000
Z day 0-25

90 80 70 50 40
phase day 0-25 phase 27

Zmod Ohmcm2

Z 27

1000

30 20 10 0

100 0.0001

0.01

1 100 Frequency Hz

10000

Fig. 4. Laboratory trial in deaerated articial district heating water. EIS Bode plot showing only slightly changing response from day 0 to 25 and the dramatic change on day 27.

- Phase

60

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the same as the value determined by LPR on the same day, but the LPR Rp is not corrected for Rs (1800 X cm2), meaning that LPR actually measured only the Rs. For a detailed analysis of the EIS data (Figs. 3 and 4), it appears in the Nyquist representation that the response consists of a high frequency eect due to the low conductivity, a straight line (h.f.) contribution, and nally at lower frequencies the start of a very large semicircle or a semi-innite diusion related part. Fig. 5 shows the h.f. part of the Nyquist data from day 0, which is after one month exposure. As illustrated, the h.f. straight line is tted with a constant phase element of Q  6 mF cm2 and n  0.6 and can be related to the formation of a diusion limiting lm. The other h.f. feature visible in Fig. 5 and on the phase angle above 10 kHz in the Bode representation (Fig. 4) only occurs in very low conductivity media and disappears at higher conductivities. For a range of conductivities (20 1500 lS cm1), it has been shown (Fig. 6) that the modulus of impedance at zero phase at 1 kHz is inversely proportional to the conductivity, and that the solution resistance Rs can,

Fig. 5. Detail of Nyquist plot of data from day 0 in laboratory trial in articial district heating water. H.f. feature refers to an artefact seen in the low conductivity media in the test setup, and h.f. straight line to straight line in the h.f. region followed by either a large semicircle or Warburg diusion.

0.05 1/conductivity cm S
-1

0.04 0.03 0.02 0.01 0.00 0 2000 4000 6000 8000

2

10000

12000

Zmod (at 1000 Hz) Ohm cm

Fig. 6. Conductivity1 vs. impedance Z at 1 kHz in laboratory trial, deaerated articial district heating water. Linearity documents that Z at 1 kHz is equal to the solution resistance Rs.

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therefore, be determined at this frequency. The response in the range of 10 kHz100 Hz is purely resistive. Comparing these data with the ER data shows that the corrosion rate in the deaerated laboratory unit system is overestimated by a factor of approximately 10 by LPR, probably due to hysteresis and cannot be fully determined even by EIS. In the corrosive media caused by oxygenation, LPR and EIS, however, reacted to the changing conditions. 3.2. Field monitoring in district heating plants The purpose of the eld test is to evaluate the performance of the dierent techniques in the actual Danish water quality and whether the corrosion monitoring data correlate with water quality. An overview of the results of all 7 bypass units is given in Table 1. Monitoring of oxygen, pH, conductivity, and temperature showed that the district heating systems met the criteria of the Danish District Heating Association on most of the parameters. The overall tendency was that corrosion problems were related to the addition of make-up water. In the VEKS plant, a slightly lower pH and slightly higher conductivity than recommended was measured with a higher uniform corrosion rate (8 lm y1 on weight loss) as a result. For the industrial central cooling system, corrosion rates were very low in spite of higher conductivity and lower pH, probably due to low temperature and low oxygen content. Higher conductivity in itself did not give higher corrosion rates, and conductivity alone cannot be used to assess corrosion risk. For the industrial central heating system, major additions of make-up water during the trial increased the oxygen content and conductivity resulting in fairly high corrosion rates. 3.2.1. Weight loss corrosion data Weight loss data averaged over 612 months from all units gave corrosion rates in the range of 019 lm y1 depending on the system. Due to the long exposure time, operational parameters for the district heating systems may have changed during the exposure time of the weight loss coupons, which makes the comparison of these long-term data with the data from the 3 week intensive monitoring dicult. However, the long-term weight loss data give values in the expected ranges and trends similar to data from the intensive monitoring campaign. Examples are given in Figs. 7 and 8 of uniform (Aalborg) versus

Table 1 Field monitoring results Plant Odensea VEKS Viborg Aalborg Ballerup Industrial cooling Industrial heatinga Oxygen (ppb) 01 01 0 35 0 0 0 pH 9.810 9.29.4 9.59.7 9.69.8 9.9 8.88.9 99.4 Conductivity (ls cm1) 70 8090 30 45 200250 330350 350 Temperature (C) 4045 3555 4752 3541 50 6.57.5 6075 Corrosion rate (ER) (lm y1) 0 12 0 0.81.7 <2 0 515 Corrosion rate (weight loss) (lm y1) 1019a 89 34 2 <2 <1 79a

Numbers are given as average values under normal operational conditions. Weight loss is averaged over 612 months, while other data are from normal conditions during the intensive 34 weeks monitoring. a System exposed to abnormal large make-up water additions during trial.

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Fig. 7. Surface of cleaned weight loss coupon from Aalborg. Average corrosion rate 2 lm y1 and uniform corrosion observed.

Fig. 8. Surface of cleaned weight loss coupon from Viborg. Average corrosion rate 3 lm y1 and localised attacks observed.

localised corrosion (Viborg) on probes with low average corrosion rates. Localised corrosion, deposit formation or uniform corrosion can be visually identied on the coupons.

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3.2.2. ER and crevice cell A fast response to changing media was found by continuous monitoring with the ER technique. Visual examination revealed that primarily uniform corrosion appeared on all the ER probes. Both high and low corrosion rates could be detected on the same probe and within hours very low rates could be determined. As an example, the data from the high water quality system in Aalborg are given in Fig. 9, where the thickness of the probe as a function of time is depicted. In the Odense plant, water quality was high and corrosion rates were low, but a test with an abnormal large make-up water addition dramatically changed water parameters and caused very high corrosion rates. The data are shown to illustrate how ER and crevice cell (Fig. 10) perform in media which turn corrosive due to poor make-up water quality (cation exchanged potable water without deaeration). Under normal operation, corrosion

100.05 Element thickness (m) 100.00 y = -9E-05x + 100.01 99.95 99.90 99.85 99.80 0 168 Time (hours) 336 Vcorr = 0.8 my-1

Fig. 9. Thickness of ER element in Aalborg unit. The thickness reduction rate gives a stable corrosion rate of 0.8 lm y1.

800 700 600 Vcorr (my-1 ) 500 400 300 200 100 0 0 168 336 504 Time / hours 672 840

80

ER Crevice cell

70 60 50 40 30 20 10 0 A

Fig. 10. Corrosion rate determined from ER measurements and crevice corrosion current in Odense unit during both normal operation and forced make-up water addition (672693 h).

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rates measured by ER are around 1 lm y1 and crevice corrosion current is negligible. Electrochemical measurements indicated larger corrosion rates of approximately 6 (EIS) to 60 (LPR) lm y1. The LPR corrosion rate of 60 lm y1 during normal operation is unrealistic, as the weight loss averaged rate over 440 days, including both normal operation and the aggressive test of make-up addition, was 1019 lm y1. The attacks on weight loss probes were localised but large, and bright non-corroded areas could still be found on the probe surfaces after one year exposure. After 28 days, make-up water was supplied for 21 h duration and resulted in oxygen levels >100 ppb, decreasing pH, increasing conductivity and decreasing temperature both during the actual make-up water addition and for approximately one day after. Corrosion rates of up to 800 lm y1 (ER) and crevice currents up to 40 lA were measured. Corrosion rates measured by electrochemical measurements doubled to approximately 115 lm y1. Both ER and crevice cell quickly responded to the change from normal operation to aggressive make-up water and data values seem reliable, although the ER rate is likely to be overestimated in the case of localised corrosion. In most systems, the crevice cell gave negligible currents indicating no localised corrosion and correlating with the fact that uniform corrosion was identied on most weight loss probes. In Viborg, corrosion rates based on ER and weight loss were very low, but visual examination of weight loss probes revealed that small localised attacks were initiated. The sensitive crevice cell also reacted to periodic small short term (max 5 h) oxygen levels of 100 ppb with current peaks of less than 1 lA (Fig. 11). The ER measurement did not react to these short time oxygen variations. Viborg is a transmission system that delivers make-up water for distribution systems. The make-up water is of high quality, and treated with cation exchange and reverse osmosis and deaerated to approximately 100 ppb oxygen. The system water normally has 5 ppb or less oxygen, 30 lS cm1 conductivity and pH 10. The monitoring shows that oxygen level was stable, but slightly aected by a number of short term make-up water additions, 6 times (from 10th to 26th day), that were a part of the normal operation. The other environmental parameters were only aected in the third make-up water addition (after 21 days), where there was a small

120 100 oxygen, ppb 80 60 40

1 oxygen 0.5 crevice cell current,A crevice current

-0.5 20 0 0 7 14 Time / days 21 28 -1

Fig. 11. Oxygen content and crevice corrosion current in Viborg unit monitored during normal operation. Peaks in oxygen content correlate with short term make-up water additions.

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increase in conductivity (max 50 lS cm1) and decrease in pH (min. 9.58). The increase in oxygen concentration was considerably higher than expected for make-up water of this quality. The data made the operators realise that the deaeration system must be temporarily out of function, and this error was immediately corrected to stop the localised corrosion. 3.2.3. Electrochemical data LPR measurements overestimated corrosion rates by a factor of 10 in the laboratory trial, but were for comparison applied in all systems with the ambition to examine if this overestimation could be eliminated. All LPR data with the higher scan rate of 0.05 mV s1 (Ballerup, Odense, VEKS, Viborg) gave a signicant overestimation of corrosion rate as compared to ER. For the lower scan rate of 0.005 mV s1 (VEKS, Viborg, Aalborg, industrial units), corrosion rates were in the same range as the ER and weight loss in Viborg and in the industrial units. In Fig. 12, LPR data obtained with both high and low scan rates on the 12 oclock positioned probe in Viborg are shown. The rst one is conducted with 10 mV amplitude going rst in the anodic and then in the cathodic direction making the hysteresis visible, while the low scan rate curve with 5 mV amplitude is conducted only in the anodic direction. The faster curve is dominated by hysteresis and almost any tangential slope can be tted to these data if the corrosion potential is shifted a little. The slower curve is very asymmetrical and does not cross zero current at the corrosion potential, but a corrosion rate (<2 lm y1) in the range of the ER rate can be determined. So the measurement conducted with a 10 times larger scan rate gives a resistance value (approximately 15 kX cm2) that is approximately 10 times smaller than that for the lower scan rate (approximately 150 kX cm2). The corresponding EIS in Fig. 13 illustrates that the phase angle is not zero at the lowest frequency measured (100 lHz) and that a pure resistive response has not been reached. The consequence of this will be further evolved in the discussion.

-145 R= 158000 Ohm*cm E mV vs iron coupon -150 0,005 -155 R= 15030 Ohm*cm2
2

-160 0,05 -165 -1.5E-03 -1.0E-03 -5.0E-04 0.0E+00 Current mAcm-2 5.0E-04

Fig. 12. LPR at two scan rates (0.05 and 0.005 mV s1), day 15, Viborg unit. The fast scan is dominated by strong curvature and hysteresis. The slower scan is only in the anodic direction, and a tangent to the curve at the corrosion potential is determined as the Rp.

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appr. freq. for 0.005 mVs-1 100000

appr. freq. for 0.05 mVs-1 90 80 70 50 40 30 20 10 - Phase 60

Zmod Ohm*cm

10000

1000 0.0001

0.01

100

0 10000

Frequency Hz
Fig. 13. EIS Bode plot, day 15, Viborg unit showing that response is only obtained at very low frequencies. Corresponding frequencies for LPR scan rates are marked to illustrate that the capacitative part of the response is very strong at those scan rates.

4. Discussion The purpose for using EIS in the systems was to evaluate whether the LPR results could be valid. Therefore, the EIS results will be briey discussed rst. The laboratory EIS data (Figs. 3 and 4) give purely resistive response in the range of 10 kHz100 Hz, and the Rs value is estimated at 1 kHz. Above 10 kHz the eect of low conductivity media shows. This is not as complex as observed by Chechirlian et al. [19] who in media of 100 lS cm1 and lower showed that the eect of low conductivity on the high frequency data can give serious misinterpretations of the EIS data. Likewise, Stewart et al. [20] indicated that high frequency artefacts may appear in low conductivity media and that the eects may be seen down to frequencies as low as 100 Hz. The EIS technique in most cases gave corrosion rates in the range correlating with ER and weight loss. The main problem is the long data acquisition time of several days, with the risk that instability may invalidate the results. Furthermore, simple tting with a Randles circuit will in many cases not be adequate to nd a correct polarisation resistance from the obtained points. The correct polarisation resistance value might only be found by going to even lower frequencies if the system is under diusion control. The data from the eld tests give high values of Rs (up to 20 kX cm2), very high values of Rp (up to 400 kX cm2) and very high values of C (up to 50 mF cm2), which are all factors dening an extremely slowly reacting system. The scan rates applied in commercial LPR equipment up to 1 mV s1 may be ideal for normal systems, but adjustments need to be made depending on the corrosion system. The correct scan rate for conducting LPR measurements without hysteresis eects may be estimated for a specic system. According to Mansfeld and Kendig [21], scan rates V in LPR measurements and frequencies f in EIS are connected by Eq. (1) V DE p f ; 1

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where DE is the peak-to-peak amplitude. A specic scan rate corresponds to a frequency in the EIS plot. For a simple Randles circuit with a capacitance C the approximation [12] can be made for the lower breakpoint frequency fbp in Eq. (2) fbp 1 ; 2 p C Rs R p 2

where fbp (Hz) represents the lower frequency at 45 point on the phase curve. To nd the low frequency plateau of the impedance, a 10 times lower frequency named the maximum frequency should be applied [21]. The maximum frequency corresponds to the maximum scan rate to be applied by Eq. (1), which is therefore inversely proportional to the size of the elements C, Rs and Rpand thus the time constant of the corrosion cell. For larger values a lower scan rate should be applied. In a similar way Bellezze et al. [22] have for passive surfaces found the appropriate scan rate for LPR based on the frequency at which the low frequency plateau could be reached by EIS. In cases where this was not possible, a default rate of 0.05 mV s1 was used. The two scan rates applied correspond according to Eq. (1) to frequencies of 1.6 mHz for 0.05 mV s1 and 10 mV amplitude, and 0.3 mHz for 0.005 mV s1 and 5 mV amplitude (marked in Fig. 13). These values are far above the maximum allowable frequency if the low frequency plateau is to be reached. So hysteresis as observed in Fig. 12 is to be expected. Based on Eqs. (1) and (2), for this system an unrealistic LPR scan rate of only 12 lV s1 should have been applied for 5 mV amplitude giving a measurement time of 20 days, during which time changes invalidate the data. Application of the LPR technique in low conductivity water is not recommended in standards [8] due to risk of underestimating the corrosion rate by measuring the combined Rs and Rp. In these studies, the opposite problem was faced, namely, overestimation as compared to ER. The high scan rate gives overestimated rates, while the slower scan rate in some of the plants gives more reliable results. The choice of 0.005 mV s1 was made from preliminary experiments and from a practical aspect of realistic monitoring times, but as illustrated, the actual performance after long exposure times in real systems was more complex as a passive system dominated by diusion reacts slowly. In Icelandic studies of district heating, a scan rate of 0.0005 mV s1 was applied with much better success than the Danish trial [23]. LPR data from the seven Danish plants seem to give correct corrosion rates in a few cases, but the risk of misinterpretation is large. Furthermore, the empirical B value of 15 mV is determined in the simulated laboratory environment, and if rate controlling mechanism changes e.g., during oxygen ingress, then the B value will also change giving an additional error. The calculated corrosion rates are a function of the true reacting surface area. In the case of localised corrosion, the true active area is smaller than the nominal, and the calculated corrosion rate will underestimate the localised rate (and overestimate the rate on passive areas). When ER probes in the laboratory trial were attacked by localised corrosion, the uniform corrosion rate was overestimated, but the reaction to the changed conditions was fast and easily detectable. Norin and Vinka [24] reported good results of monitoring in soil with ER, but accordingly found cases of localised corrosion where rates were overestimated. In the eld trial corrosion attacks on ER probes were uniform, probably due to the generally non-corrosive media, apart from in Odense, where a strong increase of the corrosion rate and localised attacks on the surfaces were observed. So in cases where the crevice cell registers localised corrosion, the absolute values from the

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ER technique are not transferable to a uniform rate. However, early warning capacity is obtained with this technique reacting directly to material loss. The crevice corrosion cell reacts to make-up water addition in Viborg, but the current output is substantially lower than in Odense. As seen in Fig. 11, an increased oxygen concentration to about 100 ppb results in currents of maximum 1.7 lA, and the current decreases with time. In Odense, current response was 40 lA (Fig. 10) and severe corrosion attacks were found on weight loss probes. In desalted water (Viborg), the range of an oxygen concentration cell will be strongly limited because of the low conductivity. Therefore, the eect in crevices and under deposits will be less critical. The absolute crevice current values do give an indication of the severity of the corrosion attack, and the variation in the current can be used to monitor the appearance of a risk. 5. Conclusion Reliable monitoring of low corrosion rates and localised corrosion in a media with low conductivity is a challenge. Monitoring of low corrosion rates (slowly reacting systems) in a low conductivity media fails with LPR, which overestimates corrosion rates. This result contradicts with the underestimation in low conductivity media predicted in the standards. By use of EIS, the overestimation has been explained by the eect of scan rate on the reliability of LPR data of slowly reacting systems. LPR reacted to the appearance of corrosive conditions in the laboratory tests, but in the eld test this warning capacity failed. The sensitive ER technique functions independent of media type and measures both high and low rates with low response times. ER fails in the case of localised corrosion in which case the crevice corrosion current measurements perform well and react promptly to the environmental changes. Based on chemical characterisation of the media, high-sensitive ER, weight loss, and visual examination of probes from all 7 units in the eld trial, it is concluded that the ER technique in combination with the crevice corrosion cell can be recommended for district heating systems to give continuous and correct uniform corrosion rates as well as to monitor risk of localised corrosion. Acknowledgements Cooperation with FORCE TECHNOLOGY and MetriCorr Aps was highly appreciated, and Nordic Innovation, the Danish District Heating Association, and the participating Danish district heating plants and industry are thanked for their support to the project. References
[1] L.R. Hilbert, R.I. Thorarinsdottir, A. Andersen, L.V. Nielsen, Optimising corrosion monitoring in district heating systems, in: Proc. EUROCORR 2002, Granada, Spain, September 2002. [2] L.R. Hilbert, A. Andersen, L.V. Nielsen, R.I. Thorarinsdottir, Comparison of applied corrosion monitoring techniques in district heating systems, in: Proc. 13th Scandinavian Corrosion Congress, Iceland, April 2004. [3] L.R. Hilbert, L.V. Nielsen, A. Andersen, Corrosion rate monitoring in district heating systems, in: Proc. NACE CORROSION 2005, Paper No. 05144, April 2005. [4] M. Pourbaix, Lectures on Electrochemical Corrosion, Plenum Press, New York, 1973. [5] A.D. Mercer, E.A. Lumbard, Corrosion of mild steel in water, Brit. Corros. J. 30 (1995) 4355. [6] DFF Vejledning, Vandbehandling og korrosionsforebyggelse i fjernvarmesystemer, Danske Fjernvarmevrkers Forening, Denmark, 1999.

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[7] ASTM Standard practice of calculation of corrosion rates and related information from electrochemical measurements, G102-89 (Reapproved 1999), ASTM International. [8] ASTM Standard guide for on-line monitoring of corrosion in plant equipment (electrical and electrochemical methods), G96-90 (Reapproved 2001), ASTM International. [9] ASTM Standard guide for conducting corrosion tests in eld applications, G4-01, ASTM International. [10] P. Kempe, A. Denzine, Evaluating corrosion monitoring techniques, Chem. Process. 64 (2001) 4245. [11] L.V. Nielsen, K.V. Nielsen, Dierential ER-technology for measuring degree of accumulated corrosion as well as instant corrosion rate, in: Proc. NACE CORROSION 2003, Paper No. 03443, March 2003. [12] R.G. Kelly, J.R. Scully, D.W. Shoesmith, R.G. Buchheit, Electrochemical Techniques in Corrosion Science and Engineering, Marcel Dekker, New York, 2003 (Chapter 4). [13] M. Houlberg, Korrosion i fjernvarmeanlg, M.Sc. Thesis, Technical University of Denmark, 2002. [14] L. Lei, F. Wang, Y. Gao, Y. Du, Studies on the construction parameter of an articial occluded cell for in-situ inspection of the propagation rate of localised corrosion, J. Mater. Sci. Technol. 17 (2001) 355358. [15] Nordic Innovation Fund, Project No. 0071, Monitoring corrosion in district heating systems, Final report, May 2004. [16] A. Hoejman, P.S. Lind, Korrosion i fjernvarmesystemer, M.Sc. Thesis, Technical University of Denmark, 2002. [17] A. Andersen, L. Hilbert, P. Jansen, R.I. Thorarinsdottir, A localized corrosion cell for industrial applications, in: Proc. EUROCORR 2003, Budapest, Hungary, September 2003. [18] A. Andersen, K. Nielsen, L.R. Hilbert, L.V. Nielsen, Development of a unit suitable for corrosion monitoring in district heating systems, in: Proc. 13th Scandinavian Corrosion Congress, Iceland, April 2004. [19] S. Chechirlian, M. Keddam, H. Takenouti, Specic aspects of impedance measurements in low conductivity media, in: J.R. Scully, D.C. Silverman, M.W. Kendig (Eds.), Electrochemical Impedance: Analysis and Interpretation, ASTM STP 1188, ASTM, 1993, pp. 2336. [20] K.C. Stewart, D.G. Kolman, S.R. Taylor, The eect of parasitic conduction pathways on EIS measurements in low conductivity media, in: J.R. Scully, D.C. Silverman, M.W. Kendig (Eds.), Electrochemical Impedance: Analysis and Interpretation, ASTM STP 1188, ASTM, 1993, pp. 7393. [21] F. Mansfeld, M. Kendig, Concerning the choice of scan rate in polarization measurements, Corrosion 37 (1981) 545555. [22] T. Bellezze, G. Roventi, R. Fratesi, Electrochemical study on the corrosion resistance of Cr III-based conversion layers on zinc coatings, Surf. Coat. Technol. 155 (2002) 221230. [23] S. Richter, R.I. Thorarinsdottir, Comparing LPR and EIS in low conductivity water systems, in: Proc. 13th Scandinavian Corrosion Congress, Iceland, April 2004. [24] M. Norin, T.-G. Vinka, Corrosion of carbon steel in lling material in an urban environment, Mater. Corros. 54 (2003) 641651.