MetriCorr

2006.25.04 - 0 DGC.FAUGT.10

AC / DC interference corrosion in pipelines

Summary Report

Distribution: Participants Report: Review: Date: Folke Galsgaard, Lars Vendelbo Nielsen Peter Cohn, Bent Baumgarten 25-4-2006

Prepared by MetriCorr for

The Danish Gas Technological Centre.

MetriCorr ApS Produktionsvej 2 DK 2600 Glostrup - Denmark Tel. +45 72 177 410 Fax +45 72 177 216 - Info@metricorr.dk www.metricorr.dk

Summary and Conclusions

This report gives an overall view of activities performed in the period June 2004 to February 2006 within the project AC/DC interference corrosion in pipelines, sponsored by the Danish Gas Technological Centre DGC. Participants in the project have included the Danish natural gas distribution and transmission companies, Balslev consulting engineers, and MetriCorr. The work has included laboratory as well as field investigations along pipelines owned by Gastra (now Energinet.dk), Greater Copenhagen Natural Gas (HNG) and Naturgas Midt/Nord. An executive group has bee responsible for the progress of the work. This group consisted of: Mr. Bent Baumgarten (Greater Copenhagen Natural Gas, HNG) Mr. Peter Cohn, Gastra Energinet.dk Mr. Per B. Srensen (Naturgas Midt-Nord) Mr. Dan B. Jensen (Naturgas Fyn) Mr. Henrik Rosenberg (Balslev Consulting Engineers) Mr. Lars Vendelbo Nielsen (MetriCorr). The original project description as approved by DGC has been included in annex 1. The individual activities within the project are all continuations from previous research activities within this field conducted by the participants in particular Gastra and HNG along with their consultants, Balslev and MetriCorr. These activities have continuously been presented at conferences, primarily CeoCor and NACE. Rather than going into great details in discussing results from the project, this report seeks to provide an overview of the problems encountered on AC/DC interference corrosion, to present state-of-theart and to pin point the results from the project in relation to this. Furthermore, the report seeks to point out investigations worth considering in the further efforts on interference corrosion. As continuations from this present project, a GERG project has been proposed, and a CeoCor working group on coupon technology has been proposed.

A short introduction to relevant corrosion mechanisms is given in section 1. AC influenced corrosion can be shown to involve the formation of very high pH at a coating defect combined with the potential vibration caused by superimposed AC. Since cathodic protection (CP) increases the pH at a coating defect, it is essential not to apply the CP in excessive amounts as the AC corrosion risk will increase. This is in contradiction to DC interference corrosion, which will require an extra amount of CP, and a conflict therefore seems to exist between CP requirements for AC corrosion mitigation and CP requirements for mitigation of corrosion caused by DC stray currents. A short description of relevant measuring techniques has been given in the report section 2. Section 3 constitutes a line up of the activities included in the work. An overall discussion on observations (field and laboratory) on AC influenced corrosion is presented in section 4, and the AC corrosion mechanisms are discussed based on the results achieved. Clear correlations have been established between CP current density and the spread resistance of the coating defect. Above a threshold level, the CP (DC) current density and consequent pH increase results in a significant lowering of the spread resistance. In turn, the lowering of the spread resistance results in an increase of the AC current density, which combined with a pH increase and potential vibration results in increased corrosion rate. Under such conditions, corrosion rates of several millimeters per year can be measured on coupons. In field and in lab, it has been demonstrated that corrosion can be reduced or even effectively stopped by reducing the CP level. In other words, the results clearly show an unintended detrimental effect of excessive CP under such circumstances. A single test post at which low AC voltages levels but high DC interference levels occur has received special attention, and results from this station are presented and discussed in section 5. In a particular study, the cathodic protection level of the pipeline (rectifier current output) was gradually lowered in steps of one week, and the corrosion rate on coupons were measured and compared with the electrical parameters describing the CP level and DC interference condition. An increased corrosion was quantified by the coupons a quite accurate correlation with the amount of current escaping the coupons under anodic interference peaks could be observed. This study clearly shows that under DC interference conditions, it is wise to maintaining a certain level of CP. Pipelines experiencing both AC and DC interference constitute a dilemma when it comes to optimized CP. The survey methods applied for AC and DC interference corrosion respectively have been used on a pipeline experiencing both AC and DC interference. The interference patterns have

been clarified and compared with the corrosion rate of the coupons. The results are discussed in section 6. It seemed to be impossible to dose a suitable amount of CP in this case. The peaks in cathodic current density seemed to be severe enough to create a critically high pH, which combined with the AC caused potential vibration creates a classic AC corrosion case with very high corrosion rates. For the purpose of protecting against the anodic DC current peaks a certain level of CP should be applied, but in such severe interference cases, the actual level of CP seemed to be less important, the corrosion proceeds anyway. These experiences lead to further investigations and measurements of line currents at several positions along the pipeline to establish the location of the source for the DC interference and consequent qualified dialog with the local traction system operators in order to identify and minimize the interference at its very source. In section 7, the effect and role in AC corrosion of selected parameters have been discussed in brief terms. The parameters include both electrical parameters like AC voltage and current density, DC potentials and current density, and spread resistance, as well as physico-chemical parameters like conductivity/soil resistivity, pH, presence of ground water, soil texture and selected chemical substances. The discussion is made in view of the results obtained in the present project, as well as in previous projects and from outside the Danish sector. The points are discussed in view of the recently published CEN/TC 15280 document and AC corrosion likelihood. Among conclusions are that a coupon DC current density and spread resistance combined with the pipeline AC voltage seems to be the best indicators of the corrosion risk. The CEN/TS 15280 document recommends to a large degree the use of coupons for quantification of the various parameters that are used for assessment of the AC corrosion likelihood. For this reason, it has been a Danish viewpoint in the ad hoc group that formed the document that techniques that could also quantify the extent of corrosion on the coupon should be implemented in the document. The whole idea of using coupons for the risk analysis seems today to be the best suited way (or perhaps the only option), although one may question the extent to which a coating fault simulated in a coupon represents an actual coating fault at the pipeline surface. The question could also be turned upside down, in the sense that one could ask why a coupon should not represent a coating fault, as long as a careful registration of the environment in which the coupon is placed is made along with appropriate electrical descriptions of the coupon behavior. One could further ask what is the difference in behavior of two different coating defects. Today, a NACE recommended practice (RP0104-2004) on use of coupons for CP monitoring purposes exists, but it is not particularly focusing on nor necessarily applicable for aspects relating the assessments of AC/DC interference 3

corrosion. In the CEN standards, the use of coupons is widespread, but no official document deals in details with the possibilities and/or limitations when using coupons. For the above reasons it has been suggested that a new working group activity is initiated in CeoCor sector A, dealing with the issue, and a proposal for a GERG project which include activities on coupon research has been forwarded through the Danish Gas Technological Centre. Other interesting spin offs from the project has included some premature ideas on optimized cathodic protection by closer CP control and thoughts on what could be called dynamic corrosion control. A rectifier system, which measures the off-potential frequently throughout the day and adjusts the rectifier current output accordingly to meet the pre-programmed CP requirement, is now operating in HNG pipelines. It has been observed here that adjustments within 200 mV in the on-potential are sometimes necessary within just a 24h period in order to keep a constant off-potential. New approaches to effective CP under interference conditions could be born within the above frames, for instance by quantifying the interference patterns continuously and dosing CP accordingly. If high DC interference is present during daytime and high AC is present at nighttime (caused by export of power for instance), the CP requirements in those two situations are quite different.

Content
Summary and Conclusions ....................................................................................................................1 Content...................................................................................................................................................5 1. Corrosion mechanisms.......................................................................................................................6 2. Measuring techniques corrosion rate ..............................................................................................9 3. Activity line-up ................................................................................................................................10 4. Observations on AC corrosion.........................................................................................................12 5. Observations on corrosion caused by DC stray currents .................................................................17 6. Observations on corrosion under combined AC/DC interference ...................................................22 7. Evaluation of selected critical parameters .......................................................................................28 7.1 Electrical parameters..................................................................................................................28 7.1.1 AC voltage, AC current density and Spread Resistance.....................................................28 7.1.2 DC potential and DC current density..................................................................................30 7.2 Fysico-chemical parameters.......................................................................................................30 7.2.1 Conductivity / resistivity.....................................................................................................30 7.2.2 Size of the coating defect ....................................................................................................32 7.2.3 pH........................................................................................................................................32 7.2.4 Humidity ground water level ...........................................................................................32 7.2.5 Depth of the coupon or pipeline coating defect ..................................................................33 7.2.6 Other chemical factors of the soil .......................................................................................34 7.2.7 Soil texture ..........................................................................................................................34 8. Summary and conclusions ...............................................................................................................36 9. Perspectives......................................................................................................................................37 10. References......................................................................................................................................39 Appendix 1. Description of project and activities ...............................................................................41 Appendix 2. Papers and presentations now and then........................................................................44

1. Corrosion mechanisms
Part of the purpose of this project has been clarifying the mechanisms of AC influenced corrosion. Corrosion caused by DC stray current seems quit straight forward, the corrosion occurs during the anodic peaks of the interference pattern. Corrosion caused by AC interference may have several faces, however, it seems now that one mechanism is particularly important; namely the alkalization mechanism. When cathodically protected, the pipeline receives a current from the rectifier / anode bed system, which lowers the potential of the pipeline and ideally keeps it within the immunity region of the Pourbaix-diagram (figure 1). The cathodic protection can be disturbed by interfering DC stray currents entering and exiting the pipeline. Where the current enters the pipeline, the potential will be further lowered (more cathodic), i.e. the interference adds to the CP current. Where the current exits the pipeline, the potential will be increased (more anodic), i.e. the corrosion risk increases. In case the pipeline is not sufficiently protected, the potential at the point where DC stray current exits the pipe may enter the active region in the Pourbaix diagram, and cause corrosion. Accordingly, the standards (e.g. EN 501621) prescribe that corrosion as a consequence of DC stray current can be avoided by adding a surplus of CP.

1,500
Fe3+

Oxygen equilibrium line Hydrogen equilibrium line

E (V vs SCE)

1,000

0,500

Hypothetical line illustrating critical pitting potential

Fe2+ Fe2O3

0,000

Domain favoring corrosion

-0,500
Fe3O4

Domain favoring passivity Domain favoring corrosion

Domain favoring immunity

-1,000
Fe

HFeO2

-1,500 0 1 2 3 4 5 6 7 8 pH 9 10 11 12 13 14 15 16

Figure 1. Potential-pH (Pourbaix) diagram for iron (steel) in water.

Intuitively, the same strategy has been applied for protection against corrosion caused by AC interference, and in case stories on AC corrosion, authors have often stressed out that they made sure that the CP system was particularly well operating, and that the pH at the coating fault has been high. Today, it is known and particularly shown in this project, that this strategy has been fatal. The plausible explanation is that the mechanism of AC influenced corrosion involves an alkalization of the environment close to the coating defect. The Pourbaix-diagram (figure 1) is a diagram based on
Fe = Fe2+ + 2eFe + 2H2O = HFeO2- + 3H+ + 2e2Fe + 3H2O = Fe2O3 + 3Fe + 4H2O = Fe3O4 + 6H+ 8H+ + + 6e8e(1) (2) (3) (4) (5) (6) (7)

theoretical

calculations,

however,

its

feasibility

and

applicability has been proved in numerous practical cases. The calculations are based on thermodynamical data for the electrochemical reactions presented in the box (here to the left). The reaction (1) states that iron in the solid state oxidizes and dissolves which is equal to a corrosion process. This is also the case for the reaction (2), while the process (5) indicates transition from one dissolved stage to another. The equilibrium potential for these three processes calculated as a function of pH dictates the positions of the two domains in the Pourbaix-diagram where corrosion is facilitated. As can be observed from the diagram, the steel can be protected from corrosion kept in the immunity area if the potential is drawn in the negative (cathodic) Under the influence of AC interference, the potential will vibrate or

Fe2+ = Fe3+ + 2e2Fe2+ + 3H2O = Fe2O3 + 6H+ + 2e3Fe2+ + 4H2O = Fe3O4 + 8H+ + 2e-

2Fe3O4 + H2O = 3Fe2O3 + 2H+ + 2e- (8)

2H+ + 2e- = H2 (9) 2H2O + 2e- = H2 + 2OH- (10) O2 + 2H2O + 4e- = 4OH- (11) O2 + 4H+ + 4e- = 2H2O (12)

oscillate, with the same frequency (50 Hz) as the frequency of the AC interference. This means that during the positive half wave of this oscillation, the potential might cross the borderline between immunity and corrosion. The question is then if the electrochemical reactions are fast enough to occur within those 10 milliseconds, or if 50 Hz potential vibration is so fast that the corrosion risk from the AC interference is practically absent. Exactly based on this, the traditional way of thinking add a surplus of CP to prevent corrosion when AC is present is fairly plausible. Experience and research has shown, though, that a dangerous element shall be found in the small area at high pH where corrosion also occurs due to reaction (2). The very high pH required here does not exist in any natural environment, and must be created locally in the coating fault in order to constitute a risk. Under cathodic protection, the pH will be raised locally in the coating defect by reaction (10) in the above box. 7

Pipe surface H2O

OH-

OH-

Time to reach critically high pH value = INCUBATION PERIOD

OH- neutralisation (BNE) Influx (IDC) Out-flux (Diffusion texture) Accumulation (pH increase)

Figure 2. Illustration of a pH increase at a cathodically protected surface. Figure 2 accordingly illustrates a mass balance at a coating defect. The CP current produces OH- ions (alkalinity), which increase pH. If the production rate is modest (small influx) or if nothing is blocking for the transport of OH- away from the surface (out-flux) then the accumulation of OH- is small and the pH increase will be low. Additionally, the situation can be harmless if the soil chemistry can react with the produced OH- then neutralizing the effect (base neutralizing effect BNE). In case the rate of production of OH- increases due to increased CP, then accumulation may or will occur locally at the coating defect, and pH increases. When sufficiently high, the combination with a vibrating potential, may lead to periodic entering the high-pH corrosion domain in the Pournax diagram. In case this mechanism is active, there seems to be some characteristic features to be expected:

It is difficult or impossible to provoke AC corrosion in pure aqueous environment without solid particles acting as diffusion barriers.

One can expect a certain incubation period due to the time needed to achieve the critically high pH.

The corrosion will increase when CP current is increased.

These features have been proved in practice, and summarized, the net consequence is that the precautions taken to protect against corrosion resulting from interference from DC stray current (increased CP) is directly conflicting with one of the precautions that can be taken to protect against corrosion resulting from AC interference. In this context, the question is where the limits are for AC and DC interference before corrosion occurs, and how can one monitor in practice that the corrosion risk is kept under proper control.

2. Measuring techniques corrosion rate

The recently published Technical Specification CEN/TS 152802 on evaluation of AC corrosion likelihood, the use of coupons is recommended as an evaluation tool. These are buried next to the pipeline and electrically coupled hereto. The coupon includes an artificial coating defect of a certain size, e.g. 1 cm2 which is anticipated thereafter to experience the same chemical and electrical conditions as a similar coating defect in the real pipeline coating. The coupon is used for measuring current densities (DC and AC), off-potentials etc, which can be compared with the pipeline AC voltage and DC on-potential. Further, the spread resistance (ohmic resistance between metal and remote earth) can be measured.
Rectifier Transformer

Field application

Test post CSE Counter

Coupon Soil box

Reference

Datalogger system AC voltage AC current Spread resistance Eon DC current Corrosion

Pipe

Corrosion coupons (simulated coating fault)

Lab application

Figure 3. Datalogger system with ER coupon used for both field and laboratory investigations.

Throughout the last decade, it has increasingly become a common practice in the Danish sector to make use of coupons, which additionally to the traditional electrical characterizations have had the feature of being able to tell the corrosion state and corrosion rate using the so-called ER (electrical resistance) technique. The basic principles of the method has been described in other papers.4-7 All results described in this report have been conducted with ER coupons with datalogger system picking up all corrosion- and associated electrical data. Figure 4 is an example of graphical illustration of the corrosion rate throughout time.

Combined AC and DC stray

1000 900 Corrosion rate - VCORR mym/yr 800 700 600 500 400 300 200 100 0
08-Jan-05 15-Jan-05 22-Jan-05 29-Jan-05 05-Feb-05

Corrosion Rate

12-Feb-05

19-Feb-05

26-Feb-05

05-Mar-05

Exposure time Date

Figure 4. Graphical presentation of corrosion rate throughout time picked up by the ER coupon datalogger system.

3. Activity line-up
Laboratory: 1. Establishment of soil boxes with inert pure quartz sand and electrolyte pore solution. Boxes were equipped with electrode system (large inert counter electrode mesh made from platinized titanium, CSE reference electrode and an ER coupon as the working electrode), a BAC rectifier type 1201, and an AC transformer system; figure 3. An attached datalogger system (MetriCorr interference corrosion logger) measured and stored the AC and DC parameters and corrosion of the coupon. 2. Performed series of experiments, each of which of three weeks duration. During each experiment, the corrosion rate and electrical data were picked up. The AC voltage and DC on-potential was kept constant throughout the entire period. 15 V AC was chosen for all 6 10

experiments, whereas 6 different on-potentials were chosen in order to study exclusively the effect of DC on corrosion rate and controlling parameters. 3. Performed series of experiments where the DC on-potential has been kept constant at a value determined under activity 2) to be a critical value. This condition was then superimposed with 15 V AC in order to create corrosion. From this critical corrosion situation, the AC voltage was decreased to 10 V and later 4 V to study if corrosion could be stopped. 4. Performed preliminary tests in the laboratory on the effects of DC stray currents. These tests were later released by actual field measurements, since it became clear that further knowledge and experiences were needed in relation to the DC pattern during DC interference, and in order to gain some experience on which environment is critical. Field investigations: 5. Performed investigations of the applicability of a range of different techniques for measurements on coupons. These included basic multimeter measurements, DONGlog measurements and Ramlog measurements. 6. Performed investigations of the soil resistivity as a function of depth at selected locations. 7. Based on the above, an electronic template file for measurements on coupons was established. 8. A number of approximately 20 locations along the Danish gas grid were picked out and sets of two ER coupons established at each location. The individual gas companies then used the template file and associated guidelines to follow corrosion conditions etc. throughout an extended period of time (+1 year) by spot wise measurements. 9. Based on the spot wise measurements, locations showing particularly problematic or interesting character were picked out for establishments of loggers and modems for continuous monitoring and special investigations.

11

4. Observations on AC corrosion
The AC current density through a coating fault probably has a large influence on the corrosion condition and therefore seems to be an obvious fingerprint. This AC current density is simply approximated as the AC voltage divided by the spread resistance of the coating defect, which is why one may reduce the AC corrosion risk by lowering the pipeline AC voltage. Spread resistance is an equally important parameter, since for a given AC voltage this will be determining the AC current density. The spread resistance depends on the geometry and size of the coating fault, as well as on the chemistry existing directly in the close proximity of the coating fault. The soil chemistry is therefore of great importance as is the humidity around the coating defect. Since the cathodic protection current causes electrochemical reactions to take place in the coating defect, and according that ions may be produced directly there, the nature and velocity of these electrochemical reactions are also of very great importance. The close chemistry may totally be controlled from this electrolysis, and therefore the spread resistance is very likely to be entirely controlled by this. As already mentioned in section 1, OH- ions (alkalinity) will be produced at the surface by the CP current, thereby increasing the pH and lowering the spread resistance. This effect has been experienced in all of the cases (in this study) where AC influenced corrosion has been detected on a coupon. Figure 5 illustrates how laboratory experiments have shown that above a certain limiting value for the DC current density (in this case around 8 A/m2) the spread resistance will decrease since OH- starts accumulating at the surface. Figure 6 illustrates the consequence hereof on the AC current density, which increases accordingly despite the AC voltage is constantly 15 V.
0.14 0.12 0.10 Rs - ohm.m2 0.08 0.06 0.04 0.02 0.00 -20 -15 -10 Idc - A/m2 -5 0 Iac - A/m2 300 250 200 150 100 50 0 -20 -15 -10 Idc - A/m2 -5 0

Figure 5. Correlation between cathodic Figure 6. Correlation between AC and DC protection current density and spread current density in the same experiment. resistance in a laboratory experiment soil box with inert sand and a dilute sodium chloride solution. Note that increased CP corresponds to a more negative current.

12

Figure 7 shows the corrosion rate in the same experiment as a function of the AC current density. It can be described as a function of the AC current density (as expected), but due to the influence of DC current on spread resistance hence on AC current density, the corrosion rate can just as well be described equally well as a function of the DC current density (figure 8).

140 120 100

140 120 100

Vcorr - mym/yr

80 60 40 20 0 0 50 100 150 Iac - A/m2 200 250 300

Vcorr - mym/yr

80 60 40 20 0 -20 -15 -10 Idc - A/m2 -5 0

Figure 7. Correlation between AC current Figure 8. Correlation between DC current density and corrosion rate. density and corrosion rate. The exact same correlations can be established for results obtained in another environment figures 9-14. This environment is inert sand + dilute (0.005M) NaOH solution. The AC voltage is maintained in all experiments at 15 V, and 6 different DC on-potentials has been applied for periods of htree weeks. The development in all parameters were logged continuously and shown in the graphs. Figure 9 shows the influence of DC current density on the spread resistance, figure 10 shows accordingly the correlation between AC and DC current density, 11 and 12 show correlations between corrosion rate and AC quantities, whereas figure 13 and 14 show the correlation between corrosion rate and DC quantities. Note particularly from figure 13, that the more negative potential, the worse the development in corrosion rate.
-850 mV DC -1200 mV DC 0.20 0.18 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 -14 -12 -10 -8 -6 Idc - A/m2 -4 -2 0 2 -950 mV DC -1250 mV DC -1100 mV DC -1300 mV DC
600 500 Iac - A/m2 400 300 200 100 0 -14 -12 -10 -8 -6 Idc - A/m2 -4 -2 0 2 -850 mV DC -1200 mV DC -950 mV DC -1250 mV DC -1100 mV DC -1300 mV DC

Figure 9. Effect of DC current density on spread resistance.

Rs - ohm.m2

Figure 10. Correlation between DC and AC current density.

13

-850 mV DC -1200 mV DC 250 Vcorr - mym/yr

-950 mV DC -1250 mV DC

-1100 mV DC -1300 mV DC
250 Vcorr - mym/yr 200 150 100 50 0

-850 mV DC -1200 mV DC

-950 mV DC -1250 mV DC

-1100 mV DC -1300 mV DC

200 150 100 50 0 0 5 10 Uac - V 15 20

100

200

300 Iac - A/m2

400

500

600

Figure 11. Corrosion rate versus AC voltage.

Figure 12. Corrosion rate versus AC current density.

-850 mV DC -1200 mV DC 250 Vcorr - mym/yr 200 150 100 50 0 -950 mV DC -1250 mV DC -1100 mV DC -1300 mV DC

-850 mV DC -1200 mV DC 250 Vcorr - mym/yr 200 150 100 50 0 -1400

-950 mV DC -1250 mV DC

-1100 mV DC -1300 mV DC

-1200

-1000 Eon - V CSE

-800

-600

-14

-12

-10

-8

-6 Idc - A/m2

-4

-2

Figure 13. Corrosion rate versus on-potential.

Figure 14. Corrosion rate versus DC current density.

Equally clear indications of the correlations have been shown for field measurements; figures 15-17. Figure 15 shows the correlation between AC current density and corrosion rate, while figure 16 shows the same correlation with DC current density.

3500 3000 2500 2000 1500 1000 500 0 0 50 100 150 Iac - A/m2 200 250 300

3500 3000 2500 2000 1500 1000 500 0 -12 -10 -8 -6 Idc - A/m2 -4 -2 0

Vcorr- mym/yr

Figure 15. Correlation between corrosion rate Figure 16. Correlation between corrosion rate and AC current density coupon exposed at and DC current density coupon exposed at M/R lstykke. M/R lstykke.

14

Vcorr- mym/yr

Another example is shown in figure 17. A constant 15 V AC combined with different levels of rectifier output. At first, the DC on-potential was adjusted to -1150 mV CSE (lower left). This caused corrosion to occur (upper left). Lower right graph shows the DC current density through. When corrosion rate increased above 500 micron/yr, the DC potential was adjusted to -850 mV CSE, and the corrosion stops. The AC current density decreases as well although the AC voltage was 15 V constantly, indicating an increase in spread resistance.

Corrosion Rate Data 1000 900 800 700 600 500 400 300 200 100 0 13-May Corrosion rate - microns/yr

AC Current Data
AC Current density - A/m2 1000

100

02-Jun

22-Jun

12-Jul

01-Aug

21-Aug

Date (2004)

10 13-May

02-Jun

22-Jun

12-Jul

01-Aug

21-Aug

Date (2004)

DC Potential Data -0.6 -0.7 E - V CSE -0.8 -0.9 -1.0 -1.1 -1.2 13-May ON OFF
Cathode DC density (A/m2) 10

Direct Cathodic Current Data

0.1

0.01

02-Jun

22-Jun

12-Jul

01-Aug

21-Aug

Date (2004)

0.001 23-May 02-Jun 12-Jun 22-Jun 02-Jul

12-Jul 22-Jul 01-Aug 11-Aug

Date (2004)

Figure 17. Example of elimination of the corrosion when cathodic protection level is lowered. Upper left: Corrosion rate throughout time. Lower left: DC-on potential, upper right: AC current density, lower right: DC current density.

The AC voltage of course also has an impact on the corrosion rate. Figures 18 and 19 give some indication of this. These are results from laboratory investigations in the diluted 0.005 M NaOH quartz sand soil box assembly. The corrosion is build up at -1500 mV CSE with 15 V AC. Lowering the AC to 10 V decreases the corrosion without stopping it (figure 18) whereas the same scenario, but lowering the AC voltage to 4 volts effectively stops corrosion in this environment.

15

Corrosion build up at 15 V AC Reduced to 10 V AC DC = -1500 mV (on) vs CSE 700

Corrosion Rate
16
Corrosion rate based on 12 hour trend Based on 2 hour trend AC voltage

600 500 Vcorr - mym/yr 400

14 12
AC Voltage (V)

10 8 300 6 200 100 0 0 24 48 Time (hours) 72 96 4 2 0

Figure 18. Corrosion builds up at -1500 mV CSE DC potential superimposed by 15 V AC. When AC is lowered to 10 V, the corrosion decreases but is not eliminated.

Corrosion build up at 15 V AC allowed to relax at 4 V AC DC = -1500 mV (on) vs CSE

500 450 400 350 Vcorr - mym/yr 300 250 200 150 100 50 0 0 24 48 72 96 Time (hours) 120 144

Corrosion Rate
16 14
Corrosion rate based on 12 hour trend Based on 2 hour trend AC voltage

12 AC Voltage (V) 10 8 6 4 2 0 192

168

Figure 19. Corrosion builds up at -1500 mV CSE DC potential superimposed by 15 V AC. When AC is lowered to 4 V, the corrosion is eliminated..

16

5. Observations on corrosion caused by DC stray currents

It is entirely a different situation when the corrosion risk is attributed to DC stray current alone. A field location (HNG / KB-1) with DC stray current activity (and no AC interference) had been chosen from the preliminary spot wise measurements and the existing ER coupons used to make a quantification of the risk of DC stray current corrosion in the existing soil environment. At this location, intensified measurements of the corrosion rate was established and the datalogger was programmed to acquire DC potential and current every 5 seconds in 5 different 20 minutes periods throughout the day (02:00h, 07:00h, 11:00h, 15:00h and 19:00h). For each of these 20-minute periods, the DC potential and current can be plotted against time (figure 20). From the plot (in practice in a spreadsheet) the maximum, minimum, and average values as well as RMS and standard deviation were determined. In the same spreadsheet, the positive and negative current measurements can be identified and directed to separate columns in the sheet, and based on this procedure, the anodic charge and the cathodic charge for each period of 20 minutes can be calculated.

Probe-Tag: Bagsvrd Probe Type: PA-0.4-10-0.1-6 Probe serial No.: PA04270009 Test initiated: 29-08-2005

Idc 1 (A/m2) Eon (V) DC Data -0.600 -0.800 -1.000

Eon (V CSE)

1.50 1.00 0.50 Idc (A/m2) 0.00 -0.50 -1.00 -1.50 -2.00
04/10 14:55 04/10 15:00 04/10 15:05 04/10 15:10 04/10 15:15

-1.200 -1.400 -1.600 -1.800 -2.000

04/10 15:20

Time

Figure 20. Example of a DC potential and current plot throughout one period of 20 minutes around 15:00h.

17

From figure 20 is observed that both anodic and cathodic currents are present throughout this period. The DC potential fluctuates over a wide range both less and more negative relative to the -850 mV CSE cathodic protection criterion. A full scale esperiment with the KB-1 pipeline was initiated. The initial rectifier output current (around 50 mA) was gradually decreased once a week, and the corrosion rate and the intense 20 minutes DC current and potential measurements were realized at these mentioned 5 periods a day. Figure 21 shows the rectifier current output (dotted line) throughout a 5 week test period. Initial value 50 mA was decreased to 25 mA after a week, 10 mA after another week, then stepwise back to the 50 mA. The maximum, minimum and mean potential resulting from the 5 daily intense measurements are shown in the figure as well.

Probe PA04270009

0.000 -0.200 -0.400

Mean potential Max potential Min potential Rectifier level

60 50 Rectifier output (mA)

Potential (V/CSE)

-0.600 -0.800

40 30

-1.000 -1.200 -1.400 10 -1.600 -1.800 29/08/05 0 05/09/05 12/09/05 19/09/05 Date 26/09/05 03/10/05 20

Figure 21. Rectifier output and max/min/mean potential detected during experiment with different rectifier output under DC stray current conditions.

18

35 30 Potential RMS noise (%) 25 20

30 60 Probe PA04270009 25 50 20 40 15 30 10 20 5 10 0 0 14/09/05 15/09/05 16/09/05 17/09/05 Date

Pot noise Rectifier level

60 50 Rectifier output (mA) 40 30

15 10 5 0 29/08/05 20 10 0 05/09/05 12/09/05 19/09/05 Date 26/09/05 03/10/05

Figure 22. Potential RMS noise throughout the experimental period. The small graph illustrates the noise measured in the 5 daily periods for three following days, just to illustrate the low noise at night and increasing noise during daytime with traffic etc. Apparently, the noise is highest (in these periods) during the afternoon (black indications).

Figure 23 illustrates the resulting charge calculations. The lower figure is the cathodic charge released whereas the upper figure illustrates the anodic charge release. In the upper figure, the corrosion rate measured on an ER coupon is illustrated as well, showing a very good correlation with the anodic charge release. Figure 24 shows the correlation between anodic charge (converted into an average anodic current density) and corrosion rate. The theoretical factor between these quantities in case all anodic charge causes corrosion is 1.16. At the location where these measurements were taken, the DC stray current corrosion risk seems to be well controlled by the 50 mA current output from the rectifier. Further, this experiment has shown that (at least in this environment and for this stray current pattern) there is some correlation between anodic charge and corrosion.

19

Probe PA04270009

3000 Corrosion rate (micrometer/year) Anodic charge (C/m2) 2500 2000 1500 1000 500 0 29/08/05

Corrosion rate Anodic charge Rectifier level

60 50 Rectifier current (mA) 40 30 20 10 0

05/09/05

12/09/05

19/09/05 Date

26/09/05

03/10/05

Probe PA04270009

60 50 Rectifier current (mA) Cathodic charge Rectifier level 40 30

Cathodic charge (C/m2)

-500

-1000

-1500 20 -2000 10 0 05/09/05 12/09/05 19/09/05 Date 26/09/05 03/10/05

-2500 29/08/05

Figure 23. Comparison between the release of cathodic charge (lower) anodic charge and corrosion rate (upper).

20

HNG - KTB 1, Hareskov Probe PA04270009 2.5 y = 1.0471x + 0.0446 Corrosion rate - mm/year 2

1.5

0.5

0 0 0.5 1 1.5 2 2.5 Anodic Current (A/m2)

Figure 24. Correlation between released anodic charge (converted into average anodic current density) and the corrosion rate.

21

6. Observations on corrosion under combined AC/DC interference

The risk AC influenced corrosion was shown to increase with increasing CP level in combination with a certain AC level. The mitigation therefore may include both lowering the AC voltage and the cathodic protection level. The risk of corrosion due to DC stray current seems to be related to the anodic current leaving the pipeline at coating faults. The mitigation therefore may include increasing the cathodic protection level. When a pipeline is infected by both AC and DC interference, there seems to be a conflict when optimizing the CP dosage. In order to illustrate this conflict in practice, test stations have been established on the HNG KB-6 distribution where test stations at the lstykke crossing (North) and at the Taastrup crossing (South) have been equipped with a number of ER coupons and dataloggers.

lstykke crossing

Taastrup crossing Distribution pipeline grit with MR stations and test posts Transmission pipeline grit HV power lines DC traction system

Figure 25. The KB-6 distribution pipeline grit positioning relative to other infrastructure high voltage power lines, DC traction systems.

22

At these test stations, a high level of both AC and DC interference exist. Figure 26 shows the corrosion rate throughout 4 months at an ER coupon established at the Taastrup crossing in south. The characteristic pattern in the first weeks of this period is illustrated in a close up in figure 27. A certain correlation is observed according to which there is no corrosion at night and elevated corrosion during daytime. During weekends, the corrosion ceases as well. This behaviour is taken as traffic related. Unfortunately, there was no DC logging in this period.

Probe-Tag: Hje Taastrup -1 Probe Type: PA-0.4-10-0.1-12 Probe serial No. PA04120004 Test initiated: 12-01-2005

Corrosion Rate
Peaks at 8000 m/y Peaks at 7000 m/y

2000 1800 1600 Corrosion rate - VCORR m/yr 1400 1200 1000 800 600 400 200 0 01/1 08/1 15/1 22/1 29/1 05/2 12/2 19/2 26/2 05/3 12/3 19/3 26/3 02/4 09/4 16/4 23/4 30/4 07/5 14/5 21/5 Exposure time Date Trend based on 96 measurements Trend based on 16 measurements

Figure 26. Corrosion rate at coupon 1 Taastrup crossing 4 month period.

Probe-Tag: Hje Taastrup -1 Probe Type: PA-0.4-10-0.1-12 Probe serial No. PA04120004 Test initiated: 12-01-2005

Corrosion Rate

500 450 400 Corrosion rate - VCORR m/yr 350 300 250 200 150 100 50 0 16.1 Trend based on 96 measurements Trend based on 16 measurements

23.1

30.1 Exposure time Date

06.2

13.2

Figure 27. Daily and weekly variations in corrosion rate coupon 1, Taastrup crossing.

23

The extremely high corrosion rates that occur medium May and ultimo April (figure 26) seems to be initiated from and related to some very powerful peaks in the AC voltage (figure 28) probably caused by fault currents.

Probe-Tag: Hje Taastrup -2 Probe Type: PA-0.4-10-0.1-12 Probe serial No. PA04120006 Test initiated: 12-01-2005

AC Voltage
11-03-2005 Peaks at 160 V 28-04-2005 Peaks at 140 V

50 45 40 AC Voltage - V AC volts 35 30 25 20 15 10 5 0 1/1 8/1 15/1 22/1 29/1 5/2 12/2 19/2 26/2 5/3 12/3 19/3 26/3 2/4 9/4 16/4 23/4 30/4 7/5 14/5 21/5 Exposure time Date

Figure 28. The AC voltage throughout the testing period Taastrup crossing. .

Figures 29-32 are examples from the measurements taken at lstykke crossing throughout a 5 months period. Fire 30 is the AC voltage in this period. High corrosion peaks are present from the very beginning of the measuring period and the coupon element was just about to corrode through. Therefore, the coupon was disconnected from the pipe for a while in order to protect the coupon and analyze conditions. This period can be identified as the period where the AC voltage is zero (figure 30). The very high corrosion rate seems to occur at AC voltages fluctuating between 2 and 14 V. Figure 31 shows the corresponding DC data in a period around 16/8, where the high corrosion peaks are present. DC data were picked up as described for the DC stray current study, i.e. 5 times a day for 20 minutes, sampling every 5 seconds. As can be seen from figure 31, there are extremely high DC fluctuations. The calm and steady potentials measured at night (short pink lines) showed that no cathodic protection was active (it had been turned off) the potential was here around -500 to -600 mV CSE. Despite the absence of CP the corrosion may be attributed to AC. From figure 31 is also observed that cathodic current densities peak in between 20 and 60 A/m2 Such level is well high enough to create alkalization even without a steady CP current. Anodic peak values are also very

24

high 20-60 A/m2. These currents should be a very serious threat in terms of DC stray current corrosion.
Probe-Tag: 5500 K11A Probe Type: PA-0.4-10-0.1-6 Probe serial No.: PA04140029 Test initiated: 08-08-2005
4000 Vcorr(Peak) >10mm/Yr

Corrosion Rate

3500

Trend based on 96 measurements Trend based on 16 measurements

3000

2500

Vcorr - mym/yr

2000

1500

1000

500

0 17/7

16/8

15/9

15/10
Dat e

14/11

14/12

13/1

12/2

Figure 29. Corrosion rate experienced on coupon 1 lstykke crossing.

Probe-Tag: 5500 K11A Probe Type: PA-0.4-10-0.1-6 Probe serial No.: PA04140029 Test initiated: 08-08-2005 18 16 14 12 AC Voltage - V 10 8 6 4 2 0 17/7 16/8 15/9 15/10 Date 14/11 14/12 13/1 12/2 AC Voltage AC voltage

Figure 30. AC-voltage at the lstykke crossing.

25

Probe-Tag: 5500 K11A Probe Type: PA-0.4-10-0.1-6 Probe serial No.: PA04140040 Test initiated: 08-08-2005
80

DC Data
3

60 2 40 1 20 Idc (A/m2) Idc 2 (A/m2) Eon (V)

-20 -1 -40 -2 -60

-80 06/08

13/08 Time

20/08

-3 27/08

Figure 31. DC measurements on coupon 2 - lstykke crossing around 16/08.

Probe-Tag: 5500 K11A Probe Type: PA-0.4-10-0.1-6 Probe serial No.: PA0510032 Test initiated: 21-09-2005
80

DC Data
3

60 2 40 1 20 Idc (A/m2) Idc 1 (A/m2) Eon (V)

-20 -1 -40 -2 -60

-80 30/11

01/12

02/12

03/12

04/12

05/12 Time

06/12

07/12

08/12

09/12

10/12

-3 11/12

Figure 32. DC measurements on coupon 1 - lstykke crossing. 3/12.

Figure 32 shows DC data in a period around 3/12 (December third), where a violent corrosion attack is observed. From the potentials measured at night can be observed that the CP system is well working. Even so, this has not affected a reduction in the anodic (nor cathodic) current peaks, and corrosion seems to occur due to a combined AC and DC stray current action without really taking notice of the CP.

26

Probe-Tag: 5500 K11A Probe Type: PA-0.4-10-0.1-6 Probe serial No.: PA0510032 Test initiated: 21-09-2005
80

DC Data
3

60 2 40 1 20 Idc (A/m2) Idc 1 (A/m2) Eon (V)

-20 -1 -40 -2 -60

-80 14/11

21/11 Time

-3 28/11

Figure 33. DC measurements on ER coupon 1 at lstykke crossing around date 21/11. Figure 33 shows DC measurements from date 14/11 and two weeks ahead. Again, the potentials at night are quite calm while during the daytime, the current and potential fluctuation is heavy. From figure 30 can be observed that there is only modest AC voltage present (1-6 V) but still from the anodic peaks of the DC stray current one would expect corrosion. The overall conclusion is however, that the severe DC stray current pattern in combination with occasionally increased AC causes unacceptable corrosion, and further investigations involving line current measurements to pinpoint the source of DC stray current as well as a good dialogue between pipeline and traction system operators have been initiated. .

27

7. Evaluation of selected critical parameters

In general, corrosion is a function of electrical / electrochemical and chemical / physical parameters. For a complete understanding of any corrosion process, one may claim that the relative influence of all such parameters should be known. A full understanding of the processes is a case for the corrosion scientist rather than the corrosion engineer, whose principal job is to be able to monitor and mitigate the corrosion process. However, the better the understanding of the parameters involved, the better the possibilities for both monitoring and mitigating the corrosion. The following sections constitute a brief and undoubtedly incomplete discussion of some the parameters involved in the AC corrosion process, and some of the parameters used to assess the risk. Included herein is the significance of the parameters in CEN/TS 15280 on AC corrosion likelihood. .

7.1 Electrical parameters 7.1.1 AC voltage, AC current density and Spread Resistance The AC voltage, the AC current density and the spread resistance of a coating fault are interconnected through Ohms law: UAC (V) = Rspread (.m2) x Iac (A/m2) The magnitude of the AC voltage is controlled by the induction caused by the parallelism with an AC power line and the effectiveness of the pipeline grounds. In TS 15280 it is stated that the AC voltage is the most significant parameter for risk assessment. The pipeline to earth AC voltage will vary along the pipeline chainage depending on the positioning and effectiveness of the grounds and the configuration of the interfering structure (length of parallelism, configuration of and current in the conductors). It is decided in TS 15280 that the AC voltage should not exceed 10 V at any time over the entire pipeline, and it should not exceed 4 V where the local soil resistivity is below 25 .m. The extent to which these limits are in line with our own experience is not a question with a straight forward answer. In figure 18 and 19, the data have been achieved in a soil box where the initial resistivity has been around 100 .m. It seems to be more evident that the spread resistance rather than the soil resistivity is the conducting parameter. From figure 9 is observed that the spread resistance decreases by a factor of at least 4.5 when DC current increases at the coating defect. If the initial spread resistance corresponds to a soil resistivity of magnitude 100 ohm.m, a decrease in this spread resistance by a factor of 4.5 corresponds to the creation of a soil resistivity locally at the coating defect below the 25 ohm.m. The spread resistance, which in TS 15280 has been called the

28

leakage resistance, is not attributed a threshold value, and it is not used as parameters for direct assessment of the corrosion likelihood. It is, however, dependant on the specific soil resistivity, the electrochemistry at the coating defect, as well as the size and shape of the coating defect. Small coating defects have lower spread resistances (ohm.m2) as compared with larger coating defects; see figure 33, and refer to earlier investigations8.

Relative solution resistance as a function of electrode area

1000

100

Rs ( .cm2)

Rs/.cm = 140 x (A/cm )

10

2 0.5

1 0.01

0.10

1.00

10.00

Area (cm )

Figure 33. Spread resistance as a function of the size of the coating defect in a certain reference environment8 The trendline in the plot can be written as:: Rs = K . s . d (.m2) where K is a constant dependant on the geometry of the coating fault, d is a measure of the size, while s is the specific resistivity of the soil (in close vicinity of the coating defect and including the effect of the electrolysis occurring here). The AC current density is measured on a coupon with known surface area (preferable 1 cm2) and is an important evaluation parameter in the TS 15280 standard. For AC current densities lower than 30 A/m2, the AC corrosion likelihood is low, in the interval between 30 and 100 A/m2, the likelihood is medium, an above 100 A/m2, the likelihood is very high. There are no conflict between these statements and the results obtained in this project. In order to use this parameter however, a

29

continuous logging must be made since the AC voltage varies throughout the day and throughout the year, the groundwater level may change, the spread resistance may change with water level, CP dosage etc.

7.1.2 DC potential and DC current density The effects of the DC parameters have been illustrated through the figures 5-16. Combined with a certain level of AC, increased level of CP will increase the risk of AC corrosion, and the DC current density seems to be a very important factor, which in case exceeding some threshold value will be totally in charge of the spread resistance. The production of OH- causes high pH and low spread resistance and initiates a wicked circuit; increased AC current density etc. In TS 15280 a criterion is defined after which the ratio between the AC and DC current density is calculated. If this ratio is less than 5, the AC corrosion likelihood is low. If the ratio is between 5 and 10, the likelihood exists, and further investigation should be necessary. If the ratio is beyond 10, the AC corrosion likelihood is considered to be high, and further actions should be taken, e.g. by using proper earthing. This current ratio criterion should be used with caution, since it may be tempting to increase the CP level to increase the DC current density in order to reduce this ratio. However, the CP level must first be adjusted so that excessive CP is not present, and then the criterion may be used. By this, the effect of the DC off-potential has also been discussed. It should be controlled to a value more negative than - but as close as possible to the CP criterion given by EN 12954 (usually -850 mV CSE) in order to avoid too excessive cathodic protection current concentrated in a coating defect. According to our investigations, the spread resistance and the DC current density should be given higher priorities in the TS 15280 standard compared with the actual case.

7.2 Fysico-chemical parameters 7.2.1 Conductivity / resistivity The specific resistivity of the soil is as already mentioned the parameter adjusting whether 10 V AC or 4 V AC is the maximum acceptable level. How this resistivity is measured is not quite clear, however, it is described as the local resistivity. If this is relative to the pipeline chainage (kilometer),

30

the pipeline depth, or at a defect is not stressed out. However, the measurement should be made in a soil box using soil from the exact position under investigation. One should take care that there is a large effect of the soil humidity and for this reason there will be a large effect of the ground water level and the seasonal variation hereof.

Soil resistivity as function of depth

0 -50 Level (0=ground) -100 -150 -200 -250 0.1 1 10 Resistivity (Ohm.m) 100 1000
Frslev M/R F-E km 0.9 F-E km 2.9 lstykke M/R Vallensbk mose SH km 91.24 Brndbyvester Boulevard SK km 94.0 (jernbane) 25 ohm.m limit

Figure 34. Soil resistivity measured as a function of depth selected test locations.

Figure 34 shows the soil resistivity measured at some of the test stations. One apparently observes two different kind of tendencies. One showing increased resistivity with increasing depth, probably indicating that the conducting ions are primarily present in the upper soil layers and drawn further down with rain. The other one is showing a decreasing resistivity with increasing depth found in totally wet peat bogs, where subsurface water movements may distribute ions and metabolites from biological activity. In conjunction with the graph (figure 34) it is noted that the measurements have been made by sampling a certain amount of soil, bringing it back to the laboratory, drying for 24 hours, weighing out 5 grams and adding hereto 10 ml of water. The conductivity measured in this suspension has then been inversed to give a measure of resistivity. Specific investigations have shown that this will

31

give a fairly true value compared with a soil box measurements using soil in a totally wet condition.

7.2.2 Size of the coating defect As already discussed, the size of the coating defect has importance in relation to the spread resistance figure 33. 7.2.3 pH The soil pH and the pH existing in close proximity of a coating defect are two entirely different factors. The increased pH which is believed to take part of most AC corrosion possesses is not connected to the bulk soil, since the surface pH is created by the CP current. The buffer capacity of the soil, i.e. the capability to neutralize the alkalinity produced by the CP, is a more obvious factor to consider in this context. In previous studies, the BNE value (base neutralizing effect) has been compared with occurrence of corrosion. These studies, which are definitely not complete, have not shown any correlation between low soil buffer capacity and corrosion. Refer to CeoCor 2004 paper9,10. One may be able to observe increased incubation period when buffer capacity is high. The discussion on pH and buffer capacities / BNE values is not part of TS 15280.

7.2.4 Humidity ground water level Humidity and ground water levels are quite important factors. Previous studies (Gastra M/R Frslev) have shown that coupons that have been buried in a certain depth in the soil initially showed very high corrosion rates, and then stopped corroding quite suddenly (and vice versa). The explanation was quite obviously that the ground water level which was monitored thereafter change dramatically by around 1 meter throughout the year figure 35.

32

-50 Level (cm) below surface

Ground water level Position of probes

-100

-150

-200

-250
01 /0 9/ 20 02 10 /1 2/ 20 02 20 /0 3/ 20 03 28 /0 6/ 20 03 06 /1 0/ 20 03 14 /0 1/ 20 04 23 /0 4/ 20 04 01 /0 8/ 20 04 09 /1 1/ 20 04 17 /0 2/ 20 05 28 /0 5/ 20 05 05 /0 9/ 20 05

Date

Figure 35. Ground water level at Gastra Frslev measured in drainage well over a period over 3 years.

Observations at HNG line KB-6 as well as the Gastra SH pipeline location GKL have shown both corrosivity and changing ground water levels. Further research experiments on AC corrosion should include a monitoring of the ground water level. For general monitoring purposes, the ground water level monitoring may be regarded as an academic issue. TS 15280 does mention the correlation between spread resistance and the better conductivity present in a water saturated soil.

7.2.5 Depth of the coupon or pipeline coating defect The depth of the coupon will play a significant role as already indicated in figure 34. The resistivity will inevitably vary with the depth, as will the spread resistance and AC current density. In the South of Jutland, around the Gastra MR Frslev station, investigations have been made directly at the station and some 900 meters away from the station. The textural type of soil seemed to be identical at those two positions. The ground water level at the station however, was found to be around 1 meter deeper than at km 0.9. Coupon buried to 1 meters depth at the km 0.9 location can 33

therefore be exposed in a totally wet environment, whereas coupons buried in the same depth at the MR station at the same time is totally dry. While the wet coupons corrode heavily, the dry ones show no sign of corrosion. In an attempt to compensate for this, a set of new coupons were buried 1 meter deeper at the MR station in a wet position. It was anticipated that these coupons would corrode, which they did not. The explanation seemed to be that the conductivity as a function of the depth were quite lower at the MR station as compared with the km 0.9 location see figure 34. Therefore, the initial spread resistance was quite higher at the MR station, and no corrosion could be provoked. While the humidity is mentioned in TS 15 280 as an important parameter, there is no information on the correlation with the depth in soil.

7.2.6 Other chemical factors of the soil The effect of other chemical factors in the soil has been studied by other research groups particularly by Dr. Stalder in Switzerland. The presence of earth alkaline cations (Ca2+ og Mg2+) is known to be able to cause an increase in spread resistance by reacting with produced OH-, forming resistive layers on the steel surface. The spread resistance can be increased by a factor of 100 by these processes. Presence of CaCO3 in the soil can be detected by adding droplets of acid to a soil sample and observe if bubbles are created. In such case, CaCO3 is present, and the probability of the presence of Ca2+ ions high. If a very high DC current density can damage the formation of resistive layers seems still to be a question to be answered. In TS 15280, the above chemical factors are mentioned and highlighted. For laboratory illustrations of the above, please refer to previous papers12-14.

7.2.7 Soil texture The effect of soil texture (grain size distribution) has been incompletely investigated in collaboration with the Geographical Institute, University of Copenhagen. Soil samples from areas where corrosion has been found has been compared with samples from area where corrosion is absent. In a range of case, one can illustrate that whether or not corrosion occur in a sediment is not (exclusively) connected to the texture. While it seems quite clear that presence of solid particles as diffusion barriers are requisites in an AC corrosion case, it is not still clear if different textures cause different

34

corrosion scenarios. This question is of course to be seen in view of humidity condition, conductivity issues etc. Further, it is usually claimed that fine particles like clay have more chemical substances attached to the surface as compared with coarse grained sand and gravel, and therefore that the conductivity is better in fine grained sediment. This seems to be a plausible statement. However, the buffer capacity of the soil is also caused by chemical substances attached to the particles, and this quantity would be affected as well.
Pipeline 1

Fraction (%)

60 40 20 0
Po sA Po sC

Position

>2 0, 1-2 0 50, ,25 1 12 - 0 0 0 ,06 5 , 5 0, ,02 3 -0 -0, 2 Grain size (mm) <0 00 0 -0 , 1 50 ,0 2 -0 , 0 25 02 , 0 63 20

Figure 36. Corrosion (red) versus no corrosion (white) in three identical sediments.

Po sE

35

8. Summary and conclusions

AC influenced corrosion can be shown to involve the formation of very high pH at a coating defect combined with the potential vibration caused by superimposed AC. Since cathodic protection (CP) increases the pH at a coating defect, it is essential not to apply the CP in excessive amounts as the AC corrosion risk will increase. This is in contradiction to DC interference corrosion, which will require an extra amount of CP, and a conflict therefore seems to exist between CP requirements for AC corrosion mitigation and CP requirements for mitigation of corrosion caused by DC stray currents. Clear correlations have been established between CP current density and the spread resistance of the coating defect. Above a threshold level, the CP (DC) current density and consequent pH increase results in a significant lowering of the spread resistance. In turn, the lowering of the spread resistance results in an increase of the AC current density, which combined with a pH increase and potential vibration results in increased corrosion rate. Under such conditions, corrosion rates of several millimeters per year can be measured on coupons. In field and in lab, it has been demonstrated that corrosion can be reduced or even effectively stopped by reducing the CP level. In other words, the results clearly show an unintended detrimental effect of excessive CP under such circumstances. A single test post at which low AC voltages levels but high DC interference levels occur has received special attention. In a particular study, the cathodic protection level of the pipeline (rectifier current output) was gradually lowered in steps of one week, and the corrosion rate on coupons were measured and compared with the electrical parameters describing the CP level and DC interference condition. An increased corrosion was quantified by the coupons a quite accurate correlation with the amount of current escaping the coupons under anodic interference peaks could be observed. This study clearly shows that under DC interference conditions, it is wise to maintaining a certain level of CP. Pipelines experiencing both AC and DC interference constitute a dilemma when it comes to optimized CP. The survey methods applied for AC and DC interference corrosion respectively have been used on a pipeline experiencing both AC and DC interference. The interference patterns have been clarified and compared with the corrosion rate of the coupons. It seemed to be impossible to dose a suitable amount of CP in this case. The peaks in cathodic current density seemed to be severe enough to create a critically high pH, which combined with the AC caused potential vibration creates

36

a classic AC corrosion case with very high corrosion rates. For the purpose of protecting against the anodic DC current peaks a certain level of CP should be applied, but in such severe interference cases, the actual level of CP seemed to be less important, the corrosion proceeds anyway. The effect and role in AC corrosion of selected parameters have been discussed in brief terms. The parameters include both electrical parameters like AC voltage and current density, DC potentials and current density, and spread resistance, as well as physico-chemical parameters like conductivity/soil resistivity, pH, presence of ground water, soil texture and selected chemical substances. The discussion is made in view of the results obtained in the present project, as well as in previous projects and from outside the Danish sector. The points are discussed in view of the recently published CEN/TC 15280 document and AC corrosion likelihood. Among conclusions are that a coupon DC current density and spread resistance combined with the pipeline AC voltage seems to be the best indicators of the corrosion risk.

9. Perspectives
The CEN/TS 15280 document recommends to a large degree the use of coupons for quantification of the various parameters that are used for assessment of the AC corrosion likelihood. For this reason, it has been a Danish viewpoint in the ad hoc group that formed the document that techniques that could also quantify the extent of corrosion on the coupon should be implemented in the document. The whole idea of using coupons for the risk analysis seems today to be the best suited way (or perhaps the only option), although one may question the extent to which a coating fault simulated in a coupon represents an actual coating fault at the pipeline surface. The question could also be turned upside down, in the sense that one could ask why a coupon should not represent a coating fault, as long as a careful registration of the environment in which the coupon is placed is made along with appropriate electrical descriptions of the coupon behavior. One could further ask what is the difference in behavior of two different coating defects. Today, a NACE recommended practice (RP0104-2004) on use of coupons for CP monitoring purposes exists, but it is not particularly focusing on nor necessarily applicable for aspects relating the assessments of AC/DC interference corrosion. In the CEN standards, the use of coupons is widespread, but no official document deals in details with the possibilities and/or limitations when using coupons.

37

For the above reasons it has been suggested that a new working group activity is initiated in CeoCor sector A, dealing with the issue, and a proposal for a GERG project which include activities on coupon research has been forwarded through the Danish Gas Technological Centre. Other interesting spin offs from the project has included some premature ideas on optimized cathodic protection by closer CP control and thoughts on what could be called dynamic corrosion control. A rectifier system, which measures the off-potential frequently throughout the day and adjusts the rectifier current output accordingly to meet the pre-programmed CP requirement, is now operating in HNG pipelines. It has been observed here that adjustments within 200 mV in the on-potential are sometimes necessary within just a 24h period in order to keep a constant off-potential. New approaches to effective CP under interference conditions could be born within the above frames, for instance by quantifying the interference patterns continuously and dosing CP accordingly. If high DC interference is present during daytime and high AC is present at nighttime (caused by export of power for instance), the CP requirements in those two situations are quite different.

38

10. References
1. EN 50162:, Protection against corrosion by stray current from direct current systems. 2. CEN/TS 15280, Evaluation of AC corrosion likelihood of buried pipelines application to cathodically protected pipelines, 3. EN 12954, Cathodic protection of buried or immersed metallic structures General principles and application for pipelines. 4. L.V. Nielsen, Monitoring cathodic protection efficiency and AC induced corrosion using new high-sensitive electrical resistance technology, Proc. Eurocorr 2001, Riva del Garda (2001), paper no. 20 5. L. Vendelbo Nielsen, Field and Laboratory Detection of AC Corrosion Using High-Sensitive ER-Technology, Paper 796, Proc. ICC2002 conference Grenada Spain, 2002. 6. L.V. Nielsen and K.V. Nielsen, Differential ER Technology for Measuring Degree of Accumulated Corrosion as well as Instant Corrosion Rate. Proc. NACE 2003, Paper 03443, 2003. 7. Lars Vendelbo Nielsen & Folke Galsgaard, Sensor technology for On-Line monitoring of AC corrosion along pipelines, NACE 2005, paper 05375. 8. L.V. Nielsen, and P. Cohn, AC-Corrosion and Electrical Equivalent Diagrams, Proc CeoCor, 2000, 9. L. V. Nielsen, B. Baumgarten , H. Breuning-Madsen , P. Cohn , H. Rosenberg, Detection and mitigation of AC induced corrosion in pipelines, Proc. Nordic corrosion conference, Reykjavik 2004. 10. L.V. Nielsen, B. Baumgarten, P. Cohn, On-site measurements of AC induced corrosion: Effect of AC and DC parameters - A report from the Danish activities, CeoCor conference June 2004 Dresden, sector A. 11. L.V. Nielsen, B. Baumgarten, P. Cohn, Investigating AC and DC stray current corrosion, CeoCor conference June 2005 Malm. 12. Thermodynamical Considerations on the Local Chemistry Formed at the Steel-Soil Interface of Cathodically Protected Pipelines, Technical Note, PCO / LVN.

39

13. AC Corrosion Rates of Cathodically Polarised Steel Exposed in a Scaling, Neutral-pH Soil Solution, Technical Note, PCO / LVN. 14. AC Corrosion Rates of Cathodically Polarised Steel Exposed in a Non-Scaling, Neutral-pH Soil Solution, Technical Note, PCO / LVN.

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Appendix 1. Description of project and activities

Parties: HNG I/S, Gastra A/S, Naturgas Midt Nord I/S, Naturags Fyn I/S, DONG Distribution A/S, MetriCorr, Aps, Balslev consulting engineers. General background In situ measurements at lstykke M/R Station have shown that AC induced corrosion at ER coupons connected to the pipe system may be reduced and perhaps even eliminated if the CP dosage is reduced hereby reducing alkalinity production. However, this may conflict with the degree of CP necessary for prohibiting corrosion due to DC stray current from the adjacent railway electrical system. Optimum CP will in this case normally be ensured by dosage of CP to a level ensuring that the amount of cathodic current supplied by the rectifier will at any time be larger than part time anodic DC stray currents supplied by the railway system. Suggestions for investigations that may contribute to a clarification of the conflict are therefore invited. Theoretical considerations In proximity of a coating fault to which CP cathodic current is flowing, the pH is expected to be elevated compared with remote soil. According to the Pourbaix diagram, an anodic peak current in the pH region 9-12 should displace the potential towards (and perhaps into) the passive domain. However, it is known that passivity requires a formation of ferrous oxides, and this is a process that lasts an amount of time a time constant can be attributed to the process. If assumed that creation of passivity is fast in comparison with a time period of anodic DC stray current, the steel is expected to passivate. In this case, the anodic DC stray current would not be expected to create ferrous dissolution (corrosion); the anodic current is escorted by some other process. Oxygen production requires a rather high anodic potential compared with the cathodic protection potential, but at very reduced conditions this may be an option? Under circumstances where a passive film may decompose, for instance under the presence of chlorides, an anodic DC stray current may be able to initiate pitting corrosion. Pitting is likewise a process to which a time constant can be associated. The pitting process can be characterized by a critical pitting potential above which pitting is initiated, and a repassivation potential below which the pitting is blocked and passivation re-established.

In relation to the above considerations, the questions seem to be: I. Can it be confirmed on a broader experimental basis that the AC corrosion risk is reduced if the CP dosage is decreased? II. Would it be possible to adjust this CP dosage so as to avoid both AC induced corrosion and DC stray current corrosion

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either by a. The CP is not dosed unnecessarily higher than needed for compensation of the DC stray current peak. or by b. Keeping a balance in the CP dosage so that pH is not elevated to a degree that induces AC corrosion, however high enough to guide the coating defect in to the passive region during an anodic stray current. Is this potential balance dependant on chloride contaminants? III. How is the above affected by specific soil conditions like level of groundwater, pH, presence of CacO3, conductivity of the soil, chloride and BNE value (base neutralizing capacity)? Suggestions for actions Point I can be investigated from different angles: 1. In situ measurements where ER probes are established on locations where AC induced corrosivity have been demonstrated. A number of probes should be established both below and above ground water levels. These probes should be varied with respect to area of the coating defect. AC corrosion detectors that measure AC parameters, spread resistance and corrosion should be installed in the measuring posts. The rectifier potential should be altered between moderate/low CP and high CP dosage. 2. Laboratory investigations in AC corrosive soil where a constant AC voltage is maintained whilst the DC cathodic potential is varied. Two different AC loads for each of which the DC level is changed within 5 levels. High sense ER measuring the corrosion rate. Point II as well can be investigated from different angles: 3. Balslev consulting engineers have pointed out 19 locations along the HNG pipeline system where DC stray currents are measurable. Soil samples should be collected from these sites and characterized with respect to chalk, chloride, pH, conductivity and ground water level. These will subsequently be categorized (wet/dry, acidic/alkaline etc.). Two ER coupons are installed and the corrosion is followed during a one-year period. In this period, the CP-level is changed from low via moderate to high, and spotwise ER measurements, spread resistance measurements. At the end of each CP condition, a measuring campaign is completed in which a close-up logging of the current and potential relations is performed. During these campaigns the probes are shortly de-coupled from the pipeline system so as to verify the open circuit potential drift under the chemical conditions formed due to the relevant CP condition. Optionally, the probes are characterized by Ramlog correal measurements. 4. Laboratory investigations where CP of ER probes exposed in a soil environment leads to a build-up of an alkaline environment. At certain intervals an anodic polarization is realized with size and duration that corresponds a typical stray current. DC parameters (current /potential) are registered. For a number of CP-level/stray current combinations the corrosion rate is recorded by the high sense equipment. In parallel investigations the probes 42

are connected to a larger steel structure that has not been cathodically polarized and for this reason does not passivate by anodic polarization. The current distribution between this structure and the probes is registered and it is investigated whether the corrosion rate is affected by the coupling procedure. Each of the 4 phases is reported continuously. Implementation The above identified 5 points of action are realized according to the below time-schedule.
2004 Activity 1. In situ AC corr. 2. Lab investigation AC corr. 3. In situ DC stray current corr. 4. Lab investigations DC stray 5. Final report 1 2 3 4 1 2 2005 3 4

Phase 1 (AC investigations in the field) is initiated in direct continuation of the present investigations along the HNG line. Phase 2 (AC investigations in lab) is initiated directly subsequent to budget approval, and will continue for the proceeding 3 months Phase 3 (DC stray current in field) involves a preliminary investigation of the soil conditions after which the actual field measurements can be initiated around 4th quarter of 2004. Phase 4 (DC stray current investigations in laboratory.) Initiated directly after the AC investigations in lab (phase 2) and will proceed for 3 months.

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Appendix 2. Papers and presentations now and then.

Previous internal reports and papers prepared in regi of DONG in collaboration between Peter Cohn and Lars Vendelbo Nielsen: 1. Thermodynamical Considerations on the Local Chemistry Formed at the Steel-Soil Interface of Cathodically Protected Pipelines 2. pH Gradients Existing in Proximity of Cathodically Charged Steel Buried in Sediment 3. EIS Investigation of the Randles Circuit Elements for Carbon Steel Exposed in Artificial Soil Solution 4. Comparison of EIS and Ramlog Measurements of Spread Resistance and Polarisation Impedance for Steel Exposed in Artificial Soil Solutions with and without Scaling Capacity at 50 Hz AC 5. Effects of 50 Hz AC on the DC Polarisation Behaviour of Steel Exposed in Artificial Soil Solutions 6. AC Corrosion Rates of Cathodically Polarised Steel Exposed in a Scaling, Neutral-pH Soil Solution 7. AC Corrosion Rates of Cathodically Polarised Steel Exposed in a Non-Scaling, Neutral-pH Soil Solution 8. AC Corrosion Rates of DC Polarised Steel Exposed in a High-pH Solution 9. The Effect of Superimposed Alternating Current on Hydrogen Absorption by Cathodically Polarised Steel Exposed in a Non-Scaling Artificial Soil Solution Papers presented at conferences: 10. K. Vendelbo Nielsen & L. Vendelbo Nielsen, Measurement of Accumulated Corrosion and Instant Corrosion Rate Using a New Differential Electrical Resistance Technique, Internal paper VN-Instrument, 1998. 11. L.V. Nielsen, and P. Cohn, AC-Corrosion and Electrical Equivalent Diagrams, Proc CeoCor 2000,

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12. L.V. Nielsen, Monitoring cathodic protection efficiency and AC induced corrosion using new high-sensitive electrical resistance technology, Proc. Eurocorr 2001, Riva del Garda (2001), paper no. 20 13. L.V. Nielsen, and P. Cohn AC-corrosion in pipelines: Field experiences from a highly corrosive test site using ER corrosivity probes, Report given at CeoCor 2002. 14. L. Vendelbo Nielsen, Field and Laboratory Detection of AC Corrosion Using HighSensitive ER-Technology, Paper 796, Proc. ICC2002 conference Grenada Spain, 2002. 15. L.V. Nielsen and K.V. Nielsen, Differential ER Technology for Measuring Degree of Accumulated Corrosion as well as Instant Corrosion Rate. Proc. NACE 2003, Paper 03443, 2003. 16. L.V. Nielsen et al, AC-Induced Corrosion in Pipelines: Detection, Characterisation and Mitigation, Proc NACE 2004, Paper 04211, 2004. 17. L. V. Nielsen, B. Baumgarten , H. Breuning-Madsen , P. Cohn , H. Rosenberg, Detection and mitigation of AC induced corrosion in pipelines, Proc. Nordic corrosion conference, Reykjavik 2004. 18. L.V. Nielsen, B. Baumgarten, P. Cohn, On-site measurements of AC induced corrosion: Effect of AC and DC parameters - A report from the Danish activities, CeoCor conference June 2004 Dresden, sector A. 19. A. Kulkarni, L.V. Nielsen, H. Rosenberg Characteristics of AC-Induced corrosion in pipelines and concepts for mitigation and monitoring. Corcon, NACEIndia, Dew Delhi 2004. 20. L.V. Nielsen, Role of Alkalization in AC induced corrosion of pipelines and consequences hereof in relation to CP requirements, NACE 2005, paper 05188. 21. Lars Vendelbo Nielsen & Folke Galsgaard, Sensor technology for On-Line monitoring of AC corrosion along pipelines, NACE 2005, paper 05375. 22. L.V. Nielsen, B. Baumgarten, P. Cohn, Investigating AC and DC stray current corrosion, CeoCor conference June 2005 Malm.

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23. Lars Vendelbo Nielsen and Folke Galsgaard, Techniques for investigating AC and DC stray current corrosion along pipelines, Proc. UK Corrosion 2005. 24. H. Rosenberg, A. Kulkarni, L.V. Nielsen, Pipeline operation and Maintenance with focus on Corrosion Protection, Corcon, NACEIndia, Chennai 2005. Planned papers/presentations CeoCor 2006 Luxemburg: 25. L.V. Nielsen, B. Baumgarten, P. Cohn, H. Rosenberg, A field study of line currents and corrosion rate measurements in a pipeline critically interfered with AC and DC stray currents. 26. L.V. Nielsen, P. Cohn, Use and limitations of coupons for corrosion monitoring applications (A working group start-up).

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