AC Corrosion of Metals Research

Politecnico di Milano Dipartimento di Chimica, Materiali e Ingegneria Chimica, G.
Natta
INFLUENCE OF ALTERNATING CURRENT ON METALS CORROSION

Sara Goidanich
Advisor: Prof. Luciano Lazzari Tutor: Prof. Pietro Pedeferri Coordinator: Prof. Giuseppe Zerbi
Ph.D. Thesis in Materials Engineering XVII Course

2002 2005
0 1 1.1 1.2
INTRODUCTION .................................................................................................................. 1 AC-INDUCED CORROSION ................................................................................................ 3 DEFINITIONS ....................................................................................................................... 3 DIRECT CURRENT (DC) INTERFERENCE ............................................................................... 4 Metallic Structures Interfered by DC........................................................................ 6 Maximum Allowable Interference............................................................................. 8
1.2.1 1.2.2 1.3 1.4 1.5
CASE HISTORIES OF AC-INDUCED CORROSION .................................................................... 8 MORPHOLOGY CHARACTERISTICS OF AC CORROSION ....................................................... 10 ALTERNATING CURRENT INTERFERENCE ............................................................................ 11 Conductive interference ......................................................................................... 12 Magnetic induction (coupling) ................................................................................ 13
1.5.1 1.5.2
Evaluation of induced peak voltage ................................................................................. 14 1.5.3 1.5.4 Steady-State or Load Conditions........................................................................... 15 Fault Conditions ..................................................................................................... 16
Conductive coupling ......................................................................................................... 16 Inductive coupling............................................................................................................. 16 Combined effect ............................................................................................................... 16 Transferred voltages ........................................................................................................ 17 1.6 1.7 1.8 CHARACTERISATION OF AC-INDUCED CORROSION ............................................................. 17 CORROSION RATE ............................................................................................................. 18 EVALUATION OF CORROSION RISKS AND CATHODIC PROTECTION MONITORING ................... 20 DC Potential Measurements in the Presence of AC.............................................. 21 AC voltage ............................................................................................................. 24 AC current densities............................................................................................... 25 AC Density/DC Density Ratio ................................................................................ 25 Cathodic Protection Criteria Based on AC and DC Densities Measured by
1.8.1 1.8.2 1.8.3 1.8.4 1.8.5
Coupons 26 1.8.6 Size of the Coating Defects ................................................................................... 27 Probabilistic approach ...................................................................................................... 27 1.8.7 1.9 1.10 1.11 1.12 1.12.1 1.12.2 ER corrosivity probes............................................................................................. 30 ER based AC corrosivity probe ........................................................................................ 30 DAMAGE TO PIPELINE EXTERNAL COATING......................................................................... 31 SAFETY FOR PERSONNEL .............................................................................................. 32 AC INFLUENCE ON CATHODIC PROTECTION ................................................................... 32 HOW AC INFLUENCES CORROSION PROCESSES ............................................................ 33 Formation of a Non Protective Oxide Layer........................................................... 34 Faradic Rectification Effect .................................................................................... 34
Limitations of the faradic rectification models...................................................................38 A model including double layer capacitance ....................................................................38 1.12.3 1.12.4 Effect on Overpotentials.........................................................................................39 Effect of the Anodic and Cathodic Half-Cycles ......................................................40
Positive half-cycle rectified AV signal...............................................................................41 Negative half-cycle rectified AV signal .............................................................................42 Full-wave sinusoidal AV ...................................................................................................43 1.12.5 1.13 1.14 1.14.1 1.15 1.15.1 1.16 1.17 1.17.1 AC-Induced Fluid Flow...........................................................................................43 EFFECT OF THE AC FREQUENCY ...................................................................................44 Effect of the waveform......................................................................................................45 AC EFFECTS ON THE CORROSION OF THE DIFFERENT METALS .......................................46 DC Potential Variation in the Presence of AC .......................................................46 PASSIVE METALS ..........................................................................................................47 Influence of Stray Currents on Corrosion of Steel in Concrete..............................47 EFFECT OF AC ON CORROSION IN SOILS .......................................................................48 INTERFERENCE MITIGATION ...........................................................................................49 DC Mitigation..........................................................................................................49 Stationary interference .....................................................................................................49 Non stationary interference ..............................................................................................50 1.17.2 Mitigation of AC Interference .................................................................................51 Lumped grounding............................................................................................................51 Cancellation wires ............................................................................................................51 Gradient control wires.......................................................................................................52 2 2.1 EXPERIMENTAL ................................................................................................................53 SETTING UP OF THE ELECTRICAL CIRCUIT ..........................................................................54 AC mesh ................................................................................................................55 Characteristics of the capacitor ........................................................................................55 2.1.2 DC mesh ................................................................................................................56 Characteristics of the inductor (L) ....................................................................................56 2.1.3 2.1.4 2.2 Common Branch ....................................................................................................56 Efficiency of the Circuit ..........................................................................................56
2.1.1
TESTS ON GALVANIC CORROSION ......................................................................................57 Experimental Conditions ........................................................................................57 Solution Composition........................................................................................................57 Cell, samples and Electrodes Characteristics ..................................................................57
2.2.1
2.2.2 2.3
Experimental Procedure ........................................................................................58
TESTS WITH SEPARATED CIRCUITS: AC AND DC OVERLAPPED ON THE SAME SAMPLE ........59 Experimental Conditions ........................................................................................59 Solution Composition........................................................................................................59 Cell, Samples and Electrodes Characteristics .................................................................59
2.3.1
II
2.3.2 2.4
Experimental Procedure ........................................................................................ 60
DETERMINATION OF THE ANODIC AND CATHODIC POLARISATION CURVES ............................ 61 Measurement Procedure ....................................................................................... 61 Experimental conditions......................................................................................... 62
2.4.1 2.4.2
Solution Composition ....................................................................................................... 64 Cell and Electrodes .......................................................................................................... 65 2.4.3 2.5 Experimental Procedure ........................................................................................ 65 WEIGHT LOSS TESTS ........................................................................................................ 67 Weight Loss Determination.................................................................................... 68 Test in Simulated Seawater Chlorinity: 35 g/L NaCl.............................................. 69 Test in Simulated Soil Solution .............................................................................. 69
2.5.1 2.5.2 2.5.3 2.6 2.7
Specimens........................................................................................................................ 69 CHARACTERISATION OF THE CORROSION MORPHOLOGY OF THE AC CORROSION ................ 71 EFFECT OF AC ON PASSIVE METALS ................................................................................. 72 Samples geometry ................................................................................................. 72 Solution composition.............................................................................................. 72 Cell and Electrodes................................................................................................ 73
2.7.1 2.7.2 2.7.3
Potentiodynamic tests ...................................................................................................... 73 Immersion Tests............................................................................................................... 73 2.7.4 Potentiodynamic Tests Procedure......................................................................... 73 Polarisation Curve ............................................................................................................ 73 Experimental Procedure................................................................................................... 74 2.7.5 Immersion Tests Procedure................................................................................... 75 Preliminary tests ............................................................................................................... 75 Second set of tests........................................................................................................... 75 2.8 CATHODIC PROTECTION MONITORING ................................................................................ 75 First set of measurements ..................................................................................... 76 Second set of measurements ................................................................................ 77
2.8.1 2.8.2 2.9 3 3.1 3.2
OSCILLOSCOPE MEASUREMENTS ....................................................................................... 79 RESULTS ........................................................................................................................... 81 TESTS ON GALVANIC CORROSION ...................................................................................... 81 TESTS WITH SEPARATED CIRCUITS: AC AND DC OVERLAPPED ON THE SAME SAMPLE ........ 84 Cathodic Polarisation (CP) Tests........................................................................... 84 Anodic Polarisation (AP) Tests .............................................................................. 86 Free Corrosion Tests ............................................................................................. 87
3.2.1 3.2.2 3.2.3 3.3
ANODIC AND CATHODIC POLARISATION CURVES................................................................. 89 Tafel Equation........................................................................................................ 89 Carbon Steel .......................................................................................................... 90
3.3.1 3.3.2
0.4 g/L Sodium Sulphate Solution.................................................................................... 90 Simulated soil solution...................................................................................................... 92 III
Simulated seawater solution: 35 g/L NaCl .......................................................................95 3.3.3 3.3.4 3.4 Galvanised Steel ....................................................................................................96 Carbon Steel, Zinc and Copper in 1 M Solution of their Ions ................................98
WEIGHT LOSS TESTS ......................................................................................................104 Simulated Seawater Solution: 35 g/L NaCl..........................................................104 Simulated Soil Solution ........................................................................................105
3.4.1 3.4.2
Aerated solution without thermostating ..........................................................................105 Aerated solution - thermostated at 20C ........................................................................110 De-aerated solution - thermostated at 20C...................................................................111 3.5 CHARACTERISATION OF THE CORROSION MORPHOLOGY IN THE PRESENCE OF AC Neither AC nor DC interference .....................................................................................113 AC = 100 and 300 A/m2 ..................................................................................................115 0.3 A/m2 DC anodic interference ....................................................................................119 Potential measurements.................................................................................................120 3.6 3.7 EFFECT OF AC ON CARBON STEEL REBAR IN CONCRETE .................................................121 Second set of measurements.........................................................................................124 EFFECT ON CATHODIC PROTECTION MONITORING ............................................................127 First set of measurements ...................................................................................127 Second set of measurements ..............................................................................129 INTERFERENCE ............................................................................................................................113
3.7.1 3.7.2 3.8 4 4.1 4.2
MEASUREMENTS BY OSCILLOSCOPE ................................................................................131 DISCUSSION....................................................................................................................133 AC DENSITY THRESHOLD ................................................................................................133 AC INFLUENCE ON CORROSION PROCESS........................................................................134 Corrosion Rate and AC Current Efficiency (CE%)...............................................134 Influence of AC on Corrosion Kinetics .................................................................136 Corrosion Potential...............................................................................................137 Analysis of the Faradaic Rectification Models .....................................................138
4.2.1 4.2.2 4.2.3 4.2.4
Oscilloscope measurements ..........................................................................................140 Results of the models .....................................................................................................140 4.2.5 4.3 4.4 4.5 Proposed Mechanism ..........................................................................................145 CORROSION MORPHOLOGY IN THE PRESENCE OF AC .......................................................146 CARBON STEEL IN ALKALINE SOLUTION ............................................................................146 CATHODIC PROTECTION MONITORING ..............................................................................148 Field Monitoring Approach ...................................................................................148
4.5.1 5
CONCLUSIONS................................................................................................................151 AC density threshold ......................................................................................................151 Corrosion rate and AC current efficiency (CE%)............................................................151 Influence of AC on Corrosion Kinetics............................................................................152
IV
Proposed mechanism.....................................................................................................152 Carbon steel in alkaline solution.....................................................................................153 Cathodic protection monitoring.......................................................................................153 6 7 ACKNOWLEDGMENTS...................................................................................................155 REFERENCES .................................................................................................................157
VI
INTRODUCTION
Alternating current enhanced corrosion has been considered since the beginning of the XX century[1]. However, for many years, corrosion experts did not recognise corrosion due to alternating currents (AC) on metallic structures as an important phenomenon as corrosion has been normally attributed to direct current. During the last 20 years pipelines failures in the USA, Canada and Europe have been ascribed to AC interference. The presence of AC caused serious damages on interfered metallic structures even when cathodic protection was applied. In some cases, failures also occurred on pipelines with OFFpotential lower than 850 mV CSE, that is normally considered a safe condition. A number of studies carried out to investigate the effect of AC on corrosion have concluded that metallic structures corrode at an accelerated corrosion rate in the presence of stray AC[2-9]. The scientific community has slowly recognised that, under certain conditions, alternating currents can cause corrosion although at a lower rate than direct current. The number of scientific publications on this topic has therefore increased during the last 15 years. [2,3,4,5,6,7,8,9] What is clear is that the increased number of AC related failures is associated to the more and more frequent parallelism between buried pipelines and AC high tension transmission lines which use the same right of way. A particularly harmful situation is when parallelism is associated with the use of high dielectric coatings, like extruded polyethylene or polypropylene, which leads to high induced AC current densities at coating defects. In the near future, at least in Italy, a new interference condition is expected because of the overlapping of high current AC traction systems (25 kV and 50 Hz) and the traditional direct current (DC) traction systems that have been operating for about a century. However, while for DC interference corrosion on buried structures is a well known problem and there is a large agreement on protection criteria to be used for corrosion mitigation and international standards are available since many years[10], AC induced corrosion continues to be a controversial subject and many aspects need to be clarified, especially the relationship between AC density and corrosion rate. Different theories have been proposed about the mechanism by which AC produces and enhances corrosion, although no one is able to fully explain the phenomenon. Furthermore it is not yet clear how to estimate the risk of AC-induced corrosion by means of AC density or alternating
Introduction
voltage. Another important aspect that needs further investigations is related to cathodic protection monitoring in the presence of AC. The experimental work dealt with the following: design of an electric circuit to allow independent control and measurement of AC and DC contributions in order to guarantee reliable measurements; study of the effect of AC current on galvanic corrosion; study of AC and DC overlapping through the designed circuit; weight loss test in order to quantify the damage caused by AC and estimation of AC corrosion threshold parameters; determination of AC effects on passive metals; cathodic protection monitoring in the presence of AC and DC stray currents; determination of anodic and cathodic polarisation curves in the presence of AC. The aim of these experiments was the evaluation of AC on the corrosion mechanism as far as corrosion kinetics is concerned; analysis of the mathematical models proposed in literature and comparison with experimental data. The analysis of the experimental data allowed to draw conclusions about the following topics: AC density threshold; mechanism of AC-induced corrosion; corrosion morphology in the presence of AC AC induced corrosion of carbon steel in alkaline solution (concrete); Cathodic protection monitoring.
The first two years of this experimental research were co-fund by MIUR (Italian Ministry of School, University and Research).
AC-INDUCED CORROSION
Before discussing the AC induced corrosion, it is important to emphasise that very often corrosion attacks are carelessly attributed to non-existent interference corrosion conditions, simply because the corrosion conditions are ignored. This is typical for internal corrosion attacks in water heaters or leakage of piping embedded in apartment floors, most often attributed to ghost stray current, through nobody knows its origins. Interference corrosion greatly worries owners of buried structures, because of the severe damages it causes. The interference can be the result of DC or AC, flowing predominantly with a frequency of 50 Hz (public electricity supply). A pipeline which shares a common path with AC transmission lines becomes energized by the magnetic and electric fields surrounding the power system in the air and soil. This AC interference can result in an electrical shock hazard for people touching the pipeline or metallic structures connected to the pipeline; furthermore, corrosion of the pipeline, damages to the pipelines coating, insulating flanges and rectifiers can occur. The induced AC-voltages can lead to an increase of the corrosion rate, the breakdown of a passive layer or increasing pitting corrosion. In this chapter a brief summary of the DC interference characteristics and the state of art of AC induced corrosion phenomena are reported.
1.1 DEFINITIONS
As a general definition, interference is any alteration in the electric field caused by a foreign structure[11]. Figure 1.1 illustrates a general scheme of interference in an electrodic system where two electrodes exchange current in the presence of a foreign body: when it is a conductor, the current is intercepted, when it is an insulator, the current is withdrawn. In both cases, there is a redistribution of current and equi-potential surfaces within the altered electric field. The first instance, when the interfered structure has ionic or electronic conductivity, leads to the classic and most well known interference conditions, the so-called stray current. When the structure is far from the electrodes, the influence on the electric field is usually negligible[11].
AC-Induced Corrosion
Conductor Current lines
Isolator
Equipotential lines
a)
b)
Figure 1.1 - General scheme of electrical interference between two electrodes on a body [11] a) conductor; b) isolator
1.2 DIRECT CURRENT (DC) INTERFERENCE

Interference can be of two types: stationary and non-stationary. Stationary interference is verified when the structure is immersed in a stationary electric field generated, for example, by a cathodic protection (CP) system, and the effect is greater as the structure is closer to the groundbed. In Figures 1.2 and 1.3, two general cases are reported. In the first case, the interfered pipeline crosses the protected one and the zone close to the groundbed tends to gather current from the soil, which is released at the crossing zone, causing local corrosion. In the second case, the two pipelines are almost parallel and the releasing current zone is usually more extensive than in the previous case, and typically occurs in low resistivity soil. In both cases, if the interfered structure is provided with an integral coating, interference cannot take place, but when the coating has a number of faults, corrosion is very severe since, current concentrates in them. Non-stationary interference takes place when the electric field is variable, as in the typical case of stray currents dispersed by traction systems, as illustrated in Figure 1.4. Interference takes place only during the trains transit, and often, in spite of the limited duration, a few minutes, the effects may be severe due to high circulating current. The mechanism of direct stray current corrosion is simple: the DC traction system has a positive aerial conductor and, for safety reasons, a grounded negative pole, so the return current path is double: track and soil, with over 50% in soil even when all precautions to reduce current dispersion in the ground have been taken[11]. A pipeline, parallel to rail, buried between the track and the substation is easily interfered, with corrosion taking place where current leaves the structure near the substation.
Interfered Pipeline Groundbed Interference current
Corrosion attacks T/R
Figure 1.2 - Scheme of stationary interference between two crossing pipelines[11]
T/R Low resistivity soil Interference current Interfered pipeline Corrosion attacks
Groundbed
Figure 1.3 - Scheme of stationary interference between two almost parallel pipelines[11]
Substation
cathodic zone E
anodic zone
protection potential time

Figure 1.4 - Scheme of non-stationary interference caused by stray current dispersed by a DC transit [11] system
Rail I R rail Pipeline i R pipe
Substation
R1
R2
Figure 1.5 - Electrical scheme of non-stationary interference
From an electrical point of view, the interference current may be evaluated from the balance of the ohmic drop through the circuit, when overpotential contributions on both pipeline and rails are neglected. With reference to Figure 1.5, where I is the current that passes through the rail (estimated to be about 50% of the total current tension) and I* is the interference current that passes through the pipeline, then:
I* =
IR r R1 + R pipe + R 2
Eq. 1.1
where, Rr, Rpipe indicate the track and pipe resistance respectively, R1 and R2 the ground resistance. Corrosion damages, quantified through I*, decrease as the track resistance Rr decreases (for instance by using welding joints to reduce the ohmic drop to about 1 mV/m) and by increasing the parallel path resistance by applying protective coatings, especially in the cathodic zone (increase in R1 + R2) and by installing insulating joints on the pipelines (increase in Rpipe).
1.2.1
Metallic Structures Interfered by DC
DC interference occurs when a metallic structure is placed in a DC electric field. The reaction that takes place over the surfaces receiving the current (cathodic zones) is primarily oxygen reduction and then hydrogen evolution at more negative potentials, by the following reactions:
O2 + 2 H2O + 4e- = 4 OH2H2O + 4e- = H2 + 2OH-
Eq. 1.2 Eq. 1.3
On anodic zones, where DC current leaves the metallic structures, the anodic reaction is metal (Me) dissolution when the metal is active:
Me = Mez+ + ze-
Eq. 1.4
When the metal is passive, the anodic reaction depends on the type of metal and environment. In alkaline media, such as pristine concrete where both stainless steel and carbon steel rebars are in passive condition, the anodic reaction is oxygen evolution, by the following reaction:
2 H2O = O2 + 4 H+ + 4e-
Eq. 1.5
Because acidity is produced, passivity may be destroyed at high currents and long time of interference, still provoking iron dissolution. For stainless steel in a neutral environment, the corrosion reaction is mainly metal dissolution, so corrosion effects are as harmful as in the case of carbon steel. According to Faradays law, the amount of metal that dissolves by reaction 1.4 is directly proportional to current and time. A flow of 1 A dissolves about 9 kg of iron in a year, equal to about 25 g/day. A current density of 1 A/m2 provokes a metal thickness loss at a rate of 1 mm/year.
Figure 1.6 - Interference on metallic structures[11]
With reference to Figure 1.6, ignoring the electrode overpotential at M and N surfaces, path 1 includes only the electrolyte ohmic drop, while path 2 includes the overpotential of the cathodic oxygen reduction and the anodic iron dissolution on the interfered structure. Therefore, introducing the IR drop within the structure, we obtain[11]:
I1
L L L L = I2 + c + str I2 + a + I2 S S S S
Eq. 1.6
or when the structures ohmic drop is ignored:
L L L I1 I2 I2 c + a E S S S
Eq. 1.7
where indicates the electrode overpotential with respect to the free corrosion potential ( = E Ecorr) localised at anodic (a) and cathodic (c) surfaces of the interfered structure. Terms and str refer to environment and metal resistivity, respectively. Assuming negligible the IR drop in the interfered metallic structure the following result is achieved: the overpotential sum E, which represents the driving voltage for current circulation in the interfered structure, is equal to the ohmic drop saving within the environment through the interference path. The term in brackets can be approximated to:
E C Iint erf L str
Eq. 1.8
where C is a geometric constant, Iinterf is interference current, Lstr is structure length. It follows that, for a fixed geometry, interference effects, determined by the available E, are increasing as structure length increases. The available driving voltage, E, is also given by:
E = EdL E L str
where E is the average electric field gradient. From Eq. 1.8 and 1.9 it follows:
Eq. 1.9
Iint erf C'
Eq. 1.10
where C is a geometric constant. Then, Iinterf increases as electric field gradient E increases and environment resistivity decreases. The interference current I which gives the corrosion rate, is generally not easy to calculate since the electric field solution is required.
1.2.2
Maximum Allowable Interference
Interference is as negligible as the interference current density is low. From a general viewpoint, it may be reasonable to assume the value at which carbon steel passivates in concrete, that is 1 mA/m2, or even double that, as an engineering compromise[11]. Unfortunately, because in practice the circulating current is not measurable, interference acceptance criteria refer to the potential measurement, to distinguish between freely corroding structures and those under CP. For the latter, potential variation should remain within the protection interval, while for the former, the maximum potential variation in the positive direction should not exceed 20-50 mV with respect to the free corrosion potential.
1.3 CASE HISTORIES OF AC-INDUCED CORROSION

High alternating current density can cause corrosion attacks on steel in soil, despite the steel surface being provided with proper cathodic protection[12,13]. Actual cases of AC corrosion on buried steel pipelines have been reported since 1986[14]. The cause of two corrosion anomalies on polyethylene coated pipelines in Germany, that were installed in 1980 paralleling a 15 kV AC powered rail transit system operating at the frequency of 16-2/3 Hz, was attributed to AC corrosion, although the instant-OFF potentials were more negative than 1.0 V CSE at those sites. Several cases of AC corrosion were reported in France where ONpotentials were at an adequately low level between 2.0 V CSE and 2.5 V CSE[15] Five cases of AC corrosion in North America were reported even if ONpotentials were sufficiently negative in all cases[16]. A field survey using coupons on a pipeline buried parallel to a 66 kV overhead AC power transmission line showed that a high level of AC current can cause corrosion on coupons even though the instantOFF potentials are more negative than 1.0 V CSE[17]. In Oregon (USA) the failure of a pipeline that had been laid in high voltage AC utility corridors was investigated. Severe AC corrosion occurred resulting in four holes in the pipeline after only five months life and before operation had begun. The pipeline was left buried in place without cathodic protection while the construction of the plant was completed. There appeared to be some 8
coating disbondment. The pits typically had a small aerial extent and were very deep. It was verified that there was no DC interference at the leak locations[18]. In Figure 1.7 the measured AC voltages taken during a survey of a pipeline which had reported AC-induced corrosion are shown[18].
100 80 AC Voltage 60 40 20 0 0 2 4 6 8 10 12 14 Distance - Miles
Figure 1.7 - Induced voltage on a AC-interfered pipeline[18]
Also in Texas a careful investigation of a pipeline failure was carried out. The review of the annual survey data, bimonthly rectifier readings and an ON/OFF close interval survey data showed apparent satisfaction of industry criteria for effective corrosion mitigation. Nothing in the review of the cathodic protection history suggested a plausible explanation for the rapid rate of corrosion experienced on this pipeline[19]. The pipe-to-soil AC potentials and the number of corrosion anomalies as a function of the location were evaluated. The plot of the AC potentials and defects are shown in Figure 1.8. This data indicated that the highest population of corrosion anomalies were located in the first five miles where the AC potentials typically exceeded 4 V. The excessive AC current densities observed on the coupon test stations and the physical and chemical analysis indicated that the likely cause of the observed corrosion anomalies was AC corrosion. This conclusion was supported by the correlation of higher defect occurrences within areas of higher AC potentials. It can be observed by the analysis of the reported case histories that AC corrosion is possible despite satisfying the conventional cathodic protection criteria such as the 0.85 V CSE potential criterion.
14 AC Potential (V CSE) 12 10 8 6 4 2 0 290 295 300 Mile Post 305 AC Potential Anomalies Per Foot
0.021 Defects per Foot 0.018 0.015 0.012 0.009 0.006 0.003 0.000 310
Figure 1.8 - AC potential and defects distribution[19]
1.4 MORPHOLOGY CHARACTERISTICS OF AC CORROSION

In DC stray current interference, the corrosion products are soluble due to the low pH at the discharge location and the corroded area is generally found to be free of corrosion products. In case of AC interference the corrosion products are generally present in the pits. Measurements performed on cathodically protected coupons and on corroded pipelines suggested a mechanism of AC induced corrosion which involves local alkalization of the soil environment close to a coating defect[7,19,20,[21,22]. This has probably to be related to the enhanced cathodic reaction during the AC interference. The enhanced corrosion due to the influence of AC voltages tends to be of a localised nature. The corrosion morphology is reported to be of a shallow saucer-shaped pit of a several millimetre diameter that is overlaid by a layer of hard encrusted earth[23]. AC corrosion can take on the appearance of generalised corrosion when the defect surface is large. These large areas are in fact several pits that have coalesced over a period of time. In Figure 1.9 the corrosion of a coupon which was placed in an Italian situ and was subjected to AC interference is shown.
10
Figure 1.9 Corroded coupon placed in an area in Italy characterised by high AC interference
The appearance of the corrosion may therefore vary depending on the duration of the interference from small point-shaped attacks distributed across the steel surface to large and deep local attacks with smooth round corrosion morphology. Generally the coating in the area surrounding the pits is damaged, often brittle and has poor adhesion[19]. Coating disbondment is often associated to AC interference. A typical aspect of failures occurred on cathodically protected pipelines is summarised in Figure 1.10.
Corrosion product placed on top of an hard oxide layer and corrosion diameter is larger than the coating defect diameter ( = a few cm )
Coating
Metal
Possibility of coating disbondment
Figure 1.10 - Specific characteristics of AC corrosion[12]
1.5 ALTERNATING CURRENT INTERFERENCE

As the DC interference, also the AC interference can be either stationary or non-stationary. Alternating current interference is generated by AC traction systems or high voltage transmission lines, through conduction and induction mechanisms. The effects of power system interference on pipelines are due to the relative voltage difference which is created between the pipeline metal and the local soil. Where a pipeline runs closely parallel to and/or crosses an AC power line, steady state and fault AC voltages can be induced on the pipeline. Induced AC voltages, which are respect to ground potential, arise as a result of electromagnetic capacitive and inductive effects. The magnitude of
11
the induced voltage depends on the AC transmission line voltage/current, the pylon dimensions, the separation distance of the pipeline from the AC transmission line, the distance over which the pipeline are in parallel with and crosses the AC transmission line, soil resistivity, coating conductivity of the pipeline and whether the AC transmission line is experiencing a fault or large transient surge associated with a switch on[23]. The AC power lines induce a secondary alternating current in the steel pipes buried nearby: field measurements indicated that this secondary AC field has a voltage drop on the order of kilovolts/km along insulated pipes[24]. The potential drop between the bare pipe and the surrounding soil was reported in the range of 5 to 70 V. An example of voltage profile induced along a pipeline by a 380kV50 Hz power line carrying balanced currents of 630 A is shown in Figure 1.11.
60 AC Voltage (V) 50 40 30 20 10 0 0 5 10 15 20 25 30 Distance (km)

Figure 1.11 - Example of voltage profile induced along a pipeline by a nearby 380kV-50Hz power line[25]
1.5.1
Conductive interference
Conductive interference due to currents flowing in the soil is of particular concern at locations where the pipeline is close to transmission line structures which may inject large currents into the soil during power line fault conditions. Such structures include transmission line tower or pile foundations and substation grounding systems[26]. Interference by conduction takes place when a buried structure spreads AC current. This is the case of grounding networks and high voltage transmission lines with a phase grounded. Stray currents choose the path of least resistance, therefore they affect buried metallic structures such as buried steel pipelines and tanks[11]. There are two typical cases of conductive interference: dispersion from a grounding network (plant earthing systems) and from AC traction systems (rails and their grounding conductor). In
12
these cases, AC voltage on interfered structures in soil can be calculated when geometry, soil resistivity and AC voltage of dispersing sources are known.
1.5.2
Magnetic induction (coupling)
Magnetic induction (coupling) acts along the entire length of pipeline which is approximately parallel to the power line and can result in significant pipeline potentials even at relatively large separation distances. Inductive coupling takes place when an high voltage transmission line with its neutral grounded is parallel to a buried well coated pipeline. In such a way, an alternating magnetic flux is linked between high voltage transmission line and soil, which induces an alternating current in the coated pipeline. In fact, the pipeline and the soil behave as the second coil of a transformer, where the first coil is the high voltage transmission line and the soil. In other words, this is an auto-transformer, with a 1:1 transformation ratio. [11]. Figure 1.12 is a schematic representation of the inductive coupling on a steel pipelines located near a high voltage AC transmission systems. The voltages are induced in the pipeline due to imbalances in the distance of the various phase wires and in the current carried in each phase. The resulting voltages in the pipeline are a function of the distance of the pipeline from the phase wires, the voltage in the system, the current carried by the system and the phase imbalance in the current.
Da
Db
Dc
Da = Db = Dc
Figure 1.12 - Induced AC interference on a pipeline[18]
Inductive coupling causes voltage peaks on the pipeline at locations where the pipeline and power line separation changes, such as when the pipeline approaches or recedes from the power line right-of way. The crossing of the pipeline from one side of the power line to the other will also cause an induced voltage peak. For example if a pipeline and transmission line are parallel to each other and one of the two changes direction, the voltages will build-up at the point of divergence. Pipelines that pass under a transmission line at an angle of 90 do not have any AC current or 13
voltage induced. Although these potential and current changes are physical in nature, they are generally considered as electrical discontinuities because they cause a change in the longitudinal electric field impressed upon the pipeline[18,27]. The AC-induced voltages can even reach values that can cause serious danger to people maintaining pipelines that are subjected to AC-induced corrosion[28]. The AC circulating within the pipeline is exchanged with soil at coating defects.
Evaluation of induced peak voltage

The following formula has been proposed to evaluate the induced pick voltage in correspondence of discontinuities [27]
V=
Ep f I 2
Eq. 1.11
where, V = induced voltage at discontinuity (V); E = coupling coefficient (V/km/A); p = voltage coupling coefficient (km); f = multiplying factor; I = power line load current (A). Equation 1.11 and the coupling parameters (Tab. 1.1) are based upon a nominal 10-meter power line to pipeline separation or less. At greater distances, the induced voltage will be reduced by approximately the inverse ratio of the pipeline distance relative to the 10-meter reference[27].
14
Tab. 1.1 Values of the coefficients in Equation 1.11[27]
Steady state power line coupling coefficient Coupling Power line coefficient configuration E (V/km/A) Single circuit horizontal Single circuit vertical 0.05 0.05
Pipeline induced voltage coefficient Voltage Resistance coefficient 2 ( m ) p (km) 100000 100000 33000 33000 10000 3000 1500 500 10.6 5.2 6.2 4.8 3.4 2 1.5 1.2
Geometrical/electrical factors Type of discontinuity Pipeline approach/recede Power line crossover Pipeline insulator Power line transposition Multiplying factor f 1 2 2
Coating description Excellent (thick) Excellent (thin<20 mils) Good (thick) Good (thin<20 mils) Fair Poor Poor Poor
Double circuit vertical Like phasing Reversed phasing 0.10 0.015
1.5.3
Steady-State or Load Conditions
Steady-state conditions designates normal operating conditions of the electric power transmission system, which can vary from low to high load conditions. As previously said during such conditions, the currents flowing in the 3 phases of each electric circuit are relatively low in magnitude (compared to fault conditions) and their effects on nearby pipelines tend to cancel one another out. As a result, AC interference levels during load conditions result from incomplete cancellation between phases, due to the difference in the relative distance of each phase from the nearby pipelines and due to any unbalance in the currents the 3 phases carry. Three conditions may exist, that is, normal, peak and emergency. For the first two conditions, all AC phase wires are used to carry the AC current. For the latter, for example, during maintenance, only one circuit (of two) is used to carry the AC current. The latter condition can be more severe with regards to the magnitude of any induced voltages on a pipeline[23]. Inductive interference is the dominant interference mechanism under normal power line conditions. The magnitude of the AC current in the AC phase wires will tend to be a controlling factor. The induced AC voltages will also tend to increase with an increase in soil resistivity, and a decrease in the distance between an AC power line and the pipeline
[23]
. Very low soil resistivity
will aid the dissipation, in particular, of fault currents to remote earth and help to minimize the 15
effect of a fault on the pipe. Induced steady-state pipeline potentials are more severe when the pipeline coating has a high electrical resistance. However, a high coating resistance is desirable from a cathodic protection standpoint, so reducing the coating resistance is not usually considered a viable solution. In spite of the relatively low magnetic field levels during steady-state conditions, induced voltages on an unprotected pipeline can reach hundreds of volts[26]. Even with extensive grounding systems connected to the pipeline, pipeline potentials can be on the order of tens of volts. This constitutes primarily a shock hazard, which can be transferred miles away from the parallel corridor.
1.5.4
Fault Conditions
In cases where the overhead line has an earthed neutral, unbalanced or fault conditions can result in substantial currents flowing in the soil. For an unbalanced single-phase supply, e.g. an electrified railway, or earth faults on the AC transmission line, hazardous voltages may be induced even for short parallel lengths[23]. Also a fault at a pylon or a lightning discharge or where a severed AC phase wire comes into contact with the ground may induce high voltages.
Conductive coupling
When a single-phase-to-ground fault occurs at a power line structure, the large fault current injected into the soil by the structure raises the local soil potential. A pipeline located nearby, however, will typically remain at a relatively low potential, due to the resistance of its coating and grounding at points distant from the fault location. The pipeline potential rise will be particularly small for a pipeline with a high resistance coating. Therefore, the earth around the pipeline will be at a relatively high potential with respect to the pipeline steel potential[26]. During a fault, the worst affected part of a pipeline will usually be that part which is the closest to the faulted power line[23]. However, for a well-coated pipeline, considerable voltages can be transferred many kilometres beyond the end of a shared corridor.
Inductive coupling
During single-phase-to-ground fault conditions on the power line, induced potentials in a pipeline with no mitigation system can reach thousands of volts, due to the intense magnetic field caused by the large current which may flow in the faulted wire[26].
Combined effect
Unless the pipeline is perpendicular to the power line, the pipeline will be simultaneously subject to both inductive and conductive interference. In most cases the inductive and conductive components are addictive and this may give rise to a very large voltage difference. In fact the change in pipeline steel potential due to induction is essentially opposite in sign to the soil potential change due to conduction, therefore inductive and conductive effects add, producing even more severe coating stress voltages and touch voltages[23,26].
16
Therefore for fault conditions, the AC voltages are a combination of both the inductive and conductive voltages arising from fault currents flowing in the phase wires and into the soil from each faulted pylon. In general, during a fault condition, the induced voltage will tend to increase with [23,26]: an increase in soil resistivity; a decrease in the distance between the faulted structure and the pipeline; a decrease in the conductivity of the pipeline external coating; close proximity to a pylon earthing assembly. The effect of a fault on the predicted induced AC voltage can extend several kilometres away from he crossing point.
Transferred voltages
Due to inductive and conductive coupling, considerable voltages can be transferred many kilometres beyond the end of a common corridor. As a result, it is necessary to properly study the entire pipeline system, as mitigation may be required, for instance, to protect sites which are far away from the transmission line exposure location[26].
1.6 CHARACTERISATION OF AC-INDUCED CORROSION

In the corrosion field it is fundamental to ascertain the causes of corrosive phenomena. This may be done by in situ measurements or by using samples that can be subsequently analysed in the laboratory. The following are some aspects that can be considered in order to identify a corrosion failure as induced by AC interference[29]: presence of AC voltage on the pipeline; protection voltage on the pipeline (negative OFF-potential greater than -850 mV CSE); presence of a defect in the coating (usually an open small defect) often associated with coating disbondment and degradation; elevated pH values of the soil in the vicinity of the corrosion (pH >10); the corrosion form is usually rounded (advanced stage) or penetrating pits (initial stage); the corroded area is larger than the coating defect; corrosion products are very bulky and could be removed as a block; high AC and high DC cathodic protection densities.
17
1.7 CORROSION RATE

The principal factors that affect AC corrosion can be summarised as follows[18,12,29,30,31], corrosion increases with increased AC density or alternating voltage (AV) (Figure 1.13); cathodic protection decreases AC corrosion, but the magnitude of the DC currents required is high; corrosion decreases with increased AC frequency; the chemical composition and resistivity of the soil have a strong influence on the corrosion rate: corrosion increases in the presence of carbonates or bicarbonates and decreases in the presence of chlorides; corrosion increases with increased temperature; the average corrosion rate decreases rapidly with time, then less slowly with the exposure time and finally stabilizes to a steady value (Figure 1.14); corrosion rates are higher when the area of exposed steel is approximately 1 cm2.
1.0 Corrosion rate (g/cm2y) 0.8 0.6 0.4 0.2 0.0 0 300 600 900 1200 1500 1800
Peak cell voltage (mV)

Figure 1.13 - Corrosion rate as a function of peak alternating voltage. Experiments were conducted at room temperature under nitrogen purge for 24 h. The 60 Hz AV was applied between a Cu-Ni alloy and a [31] counter platinum mesh
18
1.0 Corrosion rate (g/cm2 y) 0.8 0.6 0.4 0.2 0.0 0 20 40 60 80 100 120 140 160
Time (h)
Figure 1.14 - Corrosion rate as a function of exposure time (AV = 1000 mV)[31]
Studies on carbon steel specimens exposed to soil under the influence of AC and CP polarisation showed that corrosion rates due to AC corrosion are not necessarily high, but that the rates are certainly multiples of the normal corrosion rates of steel in soil in the absence of AC[32]. The results of this work are summarised in Figure 1.15. It can be noticed that AC current density in the order of 20 A/m2 could significantly increase corrosion; CP can be effective at "low" AC current densities but not at "high" AC current densities. The data also suggest that even at "Low AC + No CP" conditions, at AC densities which are considered 'safe' by many publications (20 A/m2), the observed increase in corrosion rate, relative to a control, is by a factor of 2. For "High AC + High CP" results showed that protection could not be achieved. This last result is quite unexpected. It does not seems logical to have higher corrosion rates whit higher cathodic protection. However such behaviour has been reported also by other authors[29]. In any case more analysis are needed in order to verify such experimental evidence and to explain the reason of it. Most probably the high corrosion rate reported can be explained considering the enhancement of the cathodic process that can lead to coating disbondment[32].
19
Test Category Low AC + No CP High AC + No CP
Actual AC Current Density (A/m2) <20 >300 <20 <20 >300 >300
Actual CP shift (mV) 0 0 <150 >150 <150 >150
Relative (to control specimens) corrosion rate
600 500 400 300 200 100 0
Low AC + Low CP Low AC + High CP High AC + Low CP High AC + High CP
Low AC + High AC + Low AC + Low AC + High AC + High AC + No CP No CP Low CP High CP Low CP High CP Test category
Figure 1.15 - Averaged depths of penetration (pitting rate) for tested conditions[32]
1.8 EVALUATION OF CORROSION RISKS AND CATHODIC PROTECTION MONITORING

Like stray currents, AC interference cannot be measured directly. While for DC induced corrosion on buried structures, for instance interfered pipelines, there is large agreement on criteria to be used for corrosion mitigation and international standards are available since many years[10], in the case of AC corrosion, different approaches are used and different opinions still exist[33]. AC corrosion is not controlled directly as DC corrosion is. For example, during a pipeline survey it has been reported that the most rapid corrosion did not always occur at the points of the highest induced AC voltage on the pipeline[18]. The primary factor in determining the possibility for the presence of AC corrosion is the AC current density. Helm et al. concluded from their laboratory tests that[34]: up to 20 A/m2 of AC current density there is probably no risk of accelerated corrosion using the conventional criteria; between 20 and 100 A/m2 corrosion is possible since the conventional criteria are not reliable; at AC current densities in excess of 100 A/m2 corrosion damage is to be expected.
20
The European approach is the specification of the maximum allowable AC density to be measured by means of corrosion coupons: the threshold value so far proposed is 30 A/m2[35]. The German standard, DIN 50 925 states that, for coated steel pipelines, AC current density should be less than about 30 A/m2 while DC current density should be maintained about 1 A/m2[36]. Others criteria are based on the maximum AC voltage. The NACE RP0177-2000[37] suggests 15 V, but this value has been chosen mostly considering safety criteria for the persons than ACinduced corrosion. The minimum voltage level below which AC enhanced corrosion cannot occur has not yet been defined. It has been reported that it may occur at induced AC voltage levels of only a few volts[23], therefore mitigation of AC potentials to values below 15 V may not be sufficient with respect to AC current densities at the coating holidays. Application of increased cathodic protection current may be required to control AC corrosion[32]. Evaluation of corrosion risk is achieved by several measurements. The association of several of them makes it possible to consider a situation as potentially at risk or not. The parameters influencing AC corrosion risks are[12,33]: the real level of polarisation of the structure by cathodic protection; the level of AC current density; the extent of the metal surface exposed at coating defects; the electrolyte (soil composition, resistivity, etc.). Soil composition strongly affects the AC-corrosion risk. Identical electrical parameters can result in significantly different ACcurrent densities; climatic conditions, such as surface temperature, seem strongly affect the AC-current density on coupons. AC corrosion is most likely to occur only on well-coated structures where the AC current is shown to transfer from very small defects in the coating.
1.8.1
DC Potential Measurements in the Presence of AC
Natural gas transmission pipelines are usually supplied with cathodic protection (CP) to protect coating defects against corrosion. The potential measurement is easy to carry out, but its interpretation may present some concerns when stray currents cause huge ohmic drop contributions which may lead to misinterpretation[11]. The scope of the cathodic protection monitoring is to verify the protection level of the structure by checking that the potential matches the protection criteria. In the presence of DC or AC stray currents the potential measurement may lead to misleading interpretations. The potential reading is a function of the reference electrode position with respect to the structure and is the sum of three terms (Figure 1.16):
21
E = Eeq + + IR
Eq. 1.12
Eeq is the thermodynamic contribution and represents the potential value of the electrode versus the standard hydrogen electrode; is the overpotential contribution, i.e. the polarisation due to cathodic protection or interfering currents; IR is the ohmic drop in the electrolyte, depending upon the reference electrode position with respect to the structure, on the electrolyte resistivity and on the circulating current within the electrolyte. E, which includes all terms, is often called ONpotential. The term E IR = ET + = Etrue is called true potential or OFFpotential and gives the value of the overpotential due to the current flux.
Voltmeter E Reference electrode
Reference electrode
RI
Eeq Pipeline
I'
Soil (or electrolyte)
Figure 1.16 - Potential measurement
Therefore stray currents strongly influence the potential reading because ohmic drop contribution is often high. In case of DC stray currents, the measured potential is more negative than the true potential at cathodic zones and more positive at anodic ones. To know the true polarisation level the ohmic drop contribution has to be eliminated. The ON/OFF technique is commonly used to determine the true potential of protected structures provided a correct interpretation. For continuous monitoring, a corrosion coupon is often used with a reference electrode located close to the coupon. This device is also called true potential probe. The case of AC interference seems to be particularly critical: depolarisation time lower than 1 ms and corrosion attacks on samples with instantaneous OFFpotential below of 0.85 V CSE have been reported[33]. In literature there is lack of agreement about the correct procedure to measure the true potential in the presence of AC interference[33,39,21,38, 39]. It has also been claimed that the potential measurement misinterpretations caused by the AC could be also more severe than those related to the DC. In the specific case of coating defects in cathodically protected buried pipelines influenced by induced AC current, the CP evaluation becomes complicated, and the usual potential criteria are no longer necessarily valid.
22
It has been claimed that the instantaneous OFF-potential measurement is a non suitable technique for the characterisation of the AC-corrosion risk of cathodically protected structures because the obtained data are strongly influenced by the soil composition causing a very fast depolarisation of the metal surface[33]. In Figure 1.17 the instantaneous potential of a sample interfered by AC is represented. The curve a represent the case of a non protected pipeline, while b and c represent cathodic protection. The form and the amplitude of the sinusoidal curves remain, but their position with respect to the reference axis is changed[12].
E SCE
(mV)
a b
-850 c
Time (s)
Figure 1.17 - Evolution of the potentials in the absence (a) and the presence (b and c) of cathodic protection[
The samples potential curve is a sinusoidal curve whose displacement towards the more electronegative potentials is proportional to the level of cathodic protection. Consequently, if the level of cathodic protection is increased in such a way that there is no more positive current the potential becomes more and more electronegative[12]. The case c is when total compensation of the positive AC. However, to achieve this shift in potential high DC current are required, which would result in the production of large amount of hydrogen which may be disadvantageous because of all the problems relate to overprotection as hydrogen stress cracking or coating disbondment. Unfortunately the measurement of the true potential do not give information about the instantaneous IR free pick potential. Recently a measuring technique was developed to measure the AC induced effects on metallic structures. The system, with a switch OFF method on a coupon, provide IR-free potential, the current density and the phase angle at every instant of the AC period[39]. Using this measuring technique, the pipeline is considered protected from AC corrosion if the coupon-to-soil EOFFpotential is at any moment more negative than the protective potential range.
23
1.8.2
AC voltage
AC in soil or AC intercepted by buried metallic structures is surveyed by measuring the potential with an electronic multimeter that measures AC voltage for frequencies between 15 and 100 Hz. A mobile oscilloscope is useful for verifying the type of waves, their amplitude and frequency. For safety reason, it is generally considered that the AC voltage should be lower than 15 Vrms (rms = root mean square)[37]. Unfortunately, unlike the case of DC stray currents, there is no correlation between corrosion rate and AC voltage and therefore, even today there are no criteria based on AC voltage measurements. It is however possible to estimate AC density flowing through a coating defect of a certain size by means of the following equation:
i = VF
4 r
Eq. 1.13
when soil resistivity () , defect radius (r), and voltage drop to remote earth (VF) are known[11,16, 40]. The AC voltage level alone does not allow the evaluation of AC corrosion risk. Two separate pipelines exposed to the same AC voltage may or may not be subject to AC corrosion. Nonetheless, pipelines exposed to low AC voltage seem to be subject to very little risk[12].
10000
Vcorr (m/year)
1000
100
10
Initial Vcorr Steady State Vcorr
1 0 5 10 15 VAC
Figure 1.18 - Corrosion rate measured by mean of ER corrosivity probes as a function of AC voltage (UAC) on [7] a Danish site
20
25
30
Field data showed that a relatively small-sized defect (6 to13 cm2) in the coating on the pipe in a relatively low-resistivity soil could have AC current density in excess of 100 A/m2, while the AC voltage could be as low as 6 V[32]. Others field surveys[7,13] showed that very high corrosion rates were associated to AC potentials lower than 10 V (Figure 1.18). It has also been reported[13] that coupons exposed to the same alternating voltage showed AC density which varied with time and
24
location. This was probably due to some changes in soil resistivity and in chemical conditions closest to the steel surfaces.
1.8.3
AC current densities
The determination of AC current densities is a very important parameter in order to evaluate AC corrosion risks: the higher the density, the greater the risks. Current measurements on steel coupons must be carried out with a shunt whose resistance is less than that of the pipeline, of the potential coating defects and of the coupon. If this is not the case, the values will be significantly erroneous. As previously said the threshold value suggested by standards and laboratory tests[34,35,36] ranges between 20 and 30 A/m2. Though it has been reported that an AC current density of 20 A/m2 could increase corrosion nearly two-fold relative to a control specimen; suggesting a threshold current density lower than 20 A/m2[32]. It seems that there is not a theoretical 'safe' AC current density, i.e., a threshold below which AC does not enhance corrosion; however, a practical one exists for which the increase in corrosion due to AC is not appreciably greater than the free-corrosion rate for a particular soil condition[32].
1.8.4
AC Density/DC Density Ratio
Generally higher is the AC higher is the DC cathodic protection required[32,41]. Therefore recently in France the AC/DC current density ratio was proposed as AC induced corrosion risk indicator[12]: when the ratio is above 10, AC induced corrosion is almost certain; above 3 the risk is serious; below 2, the risk is less, although not necessarily totally absent. This approach has been proposed considering the following experimental data and field measurement[12]: measurements of DC and AC current carried on field showed that, at the corrosion sites, the ratios were always higher than in those areas where no corrosion had been observed; laboratory measurements showed that in the presence of AC currents was necessary a quantity of DC current greater than that is normally applied in order to obtain 850 mV; through the calculation of the AC/DC current density ratio, errors due to individual measurements of DC and AC intensities are partially eliminated; therefore the most significant errors of measurement with regard to the internal resistance of instrumentation and measurement circuits are eliminated; even if the current densities increase in magnitude as the defects surface areas decrease, the ratio remains constant whatever the surface areas of the coupons used to perform the measurements;
25
this ratio also makes it possible to adjust the level of DC current with regard to the AC current, allowing therefore the definition of the quantity of DC current sufficient for improved polarisation of a defect compared to a level of AC influence. It should be noted that the value of the ratio provides no means of quantifying AC corrosion and that this approach alone cannot be applied since there is no mention on the potential value. In fact even if DC true potential measurements have been proven to be of difficult interpretation in the presence of AC, their values remain a fundamental parameter during corrosion monitoring and risk evaluations. Furthermore considering the experimental evidence that high alternate current with high cathodic protection levels may be associated with very high corrosion rates[32] (Figure 1.15), it is possible to have a not too high AC/DC ratio whereas the actual corrosion rate is very high.
1.8.5
Cathodic Protection Criteria Based on AC and DC Densities Measured by Coupons
New cathodic protection (CP) criteria have been developed based on AC and DC current densities measured using coupons[17]. The numerical expression of the criteria is reported in Tab. 1.2, while the graphic expressions of the current density-based criteria are illustrated in Figure 1.7. DC current density is determined as the average current density on a coupon (i.e. CP conditions). Positive values of DC current density indicate that the current is flowing from the soil to the coupon. Cathodic protection area is indicated in grey. Corrosion activity can be divided roughly into three areas corresponding to the possible main risks of DC corrosion, AC corrosion and overprotection[17]. DC corrosion is defined as the corrosion due to the lack of CP current, stray currents from DC powered transit systems or other DC interference. The lowest limit of DC current density to prevent DC corrosion was determined at 0.1 A/m2[17]. On the other side the excessive DC current density may lead to hydrogen stress cracking or coating disbondment [17]. The AC corrosion area corresponds either to low DC cathodic protection and low AC densities or to high AC densities.
Tab. 1.2 - Numerical expression of the cathodic protection criteria for buried steel pipelines based on DC [17] and AC current densities measured using coupons
0.1 A/m2 iDC < 1.0 A/m2 then iAC < 25 iDC 1.0 A/m2 iDC < 20 A/m2 then iAC < 70 Arms/m2 where: iDC = DC density (A/m2) iAC = AC density (A/m2)
26
AC Corrosion 100 70
iAC (Arms/m2)
25 10 25 1 DC Corrosion 0.1 0.01 0.1 1 10 20 100 Protection Overprotection
iDC (A/m2)
Figure 1.19 - Graphic illustration of the cathodic protection criteria for buried steel pipelines based on DC and AC current densities measured using coupons[17]
1.8.6
Size of the Coating Defects
Small rather than large coating defects are susceptible to AC corrosion since the spread resistance (in m2) associated with the defects increases with increasing area:
Rs = K s d ( m2)
Eq. 1.14
where K is a constant depending on the geometry of the defect, d is a measure of the extension of the defect, and s is the specific resistivity of the local soil environment adjacent to the defect[7]. Experience[12] showed that the diameter of coating defects on a polyethylene coating is often closer to a few millimetres than it is to a centimetre. In addition, cases of corrosion have been observed on defects of very small areas (around 1 mm2).
Probabilistic approach
The idea that the current density flowing through an holiday in the insulating coating is a meaningful parameter related to the risk of corrosion is commonly accepted within the community of experts in AC corrosion; on the other side, the assessment of corrosion conditions is only possible when the pipeline has already been laid down in the trench and the current density can be really measured on simulated holidays. These measurements in the field are affected by a possible wide variation of the spread resistance of these simulated holidays, which is connected to complex and not yet completely understood electrochemical reactions deriving from DC and AC current effects and the chemical composition of the soil in contact with the bare steel. It has been demonstrated by laboratory tests that this spread resistance may, during time, increase by as much as 100 times or decrease by as much 60 times[25]. Simulation tools able to assess the level of current density exchanged between pipe and soil through the insulating coating holidays have been proposed. The method consists in the integration of deterministic calculations, necessary for 27
the determination of the induced voltage profile along the pipeline route, with probabilistic calculations necessary for the evaluation of the holidays size and consequently of the current density. The parameters and the characteristics relevant to the random quantities (i.e. the holidays area distribution, the number of holidays per unit length) have been inferred starting from experimental data coming from the field. The probability levels are directly related to: the levels of induced voltage on the pipeline; the number of holidays per unit length besides the other statistical characteristics of the holidays distribution; the length of the pipeline section considered. Deterministic approaches are based on specific assumptions concerning the holiday size and location and are normally focused on the worst case study, whereas probabilistic approaches take into account of the random nature of some significant parameters like the holidays size and location. The proposed algorithm[25] allows the assessment of the probability associated to the exceeding of a certain threshold current density value (J*) in a generic section of pipeline; the advantage of such an approach is the possibility to individuate those pipeline sections which are more exposed to the AC corrosion risk. The algorithm is still deterministic as far as the calculation of electric quantities (voltage, current, current density) is concerned while it is statistic as far as the holidays data are concerned; therefore the results of the algorithm are given in terms of probability of exceeding a certain value of current density for a generic section (J*), of given length, along the pipeline. Thus, if the pipe under the electromagnetic influence of an AC power or of an electrified railway line assumes an alternating voltage V at the holiday location, the current density J exchanged between pipe and soil through the holiday itself is given by:
J=
V = Rh A
V h d + s 4
Eq. 1.15
where Rh is the resistance to remote earth of the pipeline through the holiday, known as spread resistance. The spread resistance is given by the sum of two contributions (Figure 1.20): Rch, which represents the resistance relevant to the small cylinder inside the coating, and Reh , which represents the earth resistance (with respect to the remote earth) of the holiday; for points inside the holiday the resistivity is h while in all the other points is s; A is the area of the holiday.
28
soil s
pipeline axis
d A insulating coating holiday h Rch Reh = Rh
pipeline wall
Figure 1.20 Spread resistance or holiday resistance Rh to remote earth
Once the threshold current density value (J*) is established the upper limit (in function of the pipe voltage V) for the holiday area A in order to have the exceeding of the limit value J* for the current density through the holiday itself can be evaluated.
16 A* 2 s
where A*(V) is the limit area.
V h d J*
Eq. 1.16
The probability (P%) of exceeding a certain value for the current density is mainly related to two important quantities[25]: the length of the pipeline section considered (the longer is the section, the higher is the probability); the mean value of the voltage assumed by the pipeline in the same section (the higher is the mean voltage the higher is the probability). It is therefore possible to obtain set of curves relating the probability of exceeding the limit value of current density J* versus the pipeline section length for a given value of the mean voltage V. In Figure 1.21 an example is shown by considering a limit value of J*=30 A/m2.
29
50 40
P%(J>J*)
30 20 10 0 10 100 Pipeline section length (m) 1000
Figure 1.21 - Per cent probability (P%) of exceeding the current density limit J*=30A/m2 versus the pipeline section length for different values of the mean voltage; the curves from top to bottom correspond to [25] V = 50, 40, 30, 20, 10V respectively; nh=0.7 holidays/km
1.8.7
ER corrosivity probes
In the specific case of CP of coating defects in buried pipelines influenced by induced AC current, the CP evaluation becomes complicated, and the usual potential criteria are no longer necessarily valid. In Denmark, the connection of high sensitivity electrical resistance (ER) sensor for evaluation of CP and corrosion rate measurements has become usual practice, particularly when studying risks of AC corrosion[7,20,21].
ER based AC corrosivity probe

The AC corrosivity probe with associated instrumentation is based on the high-resolution differential electrical resistance. The technique utilises the fact that the electrical resistance of a metal probe element increases when corrosion diminishes the thickness of the element. Considering a metal element with dimensions L (length), W (width), and (thickness), the electrical resistance of the element can be expressed by[7,20,21]:
R = (T )
L W
Eq. 1.17
where (T) is the specific resistivity of the element material, which depend on the temperature. Re-arranging the equation, the thickness of element can be obtained as a function of element resistance[7,20,21]:
= (T )
L 1 W R
Eq. 1.18
Differentiation of the equation gives the corrosion rate (vcorr) of the element as:
30
v corr =
d dR W 2 = dt dt L (T )
Eq. 1.19
Hence, once the time change of the electrical resistance of the element, the element dimensions and resistivity are known the corrosion rate can be evaluated. The period of time needed to quantify a certain corrosion rate can be calculated as follows[7,20,21]:
t =
R W 2 v corr L (T )
Eq. 1.20
The equation predicts that the necessary period of time increase with increasing W/L ratio, and increases with the square of the element thickness. Hence, high sensitivity ER probes can be produced by using thin elements, but this decreases probe lifetime as well. R can be regarded as the minimum resistance change needed to provide a reliable measurement[7,20,21]. In Figure 1.22 an examples of corrosion rate measured by mean of ER corrosivity is given. It can be noticed that, as previously said, the corrosion rate can be very high even when the AC potential is lower than 10 V.
Figure 1.22 - Corrosion rate measured by mean of ER corrosivity probes and AC voltage throughout time on a Danish site[7]
1.9 DAMAGE TO PIPELINE EXTERNAL COATING

During an AC power fault condition, current flowing from the AC power lines to earth can give rise to instantaneous very high conductive and inductive AC voltage and current on a pipeline. Fault duration and magnitude are controlled by the AC circuit protection equipment installed by the local AC power authority. Voltage levels of several thousand volts are possible and can damage external coating. To prevent undue damage to an external coating, a maximum short-term 31
AC-Induced Corrosion cumulative AC voltage level of 3 kV to 5 kV[23] is usually considered acceptable for fusion bonded epoxy and polyethylene coated pipelines that have high integrity field joint coating. For tape-wrap, coal tar enamel and asphalt coating systems 2 kV is suggested as threshold value. Also in case of AC-induced corrosion occurred during steady-state conditions, damages of the coating in the area surrounding the pits are often reported[19]. Coating disbondment is often associated to AC interference due to the enhanced cathodic process.
1.10 SAFETY FOR PERSONNEL

In terms of safety for personnel and the public, a potential shock hazard exists when someone touches an exposed part of the pipeline (such as a valve) while standing on soil which is at a different potential. The touch voltage to which a person would be subjected when standing near the pipeline and touching an exposed part of the pipeline is defined as the difference in potential between the pipeline metal and the earth surface above the pipeline. Similarly, the step voltage is the difference in potential between a persons feet, and is defined as the difference in earth surface potential between two points spaced 1 m apart[23,26]. The following AC touch voltage levels are typically considered acceptable Less than 50 V AC steady-state for buried pipeline sections that may be exposed periodically by operator personnel, who are aware of the possible voltage levels and are suitably prepared for the problem; Less than 15 V AC steady-state for aboveground appurtenances to minimize the danger to personnel and livestock. The 50 V level is based on the fibrillation current threshold (50 mA) for an infinitely long fault duration[42], for a body resistance of 1000 and assuming a person is bare-foot while touching the pipe with his/her bare hand. The 15 V level is as set by NACE RP0177-2000[37] and has become the standard value.
1.11 AC INFLUENCE ON CATHODIC PROTECTION

As previously said the AC-interference causes perturbation of cathodic protection and AC corrosion risks. One of the most serious consequences of steady state induced AC is that corrosion can occur even if cathodic protection levels satisfy the standards and despite the induced AC has been reduced to less than 15V as required by standards. The presence of alternating voltage and current on buried metallic pipelines can cause malfunctioning or even damage to the Transformer/Rectifier (T/R) units of impressed current
32
cathodic protection. This is particularly valid for T/R units that are not equipped with suitable AC filter and surge protection.
1.12 HOW AC INFLUENCES CORROSION PROCESSES

The mechanism by which AC affects the corrosion process is not yet understood: different theories and hypotheses have been proposed, but none of them is able to fully explain and describe such a phenomenon. An important aspect to consider is whether at the frequency of the interfering signal, the electrochemical processes are reversible or not[43]. In fact in the presence of alternating voltage the reversibility of the electrochemical processes is related to the frequency of the signal: if the frequency is not high enough and the chemical reaction is not reversed, then the metal could degrade, for example, because the metal ions migrate and precipitate into the solution. The irreversibility of the chemical reactions occurring at the interface may causes changes on the double layer composition and on the metal/solution interface. Since corrosion phenomena are normally associated to unidirectional current and considering that if the symmetry factor in the Butler-Volmer equation is different from
1 2
, the potential curve
would not be symmetrical and the interface would have rectifying properties leading to the Faradic rectification effect[44], different authors[5,24,28,45,46] have used a modified Butler-Volmer equation to model the AC induced corrosion. It has been suggested that AC can enhance general corrosion, under conditions where it would in any case start but would otherwise become slow as a protective layer is build up[47]. However since AC generally leads to the formation of porous and non-protective layers, in that cases there would be an high probability to have very localised attacks. The acceleration of the corrosion rates in the presence of AC has been attributed by some authors[2,9,24] to the ability of AV or AC to reduce the polarisation of both the anode and cathode areas, as well as the electrochemical passivity of the electrode materials. Generally the corrosion potential is shifted in the negative direction, and the exchange current density increase and the Tafel slopes decreases correspondingly[2,4,6,9,24, 48,49] It has also been claimed that the application of alternating voltage signals does not change the corrosion mechanism[8,31, 50]. What is evident is the lacking of agreement between the different authors and the need of finding a more reliable description of the phenomenon. Most probably more than one of the proposed theories has to be considered leading to a mixed mechanism. In the following section the most popular theories will be presented.
33
1.12.1
Formation of a Non Protective Oxide Layer
The main effect of AC currents applied to steel is the formation of hydrous oxide layers that give rise to an increase in the corrosion rate due to their mechanical detachment and to the enhancement of the rate of the oxygen reduction reaction[8]. This has been concluded analysing the result of cyclic voltammetry of steel in alkaline solution (Figure 1.23). From the voltammetric curves combined with visual inspection it was observed the growth of an oxide layer, that with time becomes too thick and fragile and easily detaches itself from the metal, then a new layer replaces it, continuing the growth and the corrosion of the material. Thus, although the ferric oxides/hydroxides are very insoluble in alkaline solutions, corrosion can proceed. The structure and nature of the layers of corrosion products are significantly altered.
Figure 1.23 - Repetitive cyclic voltammetry for a steel electrode in 0.05 M KOH between the potential limits of 1500/100 mV; sweep rate 0.05 V s-'[8].
It was also observed that the diffusion coefficient of O2 decreases when the electrode is cycled because of the lower diffusion coefficient of O2 in the hydrous layer as compared with the diffusion in the bulk of the solution. The authors[8] concluded that the mechanism of the reduction reaction remains the same for a cycled as for an uncycled electrode and that alternating currents flowing through structures can accelerate the corrosion rate if the potential excursion encompasses the reduction of an `inner' oxide layer, not only by the growth of hydrated oxide layers, but also by the enhancement of the electrocatalytic properties towards oxygen reduction of the oxide layers formed on cycling.
1.12.2
Faradic Rectification Effect
The shift of equilibrium electrode potential for a single electrode by an alternating current is called Faradaic rectification. Models based on a pure Faradaic effect[5,24,28,46,46] consider that the non-linear nature of the currentpotential relation of a corroding system is responsible for the generation of a DC-current (rectification current), when a sinusoidal potential distortion is applied. For small amplitudes of the induced voltages the increase in corrosion rate is small, however for 34
large amplitudes of the induced voltages, the corrosion rate and corrosion potential can change significantly. According to these models, if overpotentials are asymmetrical and a sinusoidal potential is applied, a net mean current density (rectification current) will appear, involving a systematic corrosion. The parameter that governs the sensitivity of the corroding system for AC-corrosion is the ratio of the anodic and cathodic Tafel slopes (r = a/c). In Figure 1.24 the results of those models are summarized.
E 0 E2 E1 E0
AC voltage amplitude V0 = 0 < V1 < V2 r = a/c > 1
E 0 E0 = E1 = E2
AC voltage amplitude V0 = 0 < V1 < V2
V0 V1 V2 r = a/c = 1
V2 V1 V0 i0 i1 i2 Log i
i0
i1
i2
Log i
a)
E 0 E0 E1 E2 AC voltage amplitude V0 = 0 < V1 < V2
b)
V0 V1 V2
r = a/c < 1
i0
i1
i2
Log i
c)
Figure 1.24 Effects of alternating voltage on Tafel plots expected by the theoretical models reported in literature[5,24,28,46,46]: r > 1 (a); r = 1 (b); r < 1 (c)
These models showed that, considering a metal sample whose kinetics behaviour is under activation control, the AC-induced voltages (Vsint) leads to changes on the Tafel curves as follows: the Tafel slopes should be independent of the amplitude of the AC-induced voltage V; when r < 1 the corrosion potential should lower to more negative values; if r > 1 the corrosion potential should shift to more positive values; 35
for r = 1 the corrosion potential should keep the same value; the value of the corrosion current density (or the exchange current density, if the plot refers to an electrode in equilibrium) should increase in an exponential way whatever the value of the ratio r. Bertocci[45] was the first who gave a full treatment of the Faradaic rectification for an electrode under charge-transfer control for a sinusoidal modulation of the electrode potential. The starting point was the relationship between current density (i) and potential (E):
+ i = Ic + i f = i c + n k n exp( A nE) m k m exp( B mE)
Eq. 1.21
He restricted the analysis to the case where only one anodic and one cathodic reaction are important. Then
i = Ic + i f = i 0 [exp( A) exp( B)] + i c

where ic is the capacitive current, given by the derivative of the electrode charge Q = CE
Eq. 1.22
ic = C
d dC +E dt dt
Eq. 1.23
i0 represent either the exchange current density (if an equilibrium situation is considered) or the corrosion current density. A and B are related to the anodic and cathodic Tafel slopes a and c (A = (ln10)/ a; B = (ln10)/ c). The overpotential (0) is the difference between the actual electrode potential and the potential at which no DC is going through the electrode in the absence of an alternating modulation. Bertocci then evaluated the current output of the electrode when a voltage signal of the form
= 0 + V sin t
is applied to the electrode. The Faradaic current then becomes:
Eq. 1.24
i f = i 0 [exp( AV sin t ) exp( A0 ) exp( BV sin t ) exp( B0 )]
Eq. 1.25
When the time averages are considered, only the DC term is not zero, and represents a current which can affect the electrode. Therefore considering only the DC component, after few mathematical steps it can be obtained:
( AV ) 2k (BV ) 2k (i f )DC = i 0 2k exp( A ) exp( B0 ) 0 2 2k 2 0 2 (k! ) k =0 2 (k! )
Eq. 1.26
If the average potential (0) is kept at zero (the open circuit voltage), the DC current may be calculated, as
36
(i f )DC,0 =0 = i 0
( V ) 2k A 2k B 2 k 2k 2 k =0 2 (k! )
Eq. 1.27
which will be zero if A = B, that is if the anodic and cathodic Tafel slopes are the same, or it may be either positive or negative, if the activation energy of the anodic reaction is, respectively, smaller or larger than the cathodic one. During this calculation the DC component of the Faradaic current has been assumed to be also the DC component of the total current, that is, it was assumed that no rectification occurred for the capacitive current. The value of the double layer capacitance is in general a function of potential and can vary quite significantly when adsorption processes take place at the electrode. Bertocci considered that, if only voltage modulations of periods large compared with the relaxation times of adsorption reactions are considered, then the double layer capacitance is only a function of the electrode potential () but not of its derivatives. In that case it can be calculated that no rectification is produced by the double layer capacitance During time, the calculation has been extended including also the case of passive metals and electrode under mixed control (activation and diffusion) by different authors[5,24,28,46]. An expression for the shift in corrosion potential ( E corr = E corr ,AC E corr ,DC ) with the ACinduced voltage signal has been obtained[28]:
E corr =
2k
ac V ln I0 V I0 ln a + c a c
Eq. 1.28
V V where: I0 = k =0 2
1 (k!)2
and therefore the corrosion current becomes
V i corr (V ) = i corr I0 a
(a +c )
V I0 c
(a +c )
Eq. 1.29
It was shown for example that when one of the Tafel slopes is , as anodic slope in case of passive metals. then the corrosion current would keep constant for any applied AV, while the corrosion potential would increase. For cathodic reaction under mixed control, a modified Butler-Volmer equation was considered (iL limiting current density):
i = i corr exp a
exp c 1 i corr + i corr exp iL iL c
Eq. 1.30
37
With increasing voltage amplitude, the cathodic part of the curve is more and more controlled by diffusion. The corrosion potential decreases with increasing voltage amplitude. The rate of decrease of the potential is dependent on the ratio i corr iL . Due to a finite value of the diffusionlimited current density, the corrosion rate increases to this limited value, which is equal to the diffusion-limited current density iL. Diffusion limits the increase of the corrosion rate till the diffusion-limited current density.
Limitations of the faradic rectification models

These models do not take into account other factors that would limit the current to much lower values than those predicted by this model, such as mass transport into the solution, the formation of films of anodic products or other alterations of the electrode surface leading to passivation which would also restrict the amount of current. Furthermore the analysis do not take into account the double layer capacity and the capacity caused by the changes in the surface concentrations of the reactants and the products when AC is following across the electrode surface. Therefore the total current consists entirely of faradaic current. As a consequence of that such analysis does not explain the fact that the effect of AC diminishes with increasing the frequency.
A model including double layer capacitance

Lalvani et al.[46] continued the Bertocci work and proposed a model that assumes activation control with negligible solution resistance, but that also incorporates the double layer capacitance. The potential (E) across the parallel arrangement of a double layer capacitance (Cd) and polarisation impedance is assumed to be the sum of a DC potential (EDC) and an alternating voltage signal (Vsint), where V is the peak potential, is the pulsation ( = 2f) and f the frequency of the signal. Thus,
E = E DC + V sin t
Eq. 1.31
The total current (i) flowing through the circuit is then the sum of double-layer current (icd) and the faradaic current (if),
i = icd + if
Eq. 1.32
But the Faradaic current (if) is the difference between the anodic (ia) and cathodic (ic) currents
i f = ia ic
According to Tafel analysis, ia and ic are given by
Eq. 1.33
i a = a1 = i corr ,DC exp(
0 ) a 0 ) c
Eq. 1.34
i c = a 2 = i corr ,DC exp(
Eq. 1.35
38
where icorr,DC and 0 are the corrosion current and the overpotential measured in the absence of AV signals, and a,and a are the anodic and cathodic Tafel slopes respectively. All the previous models were based on the evaluation of the time-average (DC) current ( i ):
i=
(2 ) 1 idt (2 ) 0
Eq. 1.36
where 2/ is the period of the applied alternating voltage of pulasation . Such approach, as previously discussed by Bertocci, leads to zero value of the time average double layer current, icd and does not take into account the effect of the frequency. Lalvani at al. proposed therefore an approach based on the root-mean-square current, defined as follows[46]:
2 irms =
(2 ) 2 1 i dt (2 ) 0
Eq. 1.37
The effect of AC current on potential-current plots can be described therefore by means of the rout mean square current by the following expression
2 irms a2 1 V 2 = 0 + a1 2 2 K =0 (K!) a
2K
1 1 1 V 2a1a 2 + 2 a c 2 K = 0 (K!)
2K
a2 2
1 V (K!)2 K =0 c
2K
where a 0 = c d V . All the considerations about the correlation between the ratio of the anodic and cathodic Tafel slopes (r = a/c) and the changes on corrosion rate and potential due to the presence of AC are equivalent to those of the previous models. The very significant difference is that this model takes into account the effect of the frequency: the total rms current increases with frequency and the absolute ratio of anodic to cathodic Tafel slopes. Unfortunately all the experimental data available gave exactly the opposite evidence: the corrosion rate decreases with the frequency[3,8,9,24,31, 51].
1.12.3
Effect on Overpotentials
Weight loss tests and polarisation curves on cor-ten and carbon steel in 0.1 N NaCl suggested that AC interference may have a strong depolarising effect in such conditions[49]. The corrosion rate increased by factors of 4 to 6 (AC = 300 A/m2) Tests with low frequency alternating anodic and cathodic current showed that both steels polarised more rapidly in the cathodic direction than in the anodic direction. Thus, the anodic half-cycle of AC did not have time to restore the potential to its original value after the previous cathodic half-cycle. The result is a net cathodic polarisation
39
which accelerates or depolarizes the anodic metal dissolution reaction by lowering the anodic Tafel slope. Depolarisation of the anodic reaction was confirmed by polarisation measurements in the presence of AC. Depolarisation of the anodic reaction by AC was also observed in aerated solutions, but the corrosion rate was controlled by diffusion of dissolved oxygen, and no increase in corrosion rate was measured. The mechanism proposed is sketched in Figure 1.25. The overpotential decreasing due to the AC interference is industrially utilised during electrodeposition: the AC overlapped to the DC decreases the hydrogen evolution overpotential.
Ecorr,air
Anodic oxidation aerated Cathodic reaction aerated
Ecorr,air E corr Ecorr icorr icorr
Anodic oxidation deaerated Anodic oxidation with AC aerated or deaerated
ilim=icorr,air=icorr,air
i
Figure 1.25 Effect of anodic depolarisation by alternating current in aerated and deaerated solutions[49]
1.12.4
Effect of the Anodic and Cathodic Half-Cycles
The cause of AC enhanced corrosion is not yet fully established, an hypothesis is the effect of the frequency controlled positive part of an AC signal. The part of the alternating current which could be utilized in the metal dissolution is the average value or DC equivalent, denoted as Iavg This can be calculated from the relation[3]:
Iavg =
2 2 Ir m s
Eq. 1.38
where Irms is the root mean square value of the current. The weight of the metal (m') that would dissolve theoretically at 100% efficiency is
m' =
Q A w 2 2 Irms tA w = F n nF
Eq. 1.39
40
where Q is the quantity of electricity (Q = lawt; t = time of interference); F = Faraday constant, A w = Atomic weight of metal, n = number of electrons involved in dissolution reaction. Hence the current efficiency (CE) is calculated as follows
CE(%) =
m 100 m'
Eq. 1.40
where m is the actual weight loss of metal during the interference. Generally, AC corrosion is only a small percentage of what it would be if an equivalent DC current density would circulate. The efficiency is a function of the frequency, the nature of the metal, and the experimental conditions. The efficiencies reported for carbon steel vary between approximately 0.1 and 5 %[39]. At lower frequencies the metal dissolution is, in general, more efficient. In anodic half-cycles, the gas evolution reactions (O2 or Cl2) are less likely to take place than the metal dissolution reaction, because of potential considerations. Similarly, in the cathodic half-cycles, the H2 evolution is more likely than metal deposition. In an anodic cycle, It may be assumed that the major part of Iavg would be consumed for metal dissolution. O2 or Cl2 evolution will only take place under the conditions of concentration polarisation. In a cathodic cycle, the major part of the Iavg would be utilized for H2 evolution. This is because usually the metals considered require higher deposition potentials associated with high overvoltages[3]. Thus the quantity of electricity expended for dissolution of metal in the anodic cycle must be greater than the quantity of electricity expended for metal deposition in the cathodic cycle[3].
Positive half-cycle rectified AV signal

Lalvani et al.[48,50] studied the influence of positive half-cycle and negative half-cycle rectified AV signals and full AV signals on the corrosion behaviour of carbon steel held constant at three different DC potentials in a chloride solution. They found that the application of positive half-cycle rectified sinusoidal potential significantly accelerated the corrosion processes and that the corrosion rate increased with the peak potential (Figure 1.26). Corrosion also increased with time although the increase in the rate of dissolution decreased with time (Figure 1.27).
41
25
Corrosion Rate (g/cm2y)
20
15
10
0 0 100 200 300 400 Alternating Peack Voltage (mV)
Figure 1.26 - Corrosion rate as a function of peak alternating potential. The DC potential of the specimen was held at the open circuit potential of -580 mV(SCE) while a positive half-cycle rectified sinusoidal AV signal at 60 Hz was superimposed. Experiments were conducted at room temperature under nitrogen purge for 4 h[50]
16
12
0 0 5 10 15 Time (h) 20 25
Figure 1.27 - Corrosion rate as a function of exposure time. Experiments were conducted at a peak potential of 180 mV (SCE)[50]
Negative half-cycle rectified AV signal

Lalvani et al.[48] found that the negative half-cycle rectified signal may increase or decrease corrosion processes, depending on the DC potential applied on the specimen (the more anodic the DC potential, the higher the corrosion rate). Therefore the choice of DC potential greatly influences the corrosion rate and thus the mechanism of corrosion. They revealed that, when a DC potential was imposed, the corrosion increased with the peak voltage (Figure 1.28), although a negative rectified half-cycle potential waveform was applied. The 42
following explanation is offered for the observed behaviour. They explained the results considering that the potential in such experiments was maintained at -580 mV (SCE), then more anodic than the corrosion potential of carbon steel. At these potentials, active alloy oxidation results in formation of corrosion products that could limit or arrest further metal dissolution. The application of negative waveforms could result in film dissolution and higher metal dissolution when the potential is maintained at -580 mV (SCE) for the time period corresponding to one-half of the cycle.
15
12
0 0 100 200 300 400 Alternating Peack (mV)
Figure 1.28 - Corrosion rate as a function of peak potential. The DC potential of the specimen was held at the open circuit potential of -580 mV (SCE) while a negative half-cycle-rectified sinusoidal AV signal at 60 Hz was superimposed. Experiments were conducted at room temperature under nitrogen purge for 4 h[48]
Full-wave sinusoidal AV
Lalvani et al.[48] found also that the arithmetic sum of materials degradation rates for the positive half-cycle and negative half-cycle rectified potentials was approximately equal to the rate for the full-wave sinusoidal potential. The dissolution rate was found to he the highest for the full-wave sinusoidal and the lowest for the negative half-cycle rectified signals. The application of sinusoidal signals reflects the combined effects of the positive and negative rectified signals on the metal dissolution[48].
1.12.5
AC-Induced Fluid Flow
Ramos et al.[52] studied the AC electroosmosis, the fluid flow due to the electroosmotic stress arising from the interaction of the electric field and the electrical double layer in the electrodes. They found that: the electrode polarisation plays a significant role in controlling the frequency dependence of the flow; the velocity of the fluid is frequency dependent;
43
the driving force for this flow arises from the interaction of the nonuniform electric field with the charge in the diffuse double layer; the velocity varies with frequency, reaching a maximum at a characteristic frequency; at high frequencies the potential is dropped entirely across the electrolyte, while at low frequencies the applied potential is dropped almost entirely across the double layer, showing that the electrodes are close to being perfectly polarisable at these frequencies. Ramos et al. suggested that the mechanism governing the fluid flow is related to electroosmosis and electrode polarisation. They termed therefore the phenomenon AC electroosmosis.
1.13 EFFECT OF THE AC FREQUENCY

The only point about which there is large agreement in literature[3,8,9,24,31,51] is the relationship between the AC-induced corrosion and the frequency of the signal: the anodic current efficiency, (CE%), for metal dissolution decreases with increasing frequency (Figures 1.29 and 1.30). Also the magnitude of the potentials shift due to the AC signal decreases with the frequency. The AC does not influence corrosion phenomena at frequencies higher than 150-200 Hz. The reasons for this behaviour can be summarised as follows: as for any process, also electrochemical reactions are characterised by their induction time, during which the current is mainly used for the electrical charging of the metal/solution interface and it is at the origin of the diminution of the proportion of the electric charge (used for the metal dissolution at each AC cycle) as a function of frequency[51]; at high frequencies, the double layer impedance decreases significantly and hence, a relatively small fraction of current flows through the polarisation resistance resulting in a lower material degradation rate[31]; with increasing AC frequency, the interval between successive anodic and cathodic halfcycles becomes progressively shorter. As time interval is short, the metal ions formed at the electrode in anodic cycles would be available for immediate redeposition in the cathodic cycles. Furthermore the hydrogen atoms formed in the cathodic half-cycle do not have time to coalesce and form hydrogen gas molecules. Thus for the next anodic cycle there exists a layer of hydrogen atoms on the electrode surface, which prevents the metal dissolution reaction to some extent and the hydrogen ionization reaction takes place instead. At very high frequencies, no effects of AC would be observed, since all current would pass through the double layer[3]. The frequency affects also the pit morphology, the pit density and passivity current density: both decreases with increasing frequency[31,24,51].
44
Effect of the waveform

Generally, a triangular wave causes the severest destruction of passivity, followed by sinusoidal and square wave[4,6].
3.0 Corrosion rate, g/cm2 y 2.5 2.0 1.5 1.0 0.5 0.0 0 200 400 600 800 1000 1200
AV frequency, Hz
Figure 1.29 - Corrosion rate as a function of frequency (AV = 1.500 V)[31].
12 10 Corrosion Rate (g/cm y)

2
8 6 4 2 0 0 25 50 75 100 125 150 Frequency (Hz)
Figure 1.30 - Corrosion rate as a function of frequency. Experiments were conducted at a peak potential of [50] 180 mV (SCE) - only the anodic part of the signal was supplied
45
1.14 AC EFFECTS ON THE CORROSION OF THE DIFFERENT METALS

As previously described generally the corrosion rate of the metals increases with the AC or AV pick value and decreases with frequency and time. The corrosion normally has a localised morphology. The attention of researchers focused primarily on the following metals: steels, copper, aluminium, titanium, zinc and lead[53,54,55]. Commonly the metals are divided into two groups depending on their corrosion behaviour in the presence of AC: first group: carbon steel, copper, zinc and lead; the AC efficiency is quite low (CE < 2%), though they can give localised attack with high penetration rate; second group: aluminium, titanium and magnesium. The efficiency of AC is higher than for the first group. The highest value has been revealed for aluminium (CE 40-50 %). The interest on the behaviour of zinc, aluminium and magnesium is connected to their use as sacrificial anodes in galvanic cathodic protection. Titanium instead is used as insoluble anode for impressed current cathodic protection.
1.14.1
DC Potential Variation in the Presence of AC
Normally the DC potential of metals shifts suddenly toward the active direction in the presence of AC. The potential shift increases with the alternate current density. Then the potential shifts back toward the noble direction reaching generally a steady-state value. The time needed to reach such steady potential and the value of it strongly depend on the experimental conditions and on the composition of the metal. The two most frequently observed behaviours are reported in Figure 1.31: once stabilised, the DC potential in the presence of AC may be less or more noble than the potential in the absence of AC.
Ecorr before AC interference b) DC potential DC potential
a)
Time
Time
Figure 1.31 DC potential as a function of time
46
1.15 PASSIVE METALS

Destruction of the passivity by AC induced current was reported in several conditions summarised as follows: the critical current density for passivity does not change with AC; for high AC density the passive may almost disappear depending on the experimental conditions; the passivity current density increases in the passive region; the effect of AC is similar to the addiction of chloride ions to the electrolyte; an AV or AC signal may reduce or destroy the ability of the material to passivate. The effect of AC appears to be similar to the addition of chloride ions to the corrosion environment. It destroys the passivity at certain localised areas, and increases the corrosion current in the passive region; the only AC alone may broke the passive film; pitting becomes more severe as the alternating voltage level increases and its frequency decreases.
[9,24,31,56]
The results reported about the behaviour of passive metals in the presence of AC can be
1.15.1
Influence of Stray Currents on Corrosion of Steel in Concrete
Consequences of stray current in reinforced concrete change according to the properties of the concrete (alkaline, carbonated or contaminated by chlorides), to the duration of the current circulation and to the current density. Steel reinforcements in concrete are in passive state due to the alkalinity produced by the hydration of cement[57]. The effects of interference are greatly influenced by the reinforcement conditions which can be passive, active due to carbonation or active due to chlorides. In chloride-free concrete, interference is unlikely to occur, unless a very intensive electric field is present for a long period. DC current can induce corrosion initiation on the reinforcement in the anodic zone only after it has circulated for a certain time[58,[59]. Passivity therefore provides resistance to stray currents. Since the reinforcement is not coated, it is rare that high current density can be induced by stray currents in concrete. The presence of chlorides favours localised interference at chloride contaminated zones. In the case of structures contaminated by chlorides, even at levels in themselves too low to initiate pitting corrosion, stray currents may have more serious consequences. In fact, stray currents stimulate initiation of pitting corrosion by taking the steel potential to values higher than the pitting potential[58].
47
AC currents are less dangerous than DC for rebars in concrete. It has been reported that alternating current densities lower than 50 A/m2 did not induce corrosion initiation on non carbonated, containing less than 0.4% chloride concrete, even after 5 months of continuous interference. Nevertheless AC current may stimulate macrocouples taking place in the concrete between passive and corroding steel and can increase the corrosion rate on corroding steel in chloride contaminated concrete[58].
1.16 EFFECT OF AC ON CORROSION IN SOILS

Dry soil is not corrosive. Corrosion can take place only in the presence of water, when soil becomes an electrolyte[11]. Soil aggressiveness is not influenced directly by its type or composition but instead is determined by the characteristics of the water it retains, such as resistivity, salt content, pH value and oxygen availability; therefore factors determining soil corrosiveness are various and sometimes even contradictory, such as the presence of oxygen and the possibility of bacterial corrosion. As previously said the soil composition can heavily influence the corrosion rate in the presence of AC interference. The cations present in the soil can be divided into two groups according to their effects, namely alkaline- and earth alkaline metal cations[12]: the earth alkaline cations Ca2+ and Mg2+ form hydroxides with relatively low dissolvability; therefore precipitation may result in the formation of high resistivity cover layers, which increase the resistance of the coupon; the alkaline cations form hydroxides (NaOH, KOH or LiOH) with very high solubility; the formation of the hygroscopic layers in the region of the holidays results in a decrease of the coupon resistance and to an increase of the protection current and also AC-current to such holidays. The presence of alkaline or earth alkaline cations in the region of coating holidays have a significant influence on their resistance. Results with coupons having an area of 1cm2[12] have shown that the resistance may increase up to a factor of 100 or may decrease to a factor of 60, depending on the composition of the soil.
48
1.17 INTERFERENCE MITIGATION

There is none particularly effective method for preventing interference in all situations. A technical-economical approach should be applied to each single case.
1.17.1
DC Mitigation
Stationary interference
Prevention methods used are based on two principles: the elimination of driving voltage E, as by drainage and cathodic protection, and the increase in resistance of the interference current path by means of coatings and electrical sectioning[11]. Drainage is the most common, effective and economic method used for crossing pipelines. It consists of an electrical connection between the pipelines at the crossing point by a calibrated resistance (Figure 1.32) to render both pipelines cathodic, so that potential is brought within the protection interval. It may be difficult to calibrate potential when pipelines have different insulation, because the well-coated one may be overprotected and the poorly insulated one insufficiently protected. When galvanic anodes are placed over the crossing zone, CP transfers the pipeline interference current to the anodes, causing only galvanic anode corrosion. The number and weight of the anodes to be used is determined by the degree of interference. To increase the resistance to the interference current, insulating joints and coatings are used. Using these two methods, the interference current can be reduced by about one order of magnitude.
Interfered pipeline Groundbed Drainage by calibrated resistance T/R
Figure 1.32 - Drainage at pipeline crossing[11]
49
Interfered pipeline Coating
Groundbed Insulated joint T/R
Figure 1.33 - Insulating joint insertion and use of coating[11]
Substation Drainage Insulating Joints
Interfered Pipeline
Figure 1.34 - Fig. 5.19
Example of drainage and insulating joint insertion to mitigate non-stationary interference[11]
Non stationary interference

It is more difficult to prevent non-stationary interference, since it changes in time. Three methods are employed. The first provides cathodic protection that operates at constant potential, then automatically contrasting stray currents by an increase of protection current when interference tends to establish anodic behaviour and by a decrease of current in the opposite case. The second method utilises insulating joints and coatings to increase the resistance of the current path (Figure 1.33). The third method directs the current through a metallic path by introducing an electric connection (drainage) between the structure and the rail near the substation (Figure 1.34). In order to avoid dangerous current inversion, as in the case of a temporary substation shutdown, the drainage consists of a diode. Forced drainage, which is an impressed current cathodic protection system operated at constant potential using the rail as groundbed, is also used.
50
1.17.2
Mitigation of AC Interference
The preventive measures are simple but must be set up judiciously[18,12,23,26]. Depending on the individual case, corrosion prevention can be obtained by the first or by both of the following actions: provide a satisfactory level of polarisation of the structure through cathodic protection; reduce the AC voltage and thus the AC current density. The induced potentials can be controlled and attenuated by earthing measures. However, a direct earthing of the pipeline counteracts cathodic protection therefore suitable DC blocking devices should be installed between the pipeline and the earthing. Introducing gradient control wires, or other mitigation types, at one location may adversely affect another location that had been thought to be safe. Consequently, the design of all the mitigation systems has to be assessed considering all the pipeline length. Software are available which model the pipeline and power transmission line interaction conditions, and help the optimisation of the mitigation design.
Lumped grounding
Localised lumped earthing systems[23,26] are probably the simplest and most commonly used method of lowering the AC interference potential of a pipeline. Localised lumped grounding provide a quite localised effect that may reduce the steady state potential locally but may not provide protection elsewhere along the pipeline. The pipeline is simply connected to a low impedance ground path. If the impedance is made low enough at the point of connection to the pipeline then the AC potential will be decreased locally. These systems may consist of many vertical rods or possibly a well groundbed containing sufficient anodes to reduce the resistance to earth. It is important to consider that the anodes will be consumed and may require future replacement to ensure continued protection against induced AC. Attaining the required impedance can require large grounding systems. Where soil resistivities are very low, if installed at regular intervals, the lumped method can result in satisfactory protection, while where the soil resistivities are high this mitigation strategy can be both impractical and exorbitantly expensive.
Cancellation wires
The cancellation wire technique[26] consists of burying long wires parallel to the transmission line; therefore the wires themselves are subject to interference from the transmission line. By carefully locating each wire, the voltages induced on it are out-of-phase with the voltages induced on the pipeline. Then, by connecting one end of the wire to the pipe, the out-of-phase voltages on the wire will cancel the voltages induced on the pipeline. The other end of the wire is left free. It is only designed to mitigate magnetically induced voltages, and does not address potentially damaging conductive interference during fault conditions. It may even worsen induced voltages for certain fault locations.
51
Gradient control wires

Gradient control wires[23,26] consist of one or more bare metallic conductors of zinc, copper or galvanised steel with or without backfill materials. They are buried parallel with and close to the pipeline with regular connection points made between the pipe and the gradient control wires. The wires are effective in both the inductive and conductive cases. In the inductive case gradient control wires provide additional grounding for the pipeline by decreasing the induced pipeline potential rise. Where gradient control wires are made of zinc they act in the same manner as a sacrificial anode. In order to do not affect cathodic protection and to be able to carry out routine surveys the gradient control wires should be connected to the pipeline through a polarisation cell, whichever material is used to provide mitigation.
52
EXPERIMENTAL
It is commonly believed that AC affects corrosion process at current densities higher than 30 A/m2, values considerably higher than the DC density that can cause serious damages on metallic structures[30,16]. Despite the number of works on this topic, many aspects of the phenomenon need further investigations. First of all there is no agreement about the mechanism by which AC influences the corrosion processes. No one of the different theories proposed is able to fully describe the AC induced corrosion. Furthermore it is not yet clear how to estimate the risk of corrosion due to AC and which level of current density or alternate voltage may cause significant damages. The aim of the experimental work was to investigate such aspects, as follows: 1. design of an electric circuit to allow independent control and measurement of AC and DC contributions in order to guarantee reliable measurements; 2. study of the effect of AC current on galvanic corrosion (first step to study the effect of AC on cathodic and anodic processes); 3. study of AC and DC overlapping through the circuit of point 1; 4. determination of the anodic and cathodic polarisation curves in the presence of AC. The aim of these experiments was the evaluation of AC effects on the corrosion mechanism as far as corrosion kinetics is concerned; 5. weight loss tests in order to quantify the damage caused by AC, and to estimate AC corrosion threshold parameters; 6. characterisation of the morphology of the AC corrosion; 7. determination of AC effects on passive metals; 8. cathodic protection monitoring in the presence of AC and DC stray currents; 9. oscilloscope measurements; 10. analysis of the mathematical models proposed in literature and comparison with experimental data.
Experimental
2.1 SETTING UP OF THE ELECTRICAL CIRCUIT

As previously said, the aim of the research project was to study how AC affects corrosion and what is the effect of the simultaneous presence of AC and DC current. In order to assure reliable and unaffected measurements, it was necessary to be able to supply and measure independently AC and DC contribute[24]. After a careful review of the available literature and with the help of Prof. Zaninelli and Prof. Ottoboni of the Electrotechnics Department of the Politecnico of Milan, the circuit represented in Figure 2.1 was build up.
C R1 R2 R3
20 H
L
variac
AC
V
DC =
Galvanostat
RE W CEAC CEDC
R1, 10
R2, 10
Capacitors
Inductor L, 20 Henry
Figure 2.1 - Electric circuit with DC and AC separation
54
Experimental
The electric circuit has two different meshes: on the left side there is the AC mesh, while on the right side there is the DC one.
2.1.1
AC mesh
The AC mesh can be described as follows: the AC current is supplied by an AC feeding system (variac) and flows between the specimen (working electrode, W) and a counter electrode (CEAC); the AC flows in this mesh and is measured by means of the shunt R1 (10 , 250 W) two capacitors prevent DC circulation in this mesh.
Characteristics of the capacitor

A capacitor is characterised by its capacity C measured in Farad (F). The charge Q stored by a capacitor is Q = CV, where V is the voltage applied between the two plate of the capacitor. In the AC circuit, after the charge of the capacitor, the DC does not flow anymore because the circuit is interrupted by the capacitor insulator. Therefore the capacitor blocks the DC flow. The capacitor has a different behaviour with the AC: it works as an high-pass filter, blocking the low frequencies (DC current included). The high-pass filter works gradually, i.e. given a constant alternate voltage the amount of AC that can flow trough the capacitor increases with the frequency. The capacitor is forced to charge, discharge and recharge with opposite sign following the alternate voltage applied to its plates. The capacitive reactance XC is the obstacle that the capacitor opposes to the AC flowing. The capacitive reactance is measured in and can be calculated by the formula:
Xc =
1 C
Eq. 2.1
where is the pulsation ( = 2f) and f the frequency. The Ohms law becomes therefore:
V = XCI
Eq. 2.2
where V and I are vectors while Xc is a constant. It was therefore necessary to apply a capacitor with high capacity to block the DC and let pass the 50 Hz frequency AC. The high capacity available on market are all electrolytic capacitors. For electrotechnical reasons, if one wants to insert an electrolytic capacitor on a circuit where the AC is flowing, it is necessary to insert two capacitors as represented in Figure 2.2. Two 1000 F capacitor were put into the AC mesh; the global capacity is therefore 500 F and the capacitive reactance is about 6 .
55
Experimental
+ -
- +
Figure 2.2 Schematic representation of the alignment of the two capacitor into the circuit
2.1.2
DC mesh
The DC mesh can be described as follows: DC current is supplied by a galvanostat and flows between the metallic specimen (W) and the counter electrode (CEDC); DC is measured by means of the shunt R2 (10 , 10 W); AC flowing in the DC mesh is prevented by a 20 H inductor.
Characteristics of the inductor (L)

The inductive reactance XL is the obstacle to AC flowing. The capacitive reactance is measured in and can be calculated by the formula:
X L = L
where is the pulsation ( = 2f) and f the frequency. The Ohms law becomes therefore:
Eq. 2.3
V = XLI
Eq. 2.4
where V and I are vectors while XL is a constant. Therefore, the higher the inductance (of the inductor), the better the filtering of AC signal. Unfortunately a 20 Henry inductor is already more than 10 kg weight, and quite big. Furthermore it was not possible to find a bigger inductor at a reasonable price. The inductive reactance XL of a 20 Henry inductor is about 6300 .
2.1.3
Common Branch
The AC and the DC meshes share a common branch, where AC and DC contributes overlap and flow to the working electrode (W). This current can be measured by means of the shunt R3. The resistance of shunt R3 is not fix and can be changed depending on experimental conditions.
2.1.4
Efficiency of the Circuit
The circuit was tested in different conditions. The efficiency of the DC filter is 100%, i.e., no DC flows in the AC mesh, whereas, despite of the 20 Henry inductance, a small part of the AC contribute flows in the DC mesh. In any case it has been verified that the AC circulating in the DC side was less than 1% of the total AC. Such a filter for the AC current was considered sufficient for the planned tests.
56
Experimental
2.2 TESTS ON GALVANIC CORROSION

The aim of these tests was to study the effects of AC current on galvanic corrosion. This was the first step in order to analyse the influence of AC on cathodic and anodic processes and on corrosion rates.
2.2.1
Experimental Conditions
Solution Composition
Tested solutions were: Soil: 0.25 g/L and 0.5 g/L of Na2SO4, simulating different soil resistivities. This electrolyte was chosen because sulphate ions are present in soil in large amount, and because the corrosiveness of soil is often related to its sulphate content; Seawater: 35 g/L of NaCl, simulating seawater chlorinity. The test solution was maintained at 20C ( 1C) by a cryostat/thermostat and circulating distilled water in an external compartment of the cell. Tests were carried out both in aerated and deaerated conditions. A first set of experiments was carried out on solution open to the atmosphere. A second set of experiments was performed scrubbing pure air into the solution in order to guarantee a continuous supply of oxygen during the experiment.
Cell, samples and Electrodes Characteristics

The cell was 150 mm in diameter and 140 mm in height. The carbon steel and the AISI 304 stainless steel specimens were 30 x 30 x 1 mm (Figure 2.3). Copper cable was glued on the surface by means of a conductive resin, and the connection was insulated with epoxy resin (the tested net surface was 900 mm2).
a)
b)
Figure 2.3 Schematic representation of the samples
57
Experimental
The galvanic coupling was obtained by connecting two specimens (carbon steel and AISI 304 stainless steel) through a shunt (R1 and R2), that was also used to measure the galvanic current (Figure 2.4). Same galvanic coupling was used as AC counter electrode (Figure 2.4). Potential measurements versus a calomel reference electrode (SCE) were performed using a Luggin capillary in order to eliminate the IR drop contribution.
R3
R1, R2 , R3 (10 W, 20 W)
Variac Thermometer
R1 SCE
R2
V H2O to the thermostat Stainless Steel Carbon steel
Stainless Steel Carbon steel
H2O from the thermostat
scrubber
Figure 2.4 - Schematic view of the cell for galvanic coupling tests
2.2.2
Experimental Procedure
The AC feeding system was 50 Hz, 220 V and 4.5 A variable output transformer (variac). AC was measured by the shunts R1, R2 and R3 (10 , 20 W, Figure 2.4). The AC current density supplied was in the range of 0150 A/m2. The galvanic coupling current was measured by shunts R1, and R2. Tests were performed as follows: measurement of carbon and stainless steel potential, before coupling; galvanic coupling and measurement of potential and current for 3 days, without AC; AC application: two or three steps, each at least one day long, until AC current density reached 150 A/m2; monitoring of DC potential and (galvanic coupling) current; AC switch off and measurement of potential and (galvanic coupling) current. During this first set of experiments the circuit previously described was not used (Par. 2.1, pag. 54). Therefore the measurements of galvanic coupling current were affected by the presence 58
Experimental
of AC current, that was four orders of magnitude higher than the DC current. Potential was measured using a high impedance voltmeter (200 M) with a suitable AC filtering device, with an acquisition frequency of 1 Hz. Though such multimeter was not able to filter such an high AC and therefore gave instable reading of the DC. The valued obtained are hence to considered as a qualitative indication rather than a quantitative measure of the corrosion rate in the presence of AC.
2.3 TESTS WITH SEPARATED CIRCUITS: AC AND DC OVERLAPPED ON THE SAME SAMPLE
The aim of these tests was to study the influence of AC interference on carbon steel under different conditions, such as free corrosion, anodic and cathodic polarisation. Anodic polarisation simulates corrosion conditions of buried structures in the presence of galvanic coupling, typically with bare copper grounding systems. Cathodic polarisation simulates the buried structures under cathodic protection. The use of the electric circuit described previously (Par. 2.1 pag.54, Figure 2.1) allowed a correct control and measurement of the AC and DC contributes.
2.3.1
Experimental Conditions
Testing environments were: sulphate (4 g/L Na2SO4) and chloride (35 g/L NaCl) containing aqueous solutions, both in aerated and de-aerated conditions, simulating soils and seawater respectively. The solution was maintained at 20C ( 1C) by using a thermostatic cell through a cryostat/thermostat and circulating distilled water in an external compartment of the cell.
Cell, Samples and Electrodes Characteristics

The test cell was the same as galvanic coupling experiments: 150 mm in diameter and 140 mm in height. The carbon steel plate specimens used were similar to those previously described (Par. 0, pag. 57), with different surface areas (200, 900, 1600 and 2500 mm2). The sample (working electrode W) was connected to the circuit as shown in Figure 2.5. As counter electrodes for the DC and AC current two MMO activated Ti net, named CEDC, and CEAC respectively.
59
Experimental
Galvanostat R2 L
G
Variac R1
R3
Thermometer H2O to the thermostat CEDC (MMO-Ti wire net) CEAC (MMO-Ti wire net)
SCE
H2O from the thermostat scrubber Carbon steel (W) Figure 2.5 - Schematic representation of the cell and the electic circuit
2.3.2
Overlapping conditions of DC and AC were studied in the following conditions: free corrosion, cathodic and anodic polarisation. The AC feeding system was a 50 Hz, 220 V and 4.5 A variable output transformer (variac). The galvanostat used to supply anodic or cathodic DC was an AMEL instruments, model 2049. AC was overlapped to the carbon steel specimens at different current densities, ranging from 0 to 6000 A/m2: free corrosion tests: AC current density was in the range of 106000 A/m2; anodic and cathodic polarisation tests: AC current density was in the range of 01000 A/m2 whereas DC densities applied were: DC cathodic current densities ranged from 0.1, 1 to 10 A/m2, where the first value corresponded to a conventional cathodic protection current density, the second and the third values corresponded to overprotection conditions; DC anodic current densities were in the range of 1 and 10 A/m2.
60
Experimental
Tests on freely corroding samples were performed following this sequence: rest potential measurement; application of AC current after one hour: three steps, each at least 2 hours long, in the range 0-6000 A/m2; AC current switch off. Tests on cathodically or anodically polarised samples were performed as follows: rest potential measurement; cathodic or anodic polarisation (for at least 1 hour); application of AC current: three steps, each at least 2 hours long, until the AC current density reached 1000 A/m2; AC current switch off, followed 2 hours later by the DC current switch off. The potential was measured by means of a calomel reference electrode (SCE) and a Luggin capillary, in order to eliminate IR drop contribution. The same high impedance (200 M) voltmeter was used.
2.4 DETERMINATION OF THE ANODIC AND CATHODIC POLARISATION CURVES

Whereas it is commonly believed that AC can cause serious damages on interfered metals, there is a lack of agreement about the mechanism by which AC affects corrosion phenomena. Different theories have been proposed, though no one is able to fully describe the phenomenon. Therefore, galvanostatic polarisation tests were performed with the purpose of investigating the effects of AC on corrosion kinetics. The influence of AC on kinetics parameters such as Tafel slope and exchange current densities was evaluated.
2.4.1
Measurement Procedure
Potential-current curves[60] plays a decisively important role in corrosion science. An variable DC flow is achieved by introducing a variable DC source in the external circuit between the working electrode and the counter electrode. To control current either a galvanostatic device can be used, which holds the current constant, or else to maintain a constant electrode potential with respect to the reference electrode a potentiostatic device can be used. The typical laboratory arrangement for the working, reference and counter electrodes and the respective electrical connections to the galvanostat or potentiostat are sketched in Figure 2.6.
61
Experimental
Potentiostat
CE RE W
Galvanostat
CE W
voltmeter
a)
b)
Figure 2.6 Schematic circuits for: a) potentiostatic; b) galvanostatic measurements of polarisation curves
To shorten the work of measuring steady-state current-voltage curves, potentiodynamic measurements have come into use: the desired voltage is changed either in small increments with a stepping circuit or continuously with time with a function generator. For a sufficiently slow potential scan rate the steady-state current voltage curve is essentially made (quasi-potentiostatic measurement). For higher scan rates, the characteristics of the curves may be changed significantly. During a galvanostatic polarisation curve, the electrode potential is measured as a function of the current density.
2.4.2 2.4.2.1
Experimental conditions Specimen Geometry

carbon steel (C 0.24%, P 0.055%, S 0.055%, N 0.013); galvanised steel; zinc (Zn 99%,Cu 0.0005, Al 0.001, Pb 0.0012; Fe 0.001); copper (Cu 99.90, Pb 0.005, Bi 0.001).
Four different metals were tested (working electrodes):
Considering the fact that the Luggin capillary positioned in front of the sample could alter the electric field, the geometry of the samples was slightly different from the one of the previous tests, as shown in Figure 2.7, with the purpose of eliminating the ohmic drop contribution. For copper and carbon steel, the working electrodes were 4040 mm squared plates with a 5 mm diameter
62
Experimental
hole in the middle (Figure 2.9a,b); the plate was sandblasted and an insulated copper cable was connected to the samples by riveting (Figure 2.9c). The connections, the backside face and the borders of the frontside face were covered with an epoxy resin-based coating; the tested net surface area was 340 mm2 or 700 mm2 (Figure 2.9d) depending on experimental conditions. The SCE reference electrode (RE) was fit in a hole on the top of the plastic box fixed on the backside of the sample (Figure 2.7). It has been verified, by comparison with measurements carried out by means of a Luggin capillary, that such sample geometry could efficiently eliminate the ohmic drop contribution.
SCE RE
Luggin capillary Exposed metal surface
Plastic box
Hole Coating
a)
b)
Figure 2.7 a) Schematic representation of the probe b) picture of a probe with Luggin capillary and SCE RE
a)
b)
c)
Figure 2.8 Picture of the 340 mm2 samples: a) carbon steel, b) copper and c) zinc
63
Experimental
a)
b)
c)
d)
Figure 2.9 Preparation of a 700 mm2 carbon steel sample: a,b) before sandblasting and coating, c) electrical connection to the insulated copper cable by rivet, d) painted with epoxy resin-based coating
Tests were performed in de-aerated conditions at 20C. Testing solutions for carbon steel samples: 4 g/L Na2SO4. This electrolyte was chosen because sulphate ions may be present in soil in large quantities, and because the corrosiveness of soil is often related to its sulphate content;
1200 ppm SO 2 4 (1.77 g/L Na2SO4) + 200 ppm Cl (0.41 g/L CaCl22H2O). This solution
will be named simulated soil solution; chlorides are often present in soils and can have a strong influence on corrosion rate. 35 g/L of NaCl solution, simulating seawater chlorinity; 1 M FeSO4 solution in order to start polarisation curves from the equilibrium potential, because carbon steel is in equilibrium with iron ions and the cathodic process is the inverse of the anodic one. Testing solution for galvanised steel was a 35 g/L of NaCl solution, simulating seawater chlorinity.
64
Experimental
1 M ZnSO4 and 1 M CuSO4 solution were used for zinc and copper to start the polarisation curves from the equilibrium potential as for previous tests on carbon steel
Cell and Electrodes

Tests were performed in a cylindrical cell 150 mm in diameter and 140 mm in height. The samples (working electrode W) were connected to the circuit as represented in Figure 2.5. As counter electrodes for the DC and AC current two MMO-Ti wire net were used, named CEDC, and CEAC respectively. The reference electrode was a calomel electrode SCE.
2.4.3
The experimental procedure for galvanostatic polarisation tests changed slightly depending on the metal/solution couple considered. The general procedure was: 1. rest potential measurement; 2. AC application at a fixed value (0, 30, 100, 300, 500 or 1000 A/m2); 3. equilibration time (the number of hours rest are reported in Tab. 2.1); 4. application of DC cathodic polarisation from DCmin to DCmax A/m2 (galvanostatic steps, each t minutes long see Tab. 2.1). Measurement of working electrode potential; 5. one hour rest (DC off but AC on, at the same value as the anodic polarisation); only for the tests on carbon steel in simulated soil solution the tests were performed both with one and 12 hours rest; 6. application of DC cathodic polarisation from DCmin to DCmax A/m2 (galvanostatic steps, each t minutes long). Measurement of working electrode potential. For the test in 1 M solution the points 4 and 6 were inverted because the anodic polarisation perturbed less the system than the cathodic one. DC polarisation (point 4) started a certain time after the working electrode immersion in the solution and the AC application, in order to allow the stabilisation of the rest potential. The time necessary to the working electrode to stabilise depended considerably changing the metal/solution couple. The time necessary to reach steady state conditions was evaluated for each metal/solution couple. For example during the test on carbon steel in 1 M FeSO4 solution the potential reached a steady value after few minute, instead for the test on carbon steel in simulated soil solution the potential didnt reached a steady value even after 12 hours. The AC current densities ranged from 30 to 1000 A/m2, whereas the range of DC density supplied varied depending on the metal/solution couple. Before each set of galvanostatic polarisation curves a set of preliminary curves without AC was performed in order to evaluate the 65
Experimental
range of DC densities of interest and the time interval (t) between the different step of galvanostatic polarisation. In fact also the time necessary to reach a steady state value of the potential after the galvanostatic polarisation varied considerably. Rest time, time interval t, DCmin and DCmax are reported inTab. 2.1.
Tab. 2.1 - Values of the time rest k, time interval t, DCmin and DCmax
Solution composition
rest time after the AC application (hours) 12 12 12 12 50 1
t, time interval between two following galvanostatic polarisation steps (minutes) GALVANISED STEEL 10 CARBON STEEL 10 10 10 10 5 ZINC 5 COPPER 5
DCmin (A/m )
2
DCmax (A/m2)
35 g/L NaCl 35 g/L of NaCl 4 g/L Na2SO4 Simulated soil solution 1 M FeSO4 1 M ZnSO4 1 M CuSO4
0.001 0.001 0.001 0.001 0.001 1 0.03 0.03
20 20 100 1 1 100 10 10
1 1
66
Experimental
2.5 WEIGHT LOSS TESTS

Effects of AC on the corrosion rate and corrosion morphology of specimens were studied as functions of exposure time and AC values by means of weight loss tests. The average corrosion rate (vcorr, m/y) is obtained as follows[61]:
v corr =
where: t = time of exposure in hours, A = area in cm2, W = weight loss in grams, = density in g/cm3.
8.76 10 7 W At
Eq. 2.5
The Eq. 2.5 gives an average penetration rate. Corrosion rates evaluated from weight losses tests can be misleading when deterioration is highly localised, as in pitting or crevice corrosion. In order to guarantee an accurate determination of the weight loss of the metal or alloy that occurred during exposure to the corrosive environment it is of paramount importance to remove corrosion products without significant removal of base metal. An ideal procedure should remove only corrosion products and not result in removal of any base metal, but in practice it is almost impossible to be obtained. Normally replicate cleaning procedures are applied to specimens which will often, even in the absence of corrosion products, result in continuing weight losses. This is because a corroded surface is often more susceptible than a freshly machined or polished surface to corrosion by the cleaning procedure. In such cases, the following method of determining the weight loss due to the cleaning procedure is preferred: rinsing carefully the sample; weighing the clean, dry specimens; repeating the chemical cleaning procedure on specimens several times; determination of the weight loss each cleaning by weighing the specimen. The weight loss should be graphed as a function of the number of equal cleaning cycles as shown in Figure 2.10. Two lines will be obtained: AB and BC. The latter will correspond to corrosion of the metal after removal of corrosion products. The weight loss due to corrosion will correspond approximately to point B[61].
67
Experimental
To minimize uncertainty associated with corrosion of the metal by the cleaning procedure, the chosen method should provide the lowest slope (near to horizontal) of line BC.
Mass Loss
A Number of Cleaning Cycles

Figure 2.10 - Weight loss of corroded specimens resulting from repetitive cleaning cycles
2.5.1
Weight Loss Determination
The procedure followed for the immersion tests was: sample degrease in acetone; sample sandblasting; electrical connection between specimen and an insulated copper cable by welding; insulation of the back face, the borders and the electrical connection with epoxy resinbased coating; soft sandblasting of the exposed surface; weight of the clean and dry specimen; start of the immersion test; application of AC current (0 900 A/m2) drawing of the samples after a proper time of exposure (Tab. 2.2); rinse and drying of the samples; repeated ultrasonic cleaning (10 minutes long) in inhibited HCl solution (5% HCl + 5 g/L hexamethylene tetramine). The samples were dried and weighed after each ultrasonic cleaning cycle following the ASTM G1-03. At least three samples were exposed to the same AC conditions.
68
Experimental
2.5.2
Test in Simulated Seawater Chlorinity: 35 g/L NaCl
Tests were performed on carbon steel specimens were 50 100 1 mm; 4 samples were tested for each AC current density condition. One face was painted so that the tested net surface area was 5000 mm2. The applied AC densities were: 0, 100 and 300 A/m2. The samples were weighed before starting the test and after 42 days in the testing conditions. The test cell was 150 mm in diameter and 140 mm in height. Tests were carried out in a 35 NaCl g/L solution maintained at 20C ( 1C). These conditions were chosen to avoid localised corrosion phenomena; indeed in literature[24,43,9] it has been reported that the enhanced corrosion due to the influence of AC voltages tends to be of a localised nature.
2.5.3
Test in Simulated Soil Solution
Weight loss tests were performed in aerated and de-aerated (continuously purged with nitrogen)
simulated soil solution: 1200 ppm SO 2 4 (1.77 g/L Na2SO4) + 200 ppm Cl (0.41 g/L CaCl22H2O).
The cells were 3 litres graduated beakers. The beakers were placed in a basin containing water that was maintained at 20C ( 1C). A set of weight loss tests was performed in aerated solution without thermostating
Specimens
10 20 2 mm and 20 20 2 mm carbon steel plates specimens were first degreased in acetone, then sandblasted; an insulated copper cable was welded on the back face. The borders and the back face were painted with an epoxy resin-based coating (Figure 2.11). The exposed net surface (20 and 40 mm2) was then softly sandblasted before the weight loss into the solution.
Figure 2.11 Picture of a 20 mm2 carbon steel sample for weight loss tests in simulated soil solution
Since corrosion rates are not necessarily constant with time of exposure, the weight loss test were performed at different exposure times. Experimental conditions, AC applied and exposure times for the weight loss tests are reported in Tab. 2.2.
69
Experimental
An alternate voltage (AV) was applied between the specimens and a MMO-Ti counter electrode. The AC current flowing through each sample was measured by means of a shunt.
Luggin
CEAC
CEAC
Figure 2.12 Schematic representation of the cell and of the samples arrangement
Tab. 2.2 Experimental conditions, AC applied and exposure times for the weight loss tests
Experimental conditions
iAC (A/m2) 0 10 18 24 42 71 94 340 460 890 0 100 300 500 0 31 100 290 500 780
days of exposure 30, 70, 134 30, 85, 150 30, 85, 150 30, 85, 150 30, 85, 150 30, 85, 150 30, 85, 150 30, 85, 150 30, 85, 150 30, 85, 150 30 30 30 30 85 150 30 85 150 30
Aerated simulated soil solution without thermostating
Aerated simulated soil solution thermostated at 20 C simulated soil solution, continuously purged with nitrogen and thermostated at 20 C
70
Experimental
2.6 CHARACTERISATION OF THE CORROSION MORPHOLOGY OF THE AC CORROSION

All tested metallic samples were examined by visual inspection in order to investigate the morphology of AC corrosion. After weight loss test a stereoscope Wild M8 was also used. Four carbon steel samples were prepared to be analysed by SEM-EDS. A 10 mm diameter carbon steel rebar (Fe b44k) was cut into pieces 20 mm long. The back transverse face was connected by a rivet with an insulated copper cable (Figure 2.13a). The electrical connection and the lateral surface were insulated with an epoxy resin (Figure 2.13b,c). The front transverse face was polished to 1 m diamond paste (Figure 2.13c).
a)
b)
c)
Figure 2.13 Preparation of the sample for the AC corrosion morphology determination
The samples were immersed in a simulated soil solution, 1200 ppm SO 2 4 (1.77 g/L Na2SO4) +
200 ppm Cl- (0.41 g/L CaCl22H2O) composition. The solution was maintained at 20C ( 1C) in 3 litres graduated beakers used as cells.. The following interfering conditions were tested: neither AC nor DC interference (control specimens); 100 A/m2 AC; 300 A/m2 AC; 0.3 A/m2 direct anodic interference, corresponding to about 300 m/year, that is the mean corrosion rate obtained during the to 100 A/m2 AC weight loss test. After 15 days test, the interfering current was switched off and the samples were removed from the solution, dried out with pure air and analysed before and after pickling in order to gather information on corrosion products and morphology.
71
Experimental
2.7 EFFECT OF AC ON PASSIVE METALS

Considering that a highly localised and rapid degradation would result in drastic losses of service life of structures that could fail in a relatively unexpected and unpredictable way, it is of paramount importance to get a better insight on the behaviour of passive metals in the presence of AC. It has been reported that an AV or AC signal reduces the ability of metals to passivate and similarly to chlorides produce local breakdown of passive film [24]. Immersion and potentiodymanic tests on carbon steel in alkaline synthetic pore solution, simulating the behaviour of rebars in concrete, were therefore performed.
2.7.1
Samples geometry
A first series of tests was performed on samples having the same geometry used for galvanic coupling tests (Figure 2.3, Par. 0, pag. 57). The carbon steel specimens were 30 30 1 mm in size and one side was painted (exposed surface area 900 mm2). Since it was noticed that an accidental contact of the Luggin capillary with the sample surface could induce the initiation of pitting corrosion, a second set of experiments was performed using samples (Figure 2.14) with the geometry described on the paragraph 2.4.2.1, pag 62.
Figure 2.14 Pictures of a 340 mm2 carbon steel sample
2.7.2
Solution composition
In order to simulate corrosion condition of rebar embedded in chloride contaminated concrete, the tests were performed in a alkaline synthetic pore solution obtained from a saturated calcium hydroxide solution with NaOH 0.01 mol/L (pH = 12.6); the solution was initially chlorides free.
72
Experimental
2.7.3
Cell and Electrodes
The reference electrode was a calomel electrode SCE.
Potentiodynamic tests
The solution was maintained at 20C ( 1C) in a 150 mm in diameter and 140 mm in height cell
Immersion Tests
The cells were 3 litres graduated beakers covered with a cap in order to avoid evaporation. The solution was not thermostated.
2.7.4
Potentiodynamic Tests Procedure
Polarisation Curve
Passivity is a state of low corrosion rate brought about under a high anodic overpotential by the presence of an interfacial solid film, usually an oxide. Passive metals are thermodynamically unstable: they possess a kinetic stability, which is engendered by a solid interfacial film, and without which corrosion would occur. The oxide film stifles the rate of further oxidation by forming a barrier between the metal surface and its environment. The typical passivating oxide film on many metals is only some 1-10 nm in thickness. Passivity always implies an ultimate steady state corrosion rate that is determined as the passive current density, ip, through polarisation experiments[62]. Localised corrosion can propagate when passivity is disrupted and regeneration of the passivating oxide film cannot take place.
E D E
Eb
C A ip
ic
Logi
Figure 2.15 - Schematic anodic polarisation curve for a metal.
Passivity is represented in the anodic curve by the passive interval: at low anodic potential (region AB) metal is active. Passivation commences at B and is complete at C; region BC
73
Experimental
comprises the active/passive transition. In the passive region (CD) the oxidation rate, passivity current density ip, is low and is nearly independent of potential. Passivity normally exists within a well defined potential range, below which the metal may activate and corrode, and above which it may or transpassivate and corrode or give localised corrosion as pitting or crevice. The potential range is characteristic of the metal/environment system, and critically, of the available cathodic reaction. In solutions containing a sufficient concentration of aggressive ions, such as chloride, premature failure of passive film may occur at potential E, named breakdown potential (Eb), and pitting corrosion starts. Failure of passivity is localised. In the absence of aggressive ions, the passivating oxide film may itself begin to be oxidised at potential D to produce soluble ions, and passivity again fails, this time by oxidative dissolution.
Potentiodynamic tests were performed in order to investigate the effect of AC on the passivity current density and on the breakdown potential. AC and DC currents were supplied through the circuit previously described (Par. 2.1, pag. 54) The potentiodynamic tests were performed as follows: immersion of the samples into the solution; 1 week of equilibration in order to obtain a good passivation of the sample; application of the AC; 24 hours rest in order to reach steady state conditions; in case of potentiodynamic tests in the presence of chlorides, the chlorides were added to the solution 10 minutes before starting the polarisation; start of the potentiodynamic scan: 50 mV potentiostatic steps, each 10 minutes long, starting from the corrosion potential. In the following table the interference conditions and the tested chloride content are reported.
Tab. 2.3 - Interference conditions and chloride content
AC (A/m2) 100 1000
Chlorides (mol/L) 0.03 0.03 -
74
Experimental
2.7.5
Immersion Tests Procedure
Preliminary tests
Carbon steel samples were left one week in a chlorides free solution to passivate. AC 0, 30, 100 and 500 A/m2 was applied at the 5th day. A first trial started by adding 5 mmol/L daily which gave almost instantaneous localised corrosion at AC 100 and 500 A/m2 current density. Accordingly, tests were carried out adding daily 1 mmol/L of chlorides. Localised corrosion initiation was detected by a sudden drop of potential below 0.3 V SCE and confirmed by visual inspection.
Second set of tests

The procedure was as follows: immersion of samples into the solution; after five days, application of AC: 0, 5, 10, 20, 30, 40, 50, 100, 300, 500, 800 A/m2; 48 hours rest in order to reach steady state conditions; 1 mmol/L daily addition of chlorides. At least two samples were tested for each AC density. One sample wes left for one week into the solution after the localised corrosion initiation in order to study the effect of AC on the propagation of corrosion. The chlorides addition was interrupted after corrosion initiation.
2.8 CATHODIC PROTECTION MONITORING

The scope of cathodic protection (CP) monitoring is to verify the protection level of the structure by checking that the potential matches the protection criteria. The potential measurement is easy to carry out, but its interpretation may present some concerns in the presence of DC or AC stray currents. As previously said, the case of AC interference seems to be particularly critical: depolarisation time lower than 1 ms and corrosion attacks on samples with instantaneous off-potential below of 0.85 V CSE have been reported[33]. Commonly for continuous monitoring, a corrosion coupon is used with a reference electrode located close to the coupon. This device is also called true potential probe. In literature there is lack of agreement about the correct procedure to measure the true potential in the presence of AC[33,39,2138]. Accordingly laboratory tests on carbon steel in soil simulating conditions were carried out focusing on potential measurement in the presence of AC through standard potential measurement procedure and the use of a potential probe. 75
Experimental
2.8.1
First set of measurements
The probes used for the first set of measurements are shown in Figure 2.16. The working electrode was a carbon steel plate (4040 mm) with a 2 mm diameter hole in the middle; the backside face was covered with an epoxy resin-based coating; a plastic box was fixed backside to insulate the MMO activated Ti reference electrode (MMO-Ti RE) from the flowing current. This geometry has been proved to eliminate the ohmic drop contribution[63]. The sample was put in the cell and covered with 100 mm of wet sand. The potential was measured both with respect to the MMO-Ti RE and with respect to four CSE RE placed at different distances from the working electrode as represented in Figure 2.17. The effect of AC current on ohmic drop was studied on freely corroding, cathodically and
anodically conditions (0.5 A/m2), in simulated soil conditions (wet sand containing SO 2 4 and
Ca 2+ ions, pH = 7, T = 25C).
Plastic box filled with sand Exposed metal surface
MMO-Ti RE Coating
Figure 2.16 - Schematic representation of the probe
Galvanostat
G
5 cm 5 cm 10 cm
CSE4
Variac
CSE1
CSE2
10 cm
Sand Working electrode hole CEDC CEAC
4 cm
Figure 2.17 Scheme of the cell and of the electrical connection to the circuit electric circuit diagram with DC and AC separation
76
CSE3
Experimental
Tests on polarised samples were performed following this sequence: cathodic or anodic polarisation, 0.5 A/m2 (for at least 12 hour); application of AC current; different steps, 10 minutes each, up to the maximum AC current density compatible with the proper working conditions of the galvanostat. Potential measurements were carried out by means of a 187 true-rms Fluke multimeter.
2.8.2
Second set of measurements
For the second set of measurements, two potential probes (Figure 2.18) were positioned in the cell as represented in Figure 2.19 the two open faces looking to the counter electrodes to allow the interfering current to intercept the potential probes.
Steel Coupon Bare Surface
alkaline mortar
Steel Coupon Connection
Reference Electrode Connection Plastic Case Reference Electrode Painted Surface
Figure 2.18 - Scheme of the potential probe
AC interference
CSE RE
DC interference Cathodic Protection source
CP
Sand Plastic box

Figure 2.19 - Scheme of the cell and of the probes installation
The two potential probes were connected, and the interfering current was measured by means of a 10 shunt. The interfering DC and AC current were applied by means of two separated counter electrodes. CP was supplied by means of an insoluble anode positioned at cell bottom. 77
Experimental
The cell was filled with wet sand. In order to apply higher currents, also experiments in Na2SO4 4 g/L solution were performed. Commercial potential probes (Figure 2.18) were used to eliminate IR drop[63]. Tests were performed as follows: Potential probes with CP: application of cathodic protection (the potential range was 0.7 e 1.2 V vs MMO-Ti RE); potential measurements after 48 hours and onset of the DC interference; potential measurements after 24 hours and onset of the AC interference. AC was increased every 24 hours up to the maximum value compatible with the equipment. Potential probes without CP application of DC interference; steel potential measurements after 24 hours and onset of the AC interference. The AC was increased every 24 hours up to the maximum value compatible with the equipment. A list of experimental conditions is reported in Tab. 2.4. The range of DC and AC interference investigated is respectively 0.0016 0.79 A/m2 (DC) and 0.125 115 A/m2 (AC). For all the conditions the potentials were measured both with respect to the CSE and the internal MMO-Ti reference electrodes.
Tab. 2.4 - Interference conditions tested
non stationary DC interference + stationary AC interference Cathodically protected probes anodic DC interference + stationary AC interference cathodic DC interference + stationary AC interference stationary AC interference non stationary DC interference + stationary AC interference Probes without CP anodic DC interference + stationary AC interference cathodic DC interference + stationary AC interference stationary AC interference
ON/OFF tests of both the DC and AC interference were performed while the potential was monitored by high sampling rate (50 Hz) voltammeter recorder. The ON/OFF tests were performed as follows: measurement of the ON potential; DC or AC switch-OFF for 3 seconds; DC or AC switch-ON .
78
Experimental
The ON/OFF tests of the DC and AC were also performed serially as follow: measure of the ON potential (both DC and AC ON); DC switch-OFF; AC switch-OFF; AC switch -ON; DC switch -ON.
2.9 OSCILLOSCOPE MEASUREMENTS

Measurements of the AC and AV signal were made by a Tektronix TDS 200 oscilloscope. The oscilloscope has two modality: AC coupling that halts the DC component but let pass the dynamic component (AC). It is useful to observe the AC signal associated with the DC signal; DC coupling that allows the observation of both the AC and DC components. The AC and AV signal were measured by the oscilloscope for all the experimental procedure previously described: AV between working electrode and SCE reference electrode; AV between working electrode and counter electrode; AC flowing through the working electrode. The AC was measured by means of the resistances R1, R2 and R3 of the circuit described previously (Figure 2.1, Par. 2.1, pag. 54).
79
Experimental
80
RESULTS
In this chapter the results of the following tests are reported: 7. effects of AC on galvanic corrosion; 8. tests carried out by separated circuits: AC and DC signals overlapped on the same sample; 9. determination of the anodic and cathodic polarisation curves; 10. weight loss tests; 11. characterisation of corrosion morphology in the presence of AC; 12. effects of AC on passive metals; 13. cathodic protection monitoring; 14. measurements by oscilloscope.
3.1 TESTS ON GALVANIC CORROSION

The aim of these tests was to study the effects of AC on anodic and cathodic processes by means of a bimetallic coupling of stainless steel and carbon steel which allowed the separation of the anodic and the cathodic processes. The corrosion condition before and after the galvanic coupling of stainless steel and carbon steel are reported in Figure 3.1. The curve a represents the anodic characteristic of stainless steel and the point A is the corrosion potential before the coupling. The curve b represents the anodic characteristic of carbon steel and the point B the corrosion potential before the coupling. The curves c and d represent the cathodic process on the two metals before and after the galvanic coupling respectively, and the point C is the corrosion potential after the galvanic coupling.
Results
a Anodic characteristic of stainless steel
A d c B C
Cathodic reaction of O2 reduction on the two metals before coupling Cathodic reaction of O2 reduction after coupling b Anodic oxidation of carbon steel Logi
Figure 3.1 - Corrosion condition before and after the galvanic coupling between stainless steel and carbon steel
Figure 3.2 and Figure 3.3 illustrate some examples of results obtained in the galvanic coupling tests: the potential of AISI 304 and carbon steel are referred to the primary y-axis while the value of the applied AC density to the secondary y-axis. Complete experimental data (steel potential E and anodic current IA) are reported in Tab. 3.1.
-650 150
E vs SCE (mV)
-700
100
Galvanic coupling
-750
E AISI 304 E Carbon Steel i AC
50
-800 0 50 100 150
0 200
Time (hour)
Figure 3.2 - Galvanic coupling tests in 0,50 g/L Na2SO4, without O2 scrubbing
The application of AC current lowers the carbon steel DC potential, and this effect is more pronounced in chloride solutions. The effect is similar both in aerated and de-aerated conditions. During this first set of experiments the circuit previously described, which allows the independent application and measurement of the AC and DC components (Par. 2.1, pag. 54), was not used. Therefore the measurements of galvanic coupling current were affected by the presence of an AC current, that was four orders of magnitude higher than the DC current. The multimeter used was not able to properly filter the AC component, giving quite instable DC measurements. The DC 82
i AC (A/m )
Results
current values obtained are hence to considered as a qualitative indication rather than a quantitative measure of the corrosion rate in the presence of AC. Nevertheless, the trend is clear: the higher the AC density, the higher the measured macro-couple current (Tab. 3.1). Since the surfaces of carbon and stainless steel specimens are equal, the rate of the anodic process (IA) is double with respect to the measured macro-couple current (IMC).
-650
150
E vs SCE (mV)
-700
100
-750
Galvanic coupling E AISI 304 E carbon Steel i AC
50
-800 0 50 100 150
0 200
Time (hour)
Figure 3.3 - Galvanic coupling tests in 35 g/L NaCl, O2 scrubbing
Tab. 3.1- Carbon steel potential (E - mV vs SCE) and anodic current density (IA - A/m2) in galvanic coupling tests
Without O2 0.25 g/L Na2SO4 Free corrosion potential (mV) After galvanic coupling (No AC) 45 A/m2 Applied AC current density 90 A/m2 145 A/m2 E steel IA E steel IA E steel IA E steel IA -685 -720 -----754 -----765 ------------0.50 g/L Na2SO4 -690 -735 0.08 -757 0.23 -774 0.38 -767 0.56
With O2 35 g/L NaCl -722 -711 0.07 -819 0.12 -810 0.24 -794 2.11 35 g/L NaCl -698 -685 0.11 -782 0.44 -773 0.70 -763 2.22
i AC (A/m )
83
Results
3.2 TESTS WITH SEPARATED CIRCUITS: AC AND DC OVERLAPPED ON THE SAME SAMPLE
In separated circuit tests (pag. 54), the DC was supplied by a 12 V 25 Ah battery and the current density was adjusted by means of a variable resistor. The battery was preferred because it is a pure DC source. Unfortunately the variable resistor didnt allowed to keep constant the DC component for all the AC applied. For that reason in the graphics both the DC and the AC current density are reported. In order to overcome such inconvenient a galvanostat was used for the rest of the experiments.
3.2.1
Cathodic Polarisation (CP) Tests
Some examples of results obtained are reported in Figure 3.4 and 3.5: working potential (primary y-axis), cathodic DC and AC densities (secondary y-axis). Complete experimental data are reported in (Tab. 3.2). In the case of cathodic polarisation, the potential trend is dependant on DC current density: at 0.1 A/m2, the DC potential lowered as AC was applied (Figure 3.4). This effect increased as AC densities increased. A similar trend was observed in chloride and sulphate solutions, with aerated and de-aerated conditions; for DC current density between 1 and 10 A/m2, a different behaviour was observed. After the application of AC, the DC potential increased (Figure 3.5) as AC current density increased. Also the cathodic current density, measured on the DC circuit, increased with the AC current density (Tab. 3.2).
-400 E carbon steel i DC i AC 10000
-600 E vs SCE (mV)
1000
-800
CP 10
-1000
-1200 0 2 4 6 Time (h) 8 10
0.1
Figure 3.4 Cathodic Polarisation (CP = 0.1 A/m2) tests in 4 g/L Na2SO4 solution without oxygen scrubbing
84
i (A/m2)
100
Results
-400 E carbon steel i DC i AC
10000
-600 E vs SCE (mV)
1000
CP
-800
10 -1000
-1200 0 2 4 6 Time (h) 8 10
0.1
Figure 3.5 Cathodic Polarisation (CP = 1 A/m2) tests in 4 g/L Na2SO4 solution without oxygen scrubbing
Tab. 3.2 - Carbon steel potential (E mV vs. SCE) and DC current density (iDC - A/m2) in cathodic polarisation (CP) tests, at different AC current densities
4 g/L Na2SO4 CP current density* Applied AC (A/m2) 0 0.1 A/m2 30 100 1000 0 1 A/m2 30 100 1000 0 10 A/m2 30 100 1000 With O2 E -657 -800 -868 -884 -1068 -1031 -1025 -986 -1200 -1175 -1142 -1048 iDC 0.10 0.16 0.33 2.45 1.00 1.32 1.49 9.38 10.00 10.52 11.15 14.00 Without O2 E -751 -725 -935 -915 -1100 -1070 -1042 -970 -1148 -1151 -1126 -934 iDC 0.10 0.14 0.28 2.60 1.12 1.35 1.62 9.50 10.15 10.60 11.30 15.30
35 g/L NaCl With O2 E -601 -668 -800 -818 -1217 -1168 -1071 -928 -1270 -1233 -1195 -934 iDC 0.10 0.10 0.10 0.27 1.00 1.74 1.24 3.20 10.00 11.08 12.70 15.25 Without O2 E -726 -830 -848 -849 -1135 -1113 -1086 -872 -1218 -1224 -1185 -960 iDC 0.10 0.10 0.10 0.24 1.00 2.19 2.33 4.32 10.00 10.16 10.44 12.92
* The reported values correspond to the applied DC cathodic polarisation current density before AC imposition.
i (A/m2)
100
85
Results
3.2.2
Anodic Polarisation (AP) Tests

and 3.7: working potential
Some examples of results obtained are reported in Figure 3.6 are reported in (Tab. 3.3).
-400
(primary y-axis), cathodic DC and AC densities (secondary y-axis). Complete experimental data
-600 E vs SCE (mV)
E carbon steel i DC i AC
10000
1000
-800 10 -1000
-1200 0 2 4 6 Time (h) 8 10
0.1
Figure 3.6 - Anodic Polarisation (AP = 1 A/m2) tests: 4 g/L Na2SO4 solution with oxygen scrubbing
-400
-600 E vs SCE (mV)
E carbon steel i AC i DC
10000
1000
AP
-800 10 -1000 i (A/m2) 100
-1200 0 2 4 6 Time (h) 8 10
0.1
Figure 3.7 - Anodic Polarisation (AP = 1 A/m2) tests: 35 g/L NaCl solution with oxygen scrubbing
In the anodic polarisation tests (AP = 110 A/m2), the specimen DC potential lowered as the AC current increased, in both aerated and de-aerated conditions (Tab. 3.3). The effect was more remarkable in chloride solutions. In sodium sulphate solution, anodic DC density was practically unaffected by the application of an AC density in the range of 30100 A/m2; some changes were observed at 1000 A/m2 AC 86
i (A/m2)
AP
100
Results (Figure 3.6). A different behaviour was obtained in chloride solutions when 1 A/m2 anodic current density was applied (Tab. 3.3). In this case the anodic current density increased when AC was imposed, also at the minimum current density value (30 A/m2).
Tab. 3.3 - Carbon steel potential (E vs SCE mV) and DC current density (i DC - A/m2) in anodic polarisation (AP) tests, at different ac current densities
4 g/L Na2SO4 CP current density* Applied AC (A/m2) 0 1 A/m2 30 100 1000 0 10 A/m2 30 100 1000 With O2 E -647 -693 -762 -763 -607 -640 -693 -749 i DC 1.00 1.00 1.00 3.12 10.00 10.70 11.56 15.11 Without O2 E -676 -707 -772 -769 -621 -654 -694 -739 i DC 1.00 1.09 1.11 3.50 10.00 11.00 11.57 13.69
35 g/L NaCl With O2 E -565 -693 -769 -772 -576 -650 -709 -759 i DC 1.00 1.61 2.04 2.43 10.00 10.70 11.12 12.00 Without O2 E -628 -704 -767 -784 -580 -612 -712 -762 i DC 1.00 2.23 2.56 2.94 10.00 10.55 11.40 12.08
* The reported values correspond to the applied DC anodic polarisation current density before AC imposition.
3.2.3
Free Corrosion Tests
Some examples of the results obtained are reported in Figure 3.8 and 3.9: working potential (primary y-axis), cathodic DC and AC densities (secondary y-axis). Complete experimental data are reported in (Tab. 3.4).
-400 E carbon steel i AC -600 E vs SCE (mV) 1000 10000
-800 10 -1000
-1200 0 2 4 6 Time (h) 8 10
0.1
Figure 3.8 Free Corrosion tests: 4 g/L Na2SO4 solution with oxygen scrubbing
i (A/m2)
100
87
Results
-400 E carbon steel i AC -600 E vs SCE (mV)
10000
1000
-800 10 -1000
-1200 0 2 4 6 Time (h) 8 10
0.1
Figure 3.9 Free Corrosion tests: 35 g/L NaCl solution with oxygen scrubbing
It can be observed that the DC potential lowered when an AC current was applied. The effect was more pronounced in aerated conditions and in chloride containing solutions (Tab. 3.4). It was noticed in all tests, that when AC current density was higher than 300 A/m2, DC potential changed its trend, starting to increase back.
Tab. 3.4 - Carbon steel potential (E mV vs. SCE) in free corroding tests, at different AC densities
4 g/L Na2SO4 Applied AC (A/m2) 0 10 17 30 36 56 100 360 560 1000 3600 With O2 E (mV) -647 -686 -693 -722 -753 -776 -801 -765 -834 -873 -757 Without O2 E (mV) -700 -714 -726 -749 -775 -810 -830 -789 -789 -853 -796 Applied AC (A/m2) 0 30 50 85 100 160 280 600 1000 1600 2800 6000
35 g/L NaCl With O2 E (mV) -667 -784 -810 -874 -826 -875 -871 -873 -772 -783 -818 -799 Without O2 E (mV) -706 -754 -820 -820 -810 -874 -880 -841 -719 -766 -756 -781
88
i (A/m2)
100
Results
3.3 ANODIC AND CATHODIC POLARISATION CURVES

The influence of AC on kinetic parameters as exchange current densities (i0,a, i0,c), Tafel slopes (a, c) and corrosion current density (icorr), was studied through polarisation curves.
3.3.1
Tafel Equation
For any given electrodic process under specified conditions, charge transfer at a finite rate will involve an activation overpotential , which provides the activation energy of the processes. Most electrode processes involve more than one stage; one of them is usually slower than the others and is thus rate determining. The activation energy is required, therefore, to maintain the rate of the rate-determining step, since the other steps may be regarded as being at equilibrium[62]. For a reaction under activation control, the activation overpotential, and hence the activation energy, varies exponentially with the rate of charge transfer per unit area of electrode surface, as defined by the Tafel equation (Figure 3.10):
= log i0 log i
Eq. 3.1
where the sign + stands for anodic processes while the for the cathodic ones[64,65,]; i is the current density; i0 the exchange current and the Tafel slope. Eeq is the equilibrium potential, Ecorr the corrosion potential and icorr the corrosion current density. i0 and vary with the nature of the electrode process and with the composition of the solution.
E
Eeq, eq, cat
E c o rr
an anodic cathodic cat
Eeq, eq, an
i0, a
ic o rr i0, c
icorr
Log i
Figure 3.10 Tafel plot for a corrosion process with both anodic and cathodic processes under activation control
89
Results
3.3.2
Carbon Steel
0.4 g/L Sodium Sulphate Solution

Figure 3.11 reports the experimental data of a polarisation curve of carbon steel in 4 g/L Na2SO4 solution in the absence of AC interference. The linear regressions (black lines) of the linear parts of the polarisation curve and the Tafel curve (grey line), calculated by using the obtained parameters (a, c and icorr) and the following formula, are also reported:
i = i corr exp a
-0.6 -0.7 E vs SCE (V) -0.8 -0.9 -1.0 -1.1 -1.2 0.001
exp c
Eq. 3.2
Experimental data in absence of AC Regression of the linear part of the polarisation curve Tafel curve calculated with the parameters obtained by regression
0.01
0.1
2
10
100
i DC (A/m )
Figure 3.11 - Polarisation curve of carbon steel in 4 g/L Na2SO4 solution in absence of AC interference
The experimental results of polarisation curves of carbon steel in a 4 g/L sodium sulphate solution in the presence of AC are reported in Figure 3.12; the regression curves obtained from the experimental data are also shown. In Figure 3.13 the corrosion current density and potential are shown. Values of Tafel slopes, corrosion current densities and corrosion potential obtained by regression of the experimental data are reported in Tab. 3.5. AC interference does not have significant effect on Tafel slopes which do not change significantly. It is evident that the corrosion current density increases with AC while the corrosion potential decreases.
90
Results
-0.7 -0.8 E vs SCE (V) -0.9 -1.0 -1.1 -1.2 -1.3 1 10 100 1000 i DC (mA/m )
Figure 3.12 Effect of AC on polarisation curves of carbon steel in 4 g/L Na2SO4 solution: experimental data and linear regression curves
2
Regression of the data at AC =

2
AC (A/m ): 0 30 100 300 1000 10000 100000
0 A/m 2 30 A/m 2 100 A/m 300 A/m 1000 A/m

2 2
200
Ecorr vs SCE (V)
-0.80
2 i corr (mA/m )
150 100 50 0 0 250 500

2 i AC (A/m )
-0.81
-0.82
-0.83
750
1000
250
500
2 i AC (A/m )
750
1000
Figure 3.13 Effect of AC on corrosion current and potential for carbon steel in 4 g/L sodium sulphate solution
Tab. 3.5 Carbon steel: kinetic parameters obtained from polarisation curves in 4 g/L Na2SO4 solution
AC (A/m2) 0 30 100 300 1000
a (V/dec) 0.063 0.055 0.064 0.065 0.066
c (V/dec) 0.123 0.120 0.124 0.129 0.131
icorr (mA/m2) 36 39 82 110 190
Ecorr (mV SCE) -805 -810 -814 -828 -824
91
Results
Simulated soil solution

As previously described (Paragraph 2.4.3, pag 65), tests in simulated soil solution, 1200 ppm
SO 2 4 (1.77 g/L Na2SO4) + 200 ppm Cl (0.41 g/L CaCl22H2O), were performed according to two
different timing procedures: 12 hours equilibration before starting the test, then 1 hour rest between cathodic and anodic polarisation;. This procedure was chosen in order to investigate the effect of AC at an intermediate step since after 12 hours the DC potential was not yet at the equilibrium (Figure 3.14); 50 hours equilibration before starting the test, then 12 hour rest between cathodic and anodic polarisation. This procedure allowed to study the effect of AC on corrosion kinetics once the equilibrium was reached, i.e steady-state conditions (Figure 3.15). The principal difference between the two sets of curves is the trend of the corrosion potential as a function of AC density. It can be noticed from the first set of curves that the corrosion potential first decreased toward less noble values (AC = 30 A/m2), then kept almost the same value (AC 100 A/m2) and for AC > 300 A/m2 started to increase into the active region (Figure 3.16 and Tab. 3.6).
-0.65 -0.70 -0.75 E vs SCE (V) -0.80 -0.85 -0.90 -0.95 -1.00 -1.05 0.001 AC (A/m2): 1000 500 300 100 30 0.01 i DC (A/m )
Figure 3.14 Effect of AC on polarisation curves of carbon steel in simulated soil solution: experimental data and regression curves (12 hours equilibration, 1 hour rest between cathodic and anodic polarisation)
2
0.1
92
Results
-0.65 -0.70 -0.75 E vs SCE (V) -0.80 -0.85 -0.90 -0.95 -1.00 -1.05 0.001
AC (A/m ): 0 100 300 500 1000
0.01 i DC (A/m )
2
0.1
Figure 3.15 Effect of AC on polarisation curves of carbon steel in simulated soil solution: experimental data and regression curves (50 hours equilibration, 12 hour rest between cathodic and anodic polarisation)
For the second set of tests the potential increases with the AC density (Figure 3.17 and Tab. 3.7). Most probably the potential variations have to be ascribed to changes on the concentration of the ions at the metal solution interface, thus leading to variation of the equilibrium potential. The formation of film of corrosion product may also have an effect on the exchange current and on the Tafel slopes. The trend of the Tafel slopes is quite articulated. The initial increase of the Tafel slopes may be related to the AC-induced formation of a layer of corrosion products; then increasing the AC density the film becomes progressively less adherent and less protective. The increase of the anodic Tafel slope for AC = 1000 A/m2 during the second set of curves is probably due to the thickness of the oxides/hydroxides layer formed on such conditions. The increased value of the corrosion current for the tests at 1000 A/m2 AC confirmed that such layer is not protective. The two sets of curves gave very close trend of the corrosion current as a function of the AC density (Figure 3.16 and Figure 3.17).
80 Ecorr vs SCE (mV) 60 40 20 0 0 250 500
2 i AC (A/m )
-710 -730 -750 -770 -790 -810 750 1000 0 250 500 i AC (A/m2) 750 1000
2 i corr (mA/m )
Figure 3.16 Effect of AC on corrosion current and potential for carbon steel in simulated soil solution (12 hours equilibration, 1 hour rest between cathodic and anodic polarisation)
93
Results
80 Ecorr vs SCE (mV) 60 40 20 0 0 250 500

2 i AC (A/m )
-710 -730 -750 -770 -790 -810 750 1000 0 250 500 i AC (A/m )
2
2 i corr (mA/m )
750
1000
Figure 3.17 Effect of AC on corrosion current and potential for carbon steel in simulated soil solution (50 hours equilibration, 12 hour rest between cathodic and anodic polarisation)
Tab. 3.6 Carbon steel: kinetic parameters obtained from polarisation curves in simulated soil solution (12 hours equilibration, 1 hour rest between cathodic and anodic polarisation)
AC (A/m2) 0 30 100 300 500 1000
a (V/dec) 0.050 0.062 0.069 0.051 0.054 0.043
c (V/dec) 0.143 0.155 0.160 0.147 0.141 0.158
icorr (mA/m2) 20 28 45 30 34 60
Ecorr (mV SCE) -790 -798 -798 -792 -789 -753
Tab. 3.7 Carbon steel: kinetic parameters obtained from polarisation curves in soil simulated solution (50 hours equilibration, 12 hour rest between cathodic and anodic polarisation)
AC (A/m2) 0 100 300 500 1000
a (V/dec) 0.052 0.070 0.069 0.023 0.074
c (V/dec) 0.153 0.159 0.128 0.157 0.185
icorr (mA/m2) 20 27 14 15 64
Ecorr (mV SCE) -791 -791 -782 -765 -719
94
Results
Simulated seawater solution: 35 g/L NaCl

The experimental results of polarisation curves of carbon steel in a 35 g/L sodium chloride solution are reported in Figure 3.18; the regression curves obtained from the experimental data are also shown. In Figure 3.19 the corrosion current density is plotted. Values of Tafel slopes, corrosion current densities and corrosion potential obtained by regression of the experimental data are summarised in Tab. 3.8. The effects of AC on carbon steel in seawater solution can be summarised as follows: DC corrosion current density raised with AC. There was a sudden increase at AC = 30 A/m2 (more than ten times), then icorr continued increasing with AC, tough more smoothly (Figure 3.19); corrosion potential generally decreased with AC; the cathodic Tafel slope kept almost constant for AC = 0, 30 and 100 A/m2, then decreased for AC = 300 A/m2 and maintained a similar value for AC = 500 and 100 A/m2; the value of anodic Tafel slope showed an oscillating behaviour: it first increased for AC = 30 A/m2), then decreased in the case of AC = 100, 300, 500 A/m2 and finally strongly increased for AC = 1000 A/m2.
-0.4 -0.5 -0.6 E vs SCE (V) -0.7 -0.8 -0.9 -1.0 -1.1 -1.2 -1.3 -1.4 1
AC (A/m2): 0 30 100 300 500 1000
Regression of the data at AC = 1000 A/m 30 A/m 100 A/m 300 A/m 500 A/m 100 1000 i DC (mA/m )
2 2
0 A/m2
2 2 2 2
10
10000
100000
Figure 3.18 Effect of AC on polarisation curves of carbon steel in 35 g/L NaCl solution: experimental data and regression curves
95
Results
1000
i corr (mA/m )
100
10
1 0 200 400 600

2
800
1000
i CA (A/m )
Figure 3.19 Effect of AC on corrosion current for carbon steel in 35 g/L NaCl solution
Tab. 3.8 Carbon steel: kinetic parameters obtained from polarisation curves in 35 g/L NaCl solution
AC (A/m2) 0 30 100 300 500 1000
a (V/dec) 0.066 0.085 0.050 0.050 0.045 0.164
c (V/dec) 0.167 0.177 0.169 0.132 0.132 0.137
icorr (mA/m2) 11 140 65 160 120 280
Ecorr (V SCE) -0.780 -0.812 -0.790 -0.818 -0.818 -0.843
3.3.3
Galvanised Steel
The main results of polarisation tests on galvanised steel in 35 g/L NaCL (Figures 3.20-3.21-3.22 and Tab. 3.9) can be summarised as follows: the corrosion current density increased as the AC density increased (Figure 3.21); Ecorr (Figure 3.21) lowered of about 100 mV in the presence of AC interference and kept almost constant for all the AC densities studied; the anodic Tafel slope doubled in the presence of AC interference and kept almost constant for all the AC densities considered (Figure 3.22); the cathodic Tafel slope decreased (30<AC<100 A/m2), then increased (AC > 100 A/m2) and then decreased again (AC > 500 A/m2) (Figure 3.22).
96
Results
-1.0 -1.1 E vs SCE (V) -1.2 -1.3 -1.4 -1.5 -1.6 0.001 0 30 100 300 500 1000
AC (A/m ):
0.01
0.1
2
10
100
i DC (A/m )
Figure 3.20 Effect of AC on polarisation curves of galvanised steel in 35 g/L NaCl solution: experimental data and regression curves
80 Ecorr (V vs SCE) 0 250 500 i AC (A/m )

2
-1.05 -1.10 -1.15 -1.20 -1.25 750 1000 0 250 500 i AC (A/m )
2
2 i corr (mA/m )
60 40 20 0
750
1000
Figure 3.21 Effect of AC on corrosion current and potential for galvanised steel in 35 g/L NaCl solution
60
160 cathodic
(mV/dec)
20 anodic 0 0 250 500 i AC (A/m )

2
(mV/dec) 750 1000
40
140
120
100 0 250 500 i AC (A/m )

2
750
1000
Figure 3.22 Effect of AC on anodic and cathodic Tafel slopes for galvanised steel in 35 g/L NaCl solution
97
Results
Tab. 3.9 Galvanised steel: kinetic parameters obtained from polarisation curves in 35 g/L NaCl solution
AC (A/m2) 0 30 100 300 500 1000
a (V/dec) 16 46 45 49 49 51
c (V/dec) 152 124 134 132 129 118
icorr (mA/m2) 16 26 30 60 70 62
Ecorr (V SCE) -1.082 -1.200 -1.200 -1.212 -1.213 -1.214
3.3.4
Carbon Steel, Zinc and Copper in 1 M Solution of their Ions
Figures 3.23-3.24-3.25 show galvanostatic polarisation curves for copper, carbon steel and zinc, obtained at different AC current densities (01000 A/m2) in 1 M solution of their ions. It is evident that AC causes a net change on the polarisation curves for all the three tested materials: variation of the equilibrium potential (less noble potentials) and flatter curves with lower overpotential were recorded as AC density increased.
0.08
2
AC (A/m ): 0 30 100 300
0.07 E vs SCE (V)
0.06
500 1000
0.05 Cu - CuSO4 1M 0.04 0.01 0.1 i DC (A/m )

Figure 3.23 Effect of AC (01000 A/m2) on polarisation curves of copper in CuSO4 1 M
2
10
98
Results
-0.5
AC (A/m ): 0 30 100 300
-0.6 E vs SCE (V)
-0.7
500 1000
-0.8 Fe - FeSO4 1M -0.9 1 10 i DC (A/m )

Figure 3.24 Effect of AC (01000 A/m2) on polarisation curves of carbon steel (Fe) in FeSO4 1 M
2
100
-1.00 -1.01 -1.02 E vs SCE (V) -1.03 -1.04 -1.05 -1.06 -1.07 0.01 Zn - ZnSO4 1M
AC (A/m ): 0 30 100 300 500 1000
0.1 i DC (A/m )
2
10
Figure 3.25 Effect of AC (01000 A/m2) on polarisation curves of Zinc in ZnSO4 1 M
For cathodic polarisation of copper without AC, the potential started to be unstable and oscillated of more than 100 mV for DC densities higher than 1 A/m2. The instability and the oscillating behaviour persisted even after 24 hours at the same DC cathodic polarisation level (1.5 A/m2). Then, polarisation curves were plotted by taking the potential reading after five minutes of polarisation and then proceeding with the subsequent current step. Such instability wasnt revealed during the polarisation in the presence of AC interference. Even though such an irregular behaviour on the cathodic curve was still present for AC = 30 and 100 A/m2, it disappeared for AC > 300 A/m2. In fact, during the polarisation tests in the presence of AC, the potential stabilised a few minutes after the DC galvanostatic step (Figure 3.23).
99
Results
The equilibrium potential variation for the three metals are reported in Figure 3.26. Generally, the equilibrium potential shifted to less noble potentials as AC increased, with the only exception being the test on carbon steel at 30 A/m2 that showed a little potential shift towards a more noble value. Copper equilibrium potential showed little variation (smaller than 3 mV) with the AC current. The highest variation was obtained with AC = 30 A/m2 (Tab. 3.10 and Figure 3.23). Carbon steel equilibrium potential ( Tab. 3.11) shifted significantly, up to 70 mV with respect to those measured in the absence of AC. Potential variations of zinc were less significant than those of carbon steel but higher than those of copper: for AC > 200 A/m2, potential stabilises at about 20 mV with respect to the test at AC = 0 A/m2 (Figure 3.26).
10 0 -10 Eeq (mV) -20 -30 -40 -50 -60 -70 0 250 500 iAC (A/m )
Figure 3.26 Effect of AC on equilibrium potential of Cu, carbon steel and Zn in 1 M solution of their ions
2
Zinc Carbon steel Copper
750
1000
At DC current densities higher than 10 A/m2, concentration overpotential contribution was high and data were therefore not used for regression analysis. Only in the case of copper it was possible to obtain by regression both the anodic and cathodic curves for all tested AC current densities. Anodic and cathodic Tafel slopes (a and c) and exchange current density (i0) are reported in Tab. 3.10 and Tab. 3.11 and in Figures 3.27-3.28-3.29. Both anodic and cathodic Tafel slopes decreased as AC density increased whereas the exchange current increased. On the cathodic polarisation of carbon steel, at AC = 0, 30 and 100 A/m2 (Figure 3.24), the potential decreased suddenly for DC higher than 1.5 A/m2. This decrease became more gradual when AC was increased and disappeared for AC 300 A/m2. It was, therefore, not possible to estimate the cathodic Tafel slope for AC = 30 and 100 A/m2 and in the absence of AC.
100
Results
Tab. 3.11 reports the anodic and cathodic Tafel slopes (a and c) and the exchange current density (i0) obtained by regression of the experimental data. As for copper, both anodic and cathodic Tafel slopes decreased whereas the exchange current density (i0) increased as AC density increased (Figures 3.28 and 3.29).
Tab. 3.10 - Copper in CuSO4 1 M: equilibrium potential, exchange current density (i0), anodic and cathodic Tafel slopes (a and c)
Applied AC (A/m2) 0 30 100 300 500 1000
Eeq vs SCE (mV) 73 70.4 72.8 72.5 72 72
i0 (A/m2) 0.338 0.446 0.618 0.508 0.712 0.941
a (V/dec.) 0.0042 0.0049 0.0022 0.0012 0.0018 0.0009
c (V/dec.) 0.0282 0.0132 0.0056 0.0029 0.0028 0.0016
Tab. 3.11 - Carbon steel (Fe) in FeSO4 1 M: equilibrium potential, exchange current density (i0), anodic and cathodic Tafel slopes (a and c)
Applied AC (A/m2) 0 30 100 300 500 1000
Eeq vs SCE (mV) -681 -677 -696 -723 -743 -750
i0 (A/m2) 0.774 1.100 1.090 1.887 1.363 1.594
a (V/dec.) 0.022 0.015 0.016 0.014 0.015 0.012
c (V/dec.)
0.058 0.017 0.011
6 5 (mV/dec) 4 3 2 1 0 0 250 500

2 i AC (A/m )
35 anodic (mV/dec) 30 25 20 15 10 5 0 750 1000 0 250 500

2 i AC (A/m )
cathodic
750
1000
Figure 3.27 Effect of AC on anodic and cathodic Tafel slopes for Cu in CuSO4 1 M
101
Results
1.0 0.8
2 i 0 (A/m )
2.0 1.8
2 i 0 (A/m )
0.6 0.4 0.2 0.0 0 250 500

2 i AC (A/m )
1.5 1.3 1.0 0.8 0.5 Fe - FeSO4 1M 0 250 500

2 i AC (A/m )
Cu - CuSO4 1M 750 1000
750
1000
Figure 3.28 Effect of AC on exchange current density for copper and carbon steel in 1 M solution of their ions
24 22 anodic
70 60 cathodic
(mV/dec)
18 16 14 12 10 0 250 500 i AC (A/m )

2
(mV/dec)
750 1000
20
50 40 30 20 10 0 0 250 500 i AC (A/m )

2
750
1000
Figure 3.29 Effect of AC on anodic and cathodic Tafel slopes for carbon steel in FeSO4 1 M
For zinc neither a linear nor exponential part of polarisation curves was recognised (Figure 3.25), therefore both Tafel slopes and exchange current density could not be evaluated. However it is possible to make some qualitative comment. To help the analysis of the AC influence on the trend of zinc polarisation curves, in Figure 3.30 overpotential as a function of DC current density are reported; as for copper and carbon steel, there is an evident reduction of overpotentials as AC current density increases. The overpotential as a function of DC current density were plotted also for copper and carbon steel (Figure 3.31 and Figure 3.32). It can be easily noticed what previously observed: the strong effect of AC on copper cathodic and anodic overpotentials. For carbon steel the overpotential reduction is higher for the cathodic process than for the anodic one.
102
Results
30 20 Overpotential (mV) 10 0 -10 -20 -30 0.01 Zn - ZnSO4 1M
AC (A/m ): 0 30 100 300 500 1000
0.1
i DC (A/m )
2
10
Figure 3.30 Effect of AC on anodic and cathodic overpotentials for zinc in ZnSO4 1 M
10 5 Overpotential (mV) 0 -5 -10 -15 -20 -25 -30 -35 -40 0.01 Cu - CuSO4 1M
AC (A/m ): 0 30 100 300 500 1000
0.1
i DC (A/m )
2
10
Figure 3.31 Effect of AC on anodic and cathodic overpotentials for copper in CuSO4 1 M
103
Results
250 200 150 Overpotential (mV) 100 50 0 -50 -100 -150 -200 -250 -300 1 10 i DC (A/m )
Figure 3.32 Effect of AC on anodic and cathodic overpotentials for carbon steel in FeSO4 1 M
2
AC (A/m2): 1000 500 300 100

Fe - FeSO4 1M
30 0 100
3.4 WEIGHT LOSS TESTS

The effects of AC on corrosion rate and corrosion morphology were studied as functions of exposure time and AC. The corrosion rate can be evaluated by the weight loss measurements. Once the initial total surface area of the specimen and the weight lost during the test are determined, the average corrosion rate (vcorr, [m/year]) can be obtained as follows[61]:
v corr =
8.76 10 7 W At
Eq. 3.3
where: t = time of exposure in hours, A = area in cm2, W = weight loss in grams ( 10-4 g), = density in g/cm3. The weight loss has been evaluated by extrapolation from the measures of the weight loss at different cycles of cleaning performed following the ASTM G1-03 standard[61] (Par. 2.5, pag. 67).
3.4.1
Simulated Seawater Solution: 35 g/L NaCl
The average corrosion rate calculated for all the AC density (0, 100 and 300 A/m2) was about 25 m/year. The visual inspection of the samples showed pits on the surface of all specimens subjected to AC (Figure 3.33 and Figure 3.34), and no localised corrosion on carbon steel sample without AC. Since in the test conditions (35 g/L NaCl, pH = 7) the carbon steel shouldnt be subjected to localised corrosion, it appears that the AC enhanced the localisation of the corrosion attack. The effect of AC seems to be the formation of an oxide layer with no good protective 104
Results proprieties. This is in agreement with the results reported in literature20: carbon steel corrosion in soil, for AC greater than 500 A/m2, took place in the form of localised pits.
Figure 3.33 - Localised corrosion attack on carbon steel in seawater in the presence of AC 100 A/m2
Figure 3.34 - Localised corrosion attack on carbon steel in seawater in the presence of AC 300 A/m2
3.4.2
Simulated Soil Solution
In this section the results of weight loss tests on carbon steel in aerated and de-aerated simulated soil solution (1.77 g/L Na2SO4 + 0.41 g/L CaCl22H2O) are reported. A set of immersion tests was performed in aerated solution without thermostating.
Aerated solution without thermostating

The tests without thermostating allowed to follow the temperature changes (Figure 3.35) due to the AC flow and to verify if that could influence the corrosion rate. Due to the Joule effect, the solution temperature increased with the AC density. For AC = 850 A/m2, the solution temperature reached 55C.
105
Results
60 55 Temperature (C) 50 45 40 35 30 25 20 15 0 5 10 15 20 Time (days) 25
AC (A/m2): 0 10 19 31 48 71 109 359 488 850
30
Figure 3.35 Temperature measurements during the weight loss tests on carbon steel without thermostating
The potential readings are reported in Figure 3.36. It can be noticed that the potential increased with time and with the AC density. In fact, though at start the AC imposition led to a sudden decrease on the corrosion potentials, few days after the samples with AC < 70 A/m2 showed a potential quite close to the samples without AC and the samples with AC > 70 A/m2 polarised to higher potentials and showed an increasing trend for all the length of the test (150 days).
-570 -590 -610 E vs SCE (mV) -630 -650 -670 -690 -710 -730 -750 0 30 60 90 Time (days) 120 150
AC (A/m2):
0 10 19 31 48 71 109 359 488
Figure 3.36 Potential readings vs SCE during the weight tests on carbon steel without thermostating
The calculated corrosion rates (vcorr) and the current efficiency (CE%) are reported in Tab. 3.12. The current efficiency CE% was evaluated as follows[3] (Par. 1.12.4, pag 40):
CE(%) =
m 100 m'
Eq. 3.4
106
Results
m' =
Q A w 2 2 Irms tA w = F n nF
2 2 Ir m s
Eq. 3.5
Iavg =
Eq. 3.6
where m = actual weight loss of metal during the electrochemical process; m = weight of the metal that would dissolve theoretically at 100% efficiency; Iavg = average value or DC equivalent; Q = quantity of charge (Q = lawt; t = time), Irms = root mean square value of the current; F = Faraday constant, Aw = atomic weight of metal, n = number of electrons involved in the dissolution reaction. Corrosion rate increased with AC density (Figure 3.37), whereas the current efficiency decreased (Figure 3.38). There was a sudden increase of both the corrosion rate and current efficiency for AC > 700 A/m2. This is most probably related to the high temperature increase related to the higher AC densities.
Tab. 3.12 - Evaluated corrosion rates (vcorr) and current efficiency (CE%) for weight loss tests on carbon steel without thermostating
iAC (A/m2) 0 10 19 31 48 71 109 359 488 850
vcorr (m/year) 101 184 210 208 227 228 299 803 1036 5506
CE% 1.72 1.04 0.63 0.44 0.30 0.26 0.21 0.20 0.62
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Results
8000 7000 6000 vcorr (m/year) 5000 4000 3000 2000 1000 0 0 200 400 600 i AC (A/m2) 800 1000 1200 measured value average value
Figure 3.37 Evaluated corrosion rates (vcorr) for weight loss tests on carbon steel without thermostatating
2.5
measured value
2 CE % 1.5 1 0.5 0 0 200 400 600 2 i AC (A/m )
average value
800
1000
Figure 3.38 Evaluated current efficiency (CE%) for weight loss tests on carbon steel without thermostating
Figure 3.39 reports the evaluated corrosion rates (vcorr) and AC current efficiency (CE%) as a function of time. It can be noticed that both the corrosion rate and the current efficiency did not changed significantly with time. Figure 3.40 reports the pictures of some carbon steel coupon after the immersion tests. It can be noticed that the corrosion became more localised as the AC increased. Therefore the actual penetration rates would be higher than the average corrosion rates evaluated by weight loss.
108
Results
400 350 vcorr (m/year) 300 250 200 150 100 50 0 0
AC (A/m ):
0 19 48 109
10 31 71
2.5 2.0 CE % 1.5 1.0 0.5 0.0
AC (A/m ):
10 31 71
19 48 109
40
80 Time (days)
120
160
40
80 Time (days)
120
160
Figure 3.39 Evaluated corrosion rates (vcorr) and current efficiency (CE%) as a function of time for immersion tests on carbon steel without thermostating
100 A/m2
300 A/m2 1000 A/m2 1000 A/m2
Figure 3.40 Picture of carbon steel coupon after the weight loss tests in simulated soil solution without thermostating
109
Results
Aerated solution - thermostated at 20C

The evaluated corrosion rates (vcorr) and current efficiency (CE%) for immersion tests on carbon steel at 20C are reported in Tab. 3.13. It can be noticed that the corrosion rate increased with AC density (Figure 3.41), whereas the current efficiency decreased (Figure 3.42). The obtained values were pretty close to those of the tests without thermostating.
Tab. 3.13 - Evaluated corrosion rates (vcorr) and current efficiency (CE%) for weight loss tests on carbon steel at 20C
iAC (A/m2) 0 101 311 493
vcorr (m/year) 85 358 820 957
CE%
0.34 0.25 0.18
1200
measured value
1000 vcorr (m/year) 800 600 400 200 0 0 100 200 300 2 i AC (A/m ) 400 500 600
average value
Figure 3.41 Evaluated corrosion rates for weight loss tests on carbon steel at 20C
110
Results
0.4 0.35 0.3 0.25 CE % 0.2 0.15 0.1 0.05 0 0 150 300 450 2 i AC (A/m ) 600
measured value average value
Figure 3.42 Evaluated current efficiency (CE%) for weight loss tests on carbon steel at 20C
De-aerated solution - thermostated at 20C

Corrosion rates (vcorr) and current efficiency (CE%) for weight loss tests on carbon steel at 20C in de-aerated solution are reported in Tab. 3.14. It can be noticed that the corrosion rate increased with AC density (Figure 3.43), whereas the current efficiency did not change significantly (Figure 3.44). The CE% first decreased, but it changed trend by increasing for AC > 300 A/m2.
Tab. 3.14 - Evaluated corrosion rates (vcorr) and current efficiency (CE%) for weight loss tests on carbon steel at 20C in de-aerated solution
iAC (A/m2) 0 31 101 289 502 779
vcorr (m/year) 14 73 301 554 1656 2143
CE%
0.22 0.28 0.18 0.31 0.26
As expected, the corrosion rate without AC in absence of oxygen was considerably lower than the one obtained in aerated conditions. Comparing the result in de-aerated and aerated conditions in the presence of AC the following can drawn: for AC = 31 A/m2 the corrosion rate was higher in aerated conditions; for AC between 30 and 300 A/m2, the corrosion rate obtained were quite close in the two different conditions;
111
Results for AC about 500 A/m2 the corrosion rate was higher in de-aerated conditions; for AC > 700 A/m2 the corrosion rate was considerably higher in aerated conditions.
2500 measured value 2000 vcorr (m/year) 1500 1000 500 0 0 200 400 600 2 i AC (A/m ) 800 1000 average value
Figure 3.43 Evaluated corrosion rates, vcorr, for weight loss tests on carbon steel at 20C in de-aerated solution
The potential measurements are reported in Figure 3.44. Though just after the AC imposition the potential decreased, after a few seconds it increased and stabilised at higher value than those of the samples without AC for all the tested conditions.
-550 -600 E (mV) -650 -700 -750 -800 0
AC (A/m ):
CE %
0 31 101 291 502 778
0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0

measured value average
10 20 30 Time (days)
40
250
500 750 2 i AC (A/m )
1000
Figure 3.44 Potential measurements and evaluated current efficiency, CE%, for weight loss tests on carbon steel at 20C in de-aerated solution
112
Results
3.5 CHARACTERISATION OF THE CORROSION MORPHOLOGY IN THE PRESENCE OF AC INTERFERENCE

In this section the results of the SEM-EDS analysis of carbon steel samples are reported. The SEM-EDS analysis were performed on carbon steel specimens after 15 days immersion in simulated soil solution. Before immerging the samples into the solution the 0.8 cm2 transverse section were polished to 1 m diamond paste. Four different interfering conditions were reproduced: neither AC nor DC interference; 100 A/m2 AC; 300 A/m2 AC; 0.3 A/m2 DC anodic interference, corresponding to about 300 m/year, that is the mean corrosion rate obtained during weight loss test at 100 A/m2 AC. The EDS analysis didnt showed any significant difference on the oxide film composition. All the samples were analysed both before and after pickling with inhibited HCl (5% HCl + 5 g/L hexamethylenetetramine).
Neither AC nor DC interference

A film of corrosion products formed on the non interfered sample (Figure 3.45). Not all the surface was corroded.
1 cm
Figure 3.45 Neither AC nor DC interference, 15 days in simulated soil solution
Considering the pictures after pickling (Figure 3.46), it was observed that the surface was almost intact in the area that was not corroded, whereas the zone that was originally covered by the corrosion products presented a number of spherical attacks (Figure 3.46 b-c-d). The number of pits increased from the middle to the bottom of the sample (left side in the picture Figure 3.45 and 113
Results
bottom in Figure 3.46). The size of the pits was in the range of few micron (5-20 m) and they were just superficial with no penetrating aspect.
1 cm
a) full sample
b) enlargement at a
c) enlargement at b
d) enlargement at b
Figure 3.46 Neither AC nor DC interference after pickling, 15 days in simulated soil solution
114
Results
AC = 100 and 300 A/m2

A thick and compact but non-adherent film formed on both the AC interfered samples (Figures 3.47-3.48). It can be noticed that the film formed, cracked, then an other non-adherent film formed underneath. Considering the pictures after pickling (Figures 3.49 and 3.50), it can be noticed that two different areas can be easily identified: the borders and the centre, characterised by highly penetrating pits with radium in the range 30-150 m; the intermediate zone between the centre and the borders (annular zone), characterised by a less severe attack with morphology quite close to the bottom area of the noninterfered sample. Though the area interested by the pits is larger and the attacks look more severe than those of the non-interfered sample.
1 cm
a) full sample
b) enlargement at border
c) enlargement at a crack
d) enlargement of the crack
Figure 3.47 AC = 100 A/m2 before pickling, 15 days in simulated soil solution
115
Results
1 cm
a) full sample
b) enlargement of a crack
c) multilayer within the crack

Figure 3.48 AC =300 A/m2 before pickling, 15 days in simulated soil solution
116
Results
b c a
1 cm
a) full sample
b) enlargement at a
c) enlargement at b
d) enlargement at c
Figure 3.49 AC = 100 A/m2 after pickling, 15 days in simulated soil solution
117
Results
1 cm
enlargement at a
Figure 3.50 AC = 300 A/m2 after pickling, 15 days in simulated soil solution
118
Results
0.3 A/m2 DC anodic interference

The applied 0.3 A/m2 DC anodic interference corresponds to a penetration rate of about 300 m/year, that is the mean corrosion rate obtained during the weight loss test at 100 A/m2 AC. As for the non-interfered sample, a layer of corrosion products formed on the surface of the sample (Figure 3.51). The pictures after pickling (Figure 3.52) showed a more severe and localised attack than those observed for non interfered sample. The corrosion appeared to be less penetrating than for the AC interfered samples.
1 cm
Figure 3.51 DC = 0.3 A/m2 (anodic interference) before pickling, 15 days in simulated soil solution
119
Results
a b
1 cm
a) full sample
b) enlargement at a
c) enlargement at b
d) enlargement at b
Figure 3.52 DC = 0.3 A/m2 (anodic interference) after pickling, 15 days in simulated soil solution
Potential measurements
The potential measurements of the four carbon steel samples are reported in Figure 3.53. After the AC imposition the potential suddenly decreased, then a few second later it started increasing and stabilised at higher value than those measured for samples without AC. This is most probably to be related to the thick oxide film formed in the presence of AC. The sample interfered by 0.3 A/m2 direct anodic current showed a potential quite close to the sample on free corrosion conditions.
120
Results
-300 -350 E vs SCE (mV) -400 -450 -500 -550 -600 -650 -700 0 5 10 Time (days)
Figure 3.53 - Potential measurements of carbon steel in simulated soil solution
A/m
AC = 0 AC = 100 AC = 300 DC = 0.3
15
20
3.6 EFFECT OF AC ON CARBON STEEL REBAR IN CONCRETE

In order to simulate corrosion condition of rebar embedded in chloride contaminated concrete, the tests were performed in alkaline synthetic pore solution obtained from a saturated calcium hydroxide solution with NaOH 0.01 M (pH = 12.6); the solution was initially chlorides free.
3.6.1.1
Potentiodynamic Tests
Potentiodynamic tests were performed in order to determine the effect of AC on breakdown potential (Eb) and passivity current (ip) (Par. 2.7.4, pag. 73). In Figure 3.54a a potentiodynamic curve of carbon steel in alkaline solution containing 0.03 M NaCl is reported. The test was performed in the absence of AC. The breakdown potential was about + 250 mV vs SCE and the passivity current was about 0.01 A/m2. The potentiodynamic curve obtained in the presence of 1000 A/m2 AC density and without chlorides in the alkaline synthetic pore solution is reported in Figure 3.54b. The visual inspection after the test revealed that there was no corrosion on the carbon steel sample. It can be noticed that, even if at start the passivity current seems firstly to decrease as the potential increases, for potential higher than 50 mV SCE it suddenly increases. For higher potentials, the value of the passivity current is very high ranging from 0.1 to 1 A/m2. Such values of the current are closer to active dissolution than to passivity.
121
Results
0.8 0.6 E vs SCE (V) E vs SCE (V) 0.4 0.2 0.0 -0.2 0.001
no AC 0.03 M NaCl
0.8 0.6 0.4 0.2 0.0 -0.2 0.001

AC 1000 A/m2 no NaCl
0.01
0.1 i DC (A/m )
2
10
0.01
0.1 i DC (A/m )
2
10
a)
b)
Figure 3.54 Potentiodynamic curve on carbon steel in alkaline solution (pH = 12.6): a) without AC with chlorides (0.03M); b) AC = 1000 A/m2 , without chlorides
The last test was performed in the presence of 100 A/m2 AC and 0.03 NaCl. The pitting corrosion initiated just after the chlorides addiction (Figure 3.55), before starting the potentiodynamic scan. This confirmed that the effect of AC on carbon steel in a alkaline solution containing chlorides is a significant decrease of the pitting potential.
0.0 -0.1 E vs SCE (V) -0.2 -0.3 -0.4 -0.5 -0.6 -0.7 0 0.2 0.4 0.6 Time (hours)
Figure 3.55 Potential monitoring before the potentiodynamic test on carbon steel in alkaline solution, AC = 100 A/m2 and NaCl = 0.03 M
no chlorides
NaCl 0.03 M
AC 100 A/m2
3.6.1.2
Immersion Tests
The aim of these tests was to determine the critical chlorides content that causes the initiation of localised corrosion of carbon steel in alkaline solution (pH = 12.6) in the presence of AC.
Preliminary tests
Two carbon steel samples were tested in alkaline solution for every AC condition; steel potential was regularly measured.
122
Results
During the first set of tests (Figure 3.56) the chlorides were added daily to the solution in the amount of 5 mmol/L. In the presence of AC current (100 and 500 A/m2) the localised corrosion occurred after the first chloride addition (5 mmol/L, Figure 3.56b), whereas, without AC interference, the localised corrosion occurred in the range of 2030 mmol/L NaCl (Figure 3.56a). Localised corrosion was revealed by a sudden potential drop below 0.3 V SCE and confirmed by visual inspection (Figure 3.57). During the second series of tests (Figure 3.58) the chlorides were added daily in a smaller amount (1 mmol/L). In the presence of a low AC current (50 A/m2) the localised corrosion occurred at a chloride concentration of 11 mmol/L (Figure 3.58a); during the test without AC interference the localised corrosion occurred in the range of 2529 mmol/L (Figure 3.58b).
0.0 -0.1 30 0.0 -0.1 30
no AC
25
AC 100 A/m 2 AC 500 A/m 2 NaCl
25 20 15 10 5 0
NaCl (mmol/L)
-0.2 -0.3 -0.4 -0.5 -0.6 0 50 100 150
20 15 10
-0.2 -0.3 -0.4 -0.5 -0.6 0 5 10
E NaCl
0 200
15
20
Time (h)
Time (h)
a)
b)
Figure 3.56 Carbon steel potential trend in alkaline solution in the presence of added chlorides (5 mmol/L per day): a) NO AC; b) AC = 100 and 500 A/m2
Figure 3.57 - Localised corrosion attack on carbon steel in synthetic alkaline solution in the presence of AC 500 A/m2 and 5 mmol/L NaCl
NaCl (mmol/L)
E vs SCE (V)
E vs SCE (V)
123
Results
0.0
30
no AC
-0.1 25
0.0 -0.1
30 25
NaCl (mmol/L)
E vs SCE (V)
-0.2 -0.3 -0.4 -0.5 -0.6 0 250 500 750
20 15 10
E vs SCE (V)
-0.2 -0.3 -0.4 -0.5
E NaCl
20 15 10
E NaCl
5 0 1000
AC 50 A/m
-0.6 0 100 200 300
5 0 400
Time (h)
Time (h)
Figure 3.58 Carbon steel potential trend in alkaline solution in the presence of added chlorides (1 mmol/L per day): a) NO AC; b) AC = 50 A/m2

Carbon steel potential was regularly measured. Two metallic samples were considered for every AC condition. The chlorides were added daily to the solution in the amount of 1 mmol/L. Localised corrosion was revealed by a sudden negative shift in the potential below 0.3 V SCE and confirmed by visual inspection. Corroded samples in the presence of AC showed potentials even lower than 700 mV SCE. An example of the potentials recorded is reported in Figure 3.59.
0.1 0.0 -0.1 E vs SCE (V) -0.2 -0.3 -0.4 -0.5 -0.6 -0.7 -0.8 0 10 20 30 40 50 36 32 28 24 20 16 12 8 4 0 [Cl ] (mmol/L) 0 6 12 57 97 323 350 435 539 800 AC ON [Cl-]
Time (days)
Figure 3.59 - Carbon steel potential trend in alkaline solution in the presence of added chlorides (1 mmol/L per day)
The pH of the solution was regularly controlled and if necessary adjusted by adding Ca(OH)2. Unfortunately despite the Ca(OH)2 surplus in order to buffer the solution pH at the desired value, 124
NaCl (mmol/L)
Results
during the third week of the tests a sudden pH decrease occurred. The pH was immediately adjusted and the samples that corroded just after this event were not considered for the results analysis. In Tab. 3.15 the obtained critical chlorides threshold as a function of AC densities for carbon steel in alkaline solution (pH = 12.6) are reported. The results can be summarised as follows: for the samples non-interfered by AC the corrosion initiate at 17 mmol/L chlorides. This value is slightly lower than the one obtained during the previous measurements. That could be explained considering the sudden pH decreased occurred during the test; AC > 40 A/m2: the critical chlorides threshold for pitting initiation is lower than 15 mmol/L; AC > 350 A/m2: the critical chlorides threshold is lower than 10 mmol/L ; only three samples (5, 11, 35 A/m2) corroded at chlorides content higher than the noninterfered samples.
Tab. 3.15 - Critical chlorides threshold
AC density (A/m2) 0 5 6 11 12 21 24 33 35 47 57 97 112 251 323 435 539 800
Critical chlorides content (mmol/L) 17 27 13 29 14 8 16 17 19 8 14 14 12 14 8 8 9 9
125
Results
In order to study the effect of AC on corrosion propagation, some samples were left into the solution for one week after the localised corrosion initiation (during this week the chloride addition was interrupted). The amount of corrosion products increased with the AC density (Figure 3.60). The surface under the corrosion products was also corroded, most probably due to the acidification related to the hydrolysis of Fe ions.
24 A/m2
0 A/m2
112 A/m2
350 A/m2
Figure 3.60 Propagation of corrosion increasing AC density
126
Results
3.7 EFFECT ON CATHODIC PROTECTION MONITORING

Cathodic protection monitoring in the presence of simultaneous AC and DC interference could lead to erroneous measurements, since IR drop contribution due to both DC and AC could heavily affect potential readings. Therefore to know the true potential (or true polarisation level), the ohmic drop contribution has to be eliminated. In literature there is a lack of agreement about the correct procedure to measure the true potential in the presence of AC. In this section the results of laboratory tests on cathodically protected carbon steel in simulated soil conditions are reported. Tests were focused on potential measurements in the presence of AC as for potential measurement procedures and the use of a potential probe are concerned.
3.7.1
First set of measurements
During the first set of measurements the potential was measured both with respect to an internal MMO-Ti RE positioned at the back of the sample (Figure 2.16, pag. 76) and with respect to four CSE RE placed at different distances from the working electrode as previously described (Par. 2.8, pag. 75). Figure 3.61 reports the plot of true rms (root mean square) alternate potential readings (EAC) as a function of AC density (iAC). It is evident that the alternate potential is high and that, in agreement with the Ohms law, increases with the RE distance. As expected, a considerably lower rms EAC was always measured in correspondence of the internal MMO-Ti RE placed at the back of the sample.
25 20 EAC (V) 15 10 5 0 0 25 50 i AC (A/m )
Figure 3.61 - True rms alternate potential measurements at different distances from the working electrode
2
Ti CSE1 CSE2 (5 cm) CSE3 (10 cm) CSE4 (20 cm)
75
100
DC potential readings (EDC) are reported in Figure 3.62. The ohmic drop due to DC current kept constant (about 40 mV between the internal MMO-Ti RE and CSE4) for all AC current densities
127
Results
applied for both anodically and cathodically conditions. Potential measurements of freely corroding samples gave the same results for the four CSE reference electrodes positioned at different distances, thus suggesting that there was no ohmic drop contribution due to AC interference. It can be noticed (Figure 3.62) that, for anodically polarised samples, the DC potential (EDC) decreases increasing the AC density, whereas EDC increases for cathodically polarised samples. Since the DC current density was kept constant at the value of 0.5 A/m2, the potential variation were associated to the presence of AC current. To better analyze this effect, the potential variation (E = Ewith AC - Ewithout AC) was plotted as a function of AC density for anodically and cathodically polarised samples (Figure 3.63). It can be noticed that no significant differences are observed between the potential variation (E) obtained measuring the potential at the different distances. Therefore it can be concluded that when the multimeter used has an efficient AC filter, both DC potential and current measurements are not affected by the presence of alternate current. Though, if the AC/DC current or potential ratio is high or the AC signal is not sinusoidal, the AC filter could not work properly. In that case multimeter does not allow a stable reading (0.1 to 0.4 V in quick oscillating variations). For these measurements a true rms 187 Fluke multimeter was used. As any multimeter, it filters the AC component when reads the DC current or potentials. The used multimeter gave stable reading when the AC/DC ratio was < 20. The obtained potential variations (E, Figure 3.63) are in good agreement with previews experiments (Par. 3.1-pag. 81, Par. 3.2-pag. 84, Par. 3.3.2-pag. 90) confirming that in soil simulating conditions an AC current overlapped to a cathodically or anodically polarised steel has a depolarising effect. Due to the higher resistivity of the sand compared to the simulated soil solution it was not possible to explore the same range of AC current densities (0-1000 A/m2).
-0.6 -0.7 EDC (V vs CSE) -0.8 -0.9 -1 -1.1 -1.2 0 25 50 i AC (A/m2) 75 100
AP: CSE1 AP: CSE2 (5 cm) AP: CSE3 (10 cm) AP: CSE4 (20 cm) CSE1 CSE2 (5 cm) CSE3 (10 cm) CSE4 (20 cm) CP: CSE1 CP: CSE2 (5 cm) CP: CSE3 (10 cm) CP: CSE4 (20 cm)
Figure 3.62 - DC potential measurements as a function of the AC density, measured at different distances from the working electrode: freely corroding (black mark), cathodically (CP) and anodically (AP) polarised carbon steel sample in wet sand at constant DC density of 0.5 A/m2
128
Results
100 E = EAC - Ewithout AC (mV) 75 50 25 0 -25 -50 -75 -100 0 25 50 i AC (A/m2) 75 100
Anodic polarization Cathodic polarization
CP: CSE1 CP: CSE2 (5 cm) CP: CSE3 (10 cm) CP: CSE4 (20 cm) CP: Ti AP: CSE1 AP: CSE2 (5 cm) AP: CSE3 (10 cm) AP: CSE4 (20 cm) AP: Ti
Figure 3.63 - DC potential variations as a function of the AC density, measured at different distances from the working electrode for cathodically (CP) and anodically (AP) polarised carbon steel sample in wet sand
3.7.2
In Figure 3.64 potential readings recorded at different interfering conditions are reported. The black line represents the potential reading with respect to MMO-Ti RE positioned inside the potential probe (Figure 2.18, pag. 77) and the grey one with respect to the external CSE reference electrode placed above the potential probe. DC and AC ON/OFF are indicated by a dotted and continuous vertical line, respectively. Considering either non-stationary DC interference (Figure 3.64a) and DC ON/OFF
measurements (Figure 3.64b), it is clear that potential readings with respect to an external CSE RE are affected by the ohmic drop contribution, whereas readings with respect to the internal MMO-Ti RE are not. If high DC densities are supplied, also the potential reading with respect to the internal Ti-MMO varies smoothly due to the depolarisation of the steel plate of the potential probe. Actually, the ohmic drop contribution cannot be completely eliminated even switching off the interfering current, because when CP or stray currents are temporary turned off, coating defects that have different size, having a different polarisation level, start exchanging current. This is evident in Figure 3.65 where the potential readings of a cathodically protected probe both with respect to the external CSE and the internal MMO-Ti RE are reported. As previously described (Par. 2.8.2, pag. 77) for these measurements, two potential probes were positioned in the cell (Figure 2.19, pag. 77) with the two open faces looking to the counter electrodes to allow the interfering current to intercept the potential probes. Such configuration allowed the simulation of the interference of two coating defects by disconnecting the two potential probes. In Figure 3.65 it is therefore indicated the instant when the sample was disconnected from the other potential
129
Results
probe. After the disconnection the potential reading with respect to CSE suddenly increases, indicating that the probe was receiving a cathodic current.
Ti
-0.8 -1.0 E (V)
E (V)
CSE
-1.0 -1.2 -1.4 -1.6 -1.8
AC on DC on DC off AC off AC on DC on AC AC on off
-1.2 -1.4 -1.6 -1.8 0 20 Time (s) 40 60
-2.0 0
20
Time (s)
40
60
a)
-0.5 -0.7 E (V) E (V) -0.9 -1.1 -1.3 -1.5 0
AC on AC off
AC AC AC AC on off AC on on off
b)
0.0 -0.2 -0.4 -0.6 -0.8
AC on AC off AC on
-1.0 0 20 Time (s) 40 60
20
Time (s)
40
60
c)
d)
Figure 3.64 - Potential readings recorded in different conditions: a) CP and non stationary DC interference; b) CP, DC (0.02 A/m2) and AC (0.4 A/m2) interference; c) CP and AC 30 A/m2 interference; d) AC 115 A/m2
Considering AC ON/OFF the following can be pointed out: for AC 30 A/m2, no potential variation are observed both with respect to the external CSE and the internal MMO-Ti RE (Figure 3.64 b and c); for AC > 30 A/m2, the same potential variations are measured with respect to both the external CSE and the internal MMO-Ti RE (Figure 3.64 d). This results are in good agreement with the first set of measurements and with previous experiment.
130
Results
-0.6
CP on
-0.8 -1 -1.2 -1.4 -1.6 0 5 10
CP off
CP on
E (V)
disconnected
E vs Ti E vs CSE
15 Time (s) 20 25 30
Figure 3.65 ON/OFF measurement on a cathodically protected probe without neither DC nor AC interference
3.8 MEASUREMENTS BY OSCILLOSCOPE

Measurements of AV signals by oscilloscope were performed for all the tested conditions. All the performed potential measurements between the working electrode and the SCE reference electrode were made by means of a Luggin capillary. In Figure 3.66 the instantaneous ohmic drop measured on a 10 resistance (AC coupling) during a test on carbon steel interfered by 1000 A/m2 AC is reported. The AC coupling measurement halts the DC component but let pass the dynamic component (AC). In Figure 3.67 the AC and DC coupling measurements for a carbon steel samples interfered by 1000 A/m2 AC are reported. The DC coupling allows the observation of both the AC and DC components. As should be expected the DC coupling signal is shifted of about 800 mV with respect to the AC coupling signal, corresponding to the DC potential of the electrode. Some authors[39,38] suggested as protection criterion under AC influence to keep the true potential (including the maximum peaks) within the immunity domain, i.e. below the equilibrium potential, at all times. It is evident that this criterion couldnt be applied in practice because it would mean to polarise the metallic structures to very negative potentials in order to guarantee that the instantaneous potential is lower than the protection potential for all the period. For example, in the case reported in Figure 3.67, the pick potential of the DC coupling measurement is about 0.8 V, keeping the true potential (including the maximum peaks) within the immunity domain at all times would mean to polarise the sample at a mean potential lower than 1.65 V SCE, leading to all the problems related to cathodic overprotection.
131
Results
8 6 4 Voltage (V) 2 0 -2 -4 -6 -8 -0.02 -0.015 -0.01 -0.005 0 Time (s)

Figure 3.66 Oscilloscope measurements (AC coupling) for a carbon steel sample in simulated soil solution, AC density 1000 A/m2: instantaneous ohmic drop measured on a 10 resistance
ohmic drop, R = 10 ohm
0.005
0.01
0.015
0.02
2 1.5 1 Voltage (V) 0.5 0 -0.5 -1 -1.5 -2 -2.5 -0.02 -0.015 -0.01 -0.005 0 Time (s) 0.005 0.01
AC coupling DC coupling
0.015
0.02
Figure 3.67 Instantaneous voltage between working electrode (w) and SCE reference electrode for a carbon steel sample in simulated soil solution, AC density 1000 A/m2; black line AC coupling; grey line DC coupling
132
DISCUSSION
In this chapter the experimental results will be discussed as follows: AC Density Threshold; AC Influence on Corrosion Process; Corrosion Morphology in the Presence of AC Carbon Steel in Alkaline Solution; Cathodic Protection Monitoring.
4.1 AC DENSITY THRESHOLD

As described in the Chapter 1, the evaluation of AC current densities is a very important parameter, considered as one of the most important indicators in order to estimate the risk of AC induced corrosion (Par. 1.8.3, pag. 25): the higher the AC density, the greater the risks. The threshold AC density suggested by standards and confirmed by laboratory tests ranges between 20 and 30 A/m2[34,35,36], even if some authors suggested lower threshold values[32]. Though, currently, a safe alternating current density below which AC does not enhance corrosion has not yet identified. However, it can be considered that if the increase in corrosion due to AC is not appreciably greater than the free-corrosion rate for a specific environmental condition, then no AC mitigation is required. The weight loss tests performed in aerated simulated soil solution (Par. 3.4.2, pag. 105) confirmed that AC > 30/m2 give rise to considerable increase of the corrosion rates. Furthermore for AC = 850 A/m2, the bulk temperature reached 55C. Weight loss tests showed also that such an increase of temperature may rise the AC current efficiency of metal dissolution. In addition the results showed that even an AC density of 10 A/m2 may increase corrosion rate nearly two-times with respect to the non-interfered samples. Furthermore it was revealed that that the corrosion localised as the AC density increased. Therefore the actual penetration rates may be higher than the average corrosion rates evaluated by weight loss. It can be concluded that 10 A/m2 AC interference is harmful for carbon steel in soil simulated solution. Further investigation are needed to evaluate the AC density threshold for different metals.
Discussion
4.2 AC INFLUENCE ON CORROSION PROCESS

As previously discussed (Par. 1.12, pag. 33) there is a lack of agreement among authors about the mechanism by which AC affects corrosion: different theories and hypotheses have been proposed, but none of them is able to fully explain and describe such a phenomenon. Since electrochemical phenomena of corrosion are normally attributed to direct current, some authors[5,24,28,46,46] have produced mathematical models based on the Faradaic rectification effect: if the symmetry factor in the Butler-Volmer equation is different from
1 2
, the potential curve would
not be symmetrical and the interface would have rectifying properties leading to the Faradaic rectification effect[44]. The Faradaic rectification models are the sole mathematical models proposed to describe the AC-induced corrosion. Before analysing in detail their reliability it would be useful to highlight some basic concepts and the main results obtained during this three years experimental research.
4.2.1
Corrosion Rate and AC Current Efficiency (CE%)
It was confirmed that AC corrosion is only a small percentage of what it would be if an equivalent DC current density would interfere the samples. This confirmed that AC induced corrosion is remarcable only for current densities 100-1000 higher than DC. The current efficiency (CE%), obtained (Figure 4.1) for carbon steel in simulated soil solution, are in good agreement with the values reported in literature which vary approximately between 0.1 % and 5 %[39,53]. CE% for carbon steel in simulated soil solution was lower than 2% and decreased as the AC density increased. Such results can be explained considering that, as for any process, also electrochemical reactions are characterised by an induction time, during which the current is mainly used for the electrical charging of the metal/solution interface. Furthermore, for current densities higher than 50-100 A/m2 the system would be reasonably under conditions of concentration polarisation, leading to a considerable increase of overpotentials. It can be noticed that there were no significant differences on CE% under different experimental conditions (aerated but non-thermostated, aerated at 20C, deaerated at 20C). It can be deduced therefore that CE% does not depend on the cathodic process involved or on the Tafel slopes ratio r = a/c. The small differences on CE% recorded between de-aerated and aerated conditions can be summarised as follows: for AC = 30 A/m2 the CE% is slightly higher in aerated conditions; for AC between 30 and 300 A/m2, the corrosion rate are quite close into the two different conditions (aerated and deaerated); for AC about 500 A/m2 the corrosion rate is higher in de-aerated conditions; for AC > 700 A/m2 the corrosion rate is considerably higher in aerated conditions.
134
Discussion The CE% increase for AC > 750 A/m2 during the test on aerated, non-thermostated solution can be explained by the considerable increase of the solution temperature up to 55C. Corrosion rate and current efficiency did not changed significantly with time.
2.0 1.6 1.2 0.8 0.4 0.0 0 250 500 2 i AC (A/m ) 750 1000 No Thermostat 20C 20C-Nitrogen
Figure 4.1 Current efficiency (CE%) for weight loss tests on carbon steel in simulated soil solution
Figure 4.2 shows corrosion rates of carbon steel which were obtained by weight loss tests (No thermostating; 20C; 20C-Nitrogen) and those obtained from cathodic characteristics by linear regression in deaerated simulated soil solution (Tafel1 and Tafel2). Tafel1 refers to the tests performed with 12 hours equilibration and 1 hour rest between cathodic and anodic polarisation, while Tafel2 refers to the tests performed with 50 hours equilibration and 12 hour rest between cathodic and anodic polarisation (Par. 3.3.2, pag. 90). On samples non-interfered by AC in deaerated conditions, there is a good agreement on corrosion rate obtained by weight loss and by extrapolation of Tafel plot (20 and 14 m/year, respectively). In the presence of AC the values obtained by Tafel extrapolation were significantly lower than those obtained by weight loss tests. Therefore, Tafel extrapolation to calculate icorr is not applicable in the presence of AC interference. Reason of this has to be further investigated. The Tafel plots allows therefore the evaluation of the effects of AC on kinetics parameters as Tafel slopes of cathodic and anodic processes, but does not allow a correct estimation of the actual metal dissolution in the presence of AC.
CE %
135
Discussion
10000
vcorr (m/year)
1000
100
no thermostat 20C 20C-Nitrogen Tafel1 Tafel2
10 0 250 500 750 2 i AC (A/m ) 1000 1250
Figure 4.2 Carbon steel in soil simulated solution: corrosion rates evaluated during the weight loss tests (no thermostat, 20C, 20C-Nitrogen) and from the interception of the anodic and cathodic characteristics obtained by linear regression of the polarisation curves. Tafel1 refers to the tests performed with 12 hours equilibration and 1 hour rest between cathodic and anodic polarisation; Tafel2 refers to the tests performed with 50 hours equilibration and 12 hour rest between cathodic and anodic polarisation
4.2.2
Influence of AC on Corrosion Kinetics
Polarisation tests on carbon steel, galvanised steel, zinc and copper (Par. 3.3, pag. 89) confirmed that AC current has a strong influence on corrosion kinetics and on corrosion or equilibrium potential. The effects of AC on parameters as Tafel slopes and exchange current density depends on the system studied (metal/environment) and on the AC density supplied. The results are summarised in Tab. 4.1; the variation of the values as a function of the AC density are symbolised as follows: increase, decrease, no significant changes. When more than one symbol is present, it means that AC had different effects depending on the current density. icorr and Ecorr refer to tests where the anodic process was metal dissolution and the cathodic one hydrogen evolution, while i0 and Eeq to the tests on metals in 1 M solution of their ions. A general decrease of overpotentials and increase of corrosion or exchange current density was observed for the different tested conditions. Such decreases on overpotentials would most probably persist for a while even if the AC is turned off. With the only exception of the tests in simulated soil solution, the corrosion or equilibrium potential decreased. These results can be explained considering that the AC leads to the growth of thick, non-adherent films of corrosion product on the metal surface (Par. 3.5, pag. 113). The nature, thickness and adhesion of the film change with the AC density, the metal and solution composition. AC flow may also cause variation on the double layer chemical composition with consequent change of the equilibrium potential. The changes on the metal/solution interface and 136
Discussion
the continuous alternation of anodic and cathodic cycles may also lead to increases of the exchange current. All these combined effects may lead to the observed changes of kinetics parameters.
Tab. 4.1 Schematic summary of the AC effects of on corrosion kinetics
Solution
a
Carbon steel
icorr or i0
Ecorr or Eeq
0.4 g/L NaSO4 simulated soil solution* (initial state and steady state conditions) 35 g/L NaCl 1 M FeSO4
Galvanised steel 35 g/L NaCl Copper 1 M CuSO4 Zinc 1 M ZnSO4

*1200 ppm
not valuable numerically overpotential decrease
SO 2 4 (1.77 g/L Na2SO4) + 200 ppm Cl (0.41 g/L CaCl22H2O)
4.2.3
Corrosion Potential
The potential variations in the presence of AC are in agreement with the two most frequently behaviours reported in literature (Figure 1.31): the potential always shifted suddenly toward the active direction; the potential drop increased with the alternate current density. Then the potential shifted back toward the noble direction reaching generally a steady state value or continuing changing, but very slowly. The time needed to reach such a steady potential and the value of it depend on the experimental conditions and on the composition of the metal. Once stabilised, the DC potential in the presence of AC may be either less or more noble than the potential in the absence of AC. All tested metals in the different conditions, with the only exception of the carbon steel in simulated soil solution (b), gave steady-state corrosion potential less noble than in the absence of AC (a).
137
Discussion
Ecorr before AC interference b) DC potential DC potential
a)
Time
Time
Figure 4.3 DC potential as a function of time
In simulated soil solution tests, potential readings of carbon steel during the weight loss tests were in good agreement with the corrosion potential variation observed during the polarisation tests at the steady state conditions: after the AC application, the potential suddenly decreased, but a few seconds after it started increasing and stabilised at higher value than those of the samples without AC; the potential increased with time and with the AC density. This can be explained by the formation of a thick film of corrosion products. The increased concentration of Fe ions close to the metal surface may shift the equilibrium potential toward more noble values. The potential increase may also be related to an increase of the cathodic exchange current.
4.2.4
Analysis of the Faradaic Rectification Models
As previously said it has been suggested that, considering a modified Butler-Volmer model, a first fundamental origin of the AC induced corrosion is the asymmetry of the anodic and cathodic processes and mathematical models have been proposed[5,24,28,46,46]. If the over-potentials are nonsymmetrical, when a sinusoidal potential is applied a mean current density (rectification current) will appear, involving a systematic corrosion. According to these models the values of the Tafel parameters, namely the ratio of the anodic and cathodic Tafel parameter (r= a/c), has a strong influence on the sensitivity of the corroding system for AC-corrosion. In Figure 4.4 the two cases of a surface with no rectifying properties (black line) and with rectifying properties (grey line) are reported. When an alternating signal passes through a surface that is asymmetric, i.e. the effects of the positive half-cycle are different than those of the negative one, then the signal will be distorted. The average value of the distorted alternating signal is not anymore nil (as it is for a sinusoidal signal), but it would be a positive or negative value depending on the type of asymmetry of the surface.
138
Discussion
Istantaneous current or voltage
surface with rectifying properties surface with NO rectifying properties
Time
Figure 4.4 Rectification effect. Black line: surface with no rectifying properties; grey line surface with rectifying properties
Experimentally, there are two different methods of applying a sinusoidal signal to a working electrode: alternating voltage modulation and alternating current modulation methods. In the former, a sinusoidal voltage is applied between the working electrode and the reference electrode, and the resulting AC and DC are measured as a function of the DC electrode potential. In the current modulation method a sinusoidal current is supplied to the working electrode and the AC and DC potentials are measured as a function of the DC current. In Figure 4.5 the two methods are exemplified. It is represented a case where a < c (r= a/c <1), that is the most frequent case for active metals as carbon steel in aerated or deaerated conditions.
E Voltage Modulation
a Ecorr
ic Current Modulation
ia
Log i
Figure 4.5 Faradaic rectification in case of current modulation and voltage modulation
139
Discussion
Voltage modulation (VM). Lets consider a single value within the sinusoidal period Vist = Vsint (where V is the peak potential, is the pulsation ( = 2f) and f the frequency of the signal). During the positive half-cycle an anodic current ia is associated to Vist, while during the negative half-cycle a cathodic current ic is associated to the applied Vist. It can be noticed (Figure 4.5) that ia > ic. The same consideration can be applied for all the period. Therefore the average value of the current over the period (obtained by integration) would give a net anodic current. Such consideration applies in case of r < 1. Obviously for r > 1 a net cathodic current should be expected. Current modulation (CM). Similar consideration can be made for the current modulation method. In that case a single value Iist = Isint is considered. During the positive half-cycle an anodic overpotential a is associated to Iist, while during the negative half-cycle a cathodic overpotential c is associated to Iist. It can be noticed that a < c. Therefore the average value of the overpotential over the period would give a net shift of the potential toward a less noble value.
Oscilloscope measurements
All the oscilloscope measurements of both current and potential (Par. 3.8, pag. 131) performed during this experimental research didnt showed any particular distortion of the signal suggesting that the rectifying effect was negligible. Though it is possible that a particular measuring methodology should be applied in order to detect the rectified current or voltage at the metal/solution interface. In order to verify whether the corrosion rates obtained were to be ascribed to a Faradaic rectification effect or not, the results of the model proposed in literature were compared with the experimental results.
Results of the models

These models (Par. 1.12.2, pag. 34) state that, considering a metal sample whose kinetics behaviour is under activation control, the AC voltages (Vsint) would lead to changes on the Tafel curves as follows: the Tafel slopes should be independent of the amplitude of the AC voltage V; when r < 1 the corrosion potential should lower as AC increases; if r > 1 the corrosion potential should shift to more positive values as AC increases; for r = 1 the corrosion potential should keep the same value; in case of both cathodic and anodic processes under charge-transfer control, the value of the corrosion current density (or the exchange current density, if the plot refers to an electrode in equilibrium) should increase in an exponential way whatever the value of the ratio r is. In case of cathodic process under mixed control the corrosion current should increase to the diffusion-limited current density iL.
140
Discussion
First of all, it should be underlined that such models consider as result a positive (anodic) current whatever the ratio r is, while, as previously showed, for r > 1 a cathodic rectified current should be expected. In addition the following discrepancies between the models and the experimental data can be noticed: in soil simulated solution, with r < 1, the corrosion potential of carbon steel increased while the model foresee a decrease; even when the potential decreased, the trend was not as foreseen by the models (e.g. polarisation curves on galvanised steel in 35 g/L NaCl solution (Par. 3.3.3, pag. 96): the corrosion potential lowered of about 100 mV in the presence of AC interference and kept almost constant for all the AC densities analysed; the Tafel slopes changed almost in all the tested conditions while the model states it should be constant; in deaerated corrosion rate obtained by weight loss did not increase exponentially as expected by the model; in aerated conditions (cathodic process under mixed control), corrosion rate increased to value considerably higher than the limiting current iL, while the models foresee iL as maximum value. Tafel slopes and corrosion current, obtained for carbon steel in soil simulated solution in the absence of AC, were input into the formula of the models proposed by Bertocci[45]and Lalvani et al.[46]. The difference between the two models is that Lalvani et al. considered the root mean square (rms) current instead of the mean value in order to incorporate the double layer capacitance into the model. Bertocci model:
0 0 ( V ) 2k ( V ) 2k exp exp (i f )DC = i 0 2k 2k 2 2 ( ) ( ) 2 ( k ! ) 2 ( k ! ) k 0 0 = c a c a

Lalvani et al. model:
2 irms
a2 1 V 2 = 0 + a1 2 2 K =0 (K!) a
2K
1 1 1 V 2a1a 2 + 2 a c 2 K = 0 (K!)
2K
a2 2
1 V (K!)2 K =0 c
2K
where icorr,DC and 0 are the corrosion current and the overpotential measured in the absence of AV; a, and c are the anodic and cathodic Tafel slopes respectively; a 0 = c d V (cd = double layer capacitance); i a = a1 = i corr ,DC exp(
0 ) ; i c = a 2 = i corr ,DC exp( 0 ) . a c
141
Discussion
Figures 4.6 and 4.7 show the comparison of the results of the models of Bertocci and Lalvani et al. for carbon steel in simulated soil solution. The parameter introduced were: a = 50 mV/dec, c = 143 mV/dec (r = 0.35), icorr = 20 mA/m2.
Bertocci model 2 AC = 0 - 30 - 100 - 300 - 500 - 1000 A/m -0.60 -0.70 -0.80 E vs SCE (V) -0.90 -1.00 -1.10 -1.20 -1.30 -1.40 -1.50 -1.60 1.E-03 1.E+00 1.E+03 1.E+06 1.E+09 1.E+12 Experimental data 2 AC (A/m ) 0 30 100 300 500 1000
iDC (A/m )
Figure 4.6 Results of the Bertocci model (a = 50 mV/dec, c = 143 mV/dec (r = 0.35), icorr = 20 mA/m2), compared with the experimental result in simulated soil solution
Lalvani model 2 AC = 0 - 30 - 100 - 300 - 500 - 1000 A/m

-0.60 -0.70 -0.80 E vs SCE (V) -0.90 -1.00 -1.10 -1.20 -1.30 -1.40 -1.50 -1.60 1.E-03 1.E+00 1.E+03 1.E+06
2
Experimental data AC (A/m2) 0
30 100 300 500 1000
1.E+09
1.E+12
iDC.rms (A/m )
Figure 4.7 Results of the Lalvani model (a = 50 mV/dec, c = 143 mV/dec (r = 0.35), icorr = 20 mA/m2), compared with the experimental result in simulated soil solution
142
Discussion
The huge difference between experimental and theoretical curves may be explained considering that the equations of the models include the rectified alternating current into the expression of i, therefore in the potential vs current graph, i is the total current including both the AC and DC contributes. During the experimental determination of the polarisation curves, as previously discussed, the rectified AC component may be present but not correctly evaluated. With the purpose of verifying the reliability of the models, the corrosion rates given by the models were compared with those evaluated by weight loss tests and polarisation curves. Before discussing such results it is important to point out a limit of such models: they do not take into account other factors that would limit the current to much lower values than those predicted by the model itself, such as mass transport into the solution, the formation of films or other alterations of the electrode surface leading to passivation which would also restrict the amount of current. In fact for current density higher than 50-100 A/m2 most of the electrodes are under conditions of concentration polarisation. Up to now, there are no models which take into account the concentration polarisation at high current densities. The problem was faced considering a modified Butler-Volmer equation for a process with both anodic and cathodic reaction under mixed control which was used in order to evaluate the rectified current. The limiting current density (iL) considered were 10, 50 and 100 A/m2 (the three cases will be indicated as VM10, VM50 and VM100 respectively).
exp a i = i corr i i 1 corr + corr exp iL iL a

400 Overpotential (mV) 200 0 -200 -400 -600 -800 0
exp c i i 1 corr + corr exp iL iL c
Eq. 4.1
0.01 0.1 1 10 2 iDC (A/m )
100 1000
Figure 4.8 Process with both anodic and cathodic reaction under mixed control (iL = 100 A/m2)
A voltage modulation (VM) method was considered. The pick voltages of the modulating signals were evaluated by means of oscilloscope measurements on 4 cm2 samples interfered by 30, 100,
143
Discussion 300, 500 and 1000 A/m2 AC. The obtained pick voltages were 39, 137, 453, 594 and 1131 mV respectively. The evaluated sinusoidal modulating signals and the distorted current signals are represented in Figure 4.9 for the case of iL = 100 A/m2. It can be noticed that the maximum current density the system can reach is equal to iL. The rectified current was calculated integrating the instantaneous current signal.
1200 Istantaneous Voltage (mV) 800 400 0 -400 -800 -1200 0 0.005 0.01 Time (s) 0.015 0.02
1000 A/m 2 500 A/m 2 300 A/m 2 100 A/m 2 30 A/m
2
120 Istantaneous current (A/m2) 80 40 0 -40 -80 -120 0 0.005 0.01 Time (s)
1000 A/m 2 500 A/m 2 300 A/m 2 100 A/m 2 30 A/m
0.015
0.02
Figure 4.9 Evaluated voltage modulating signals and distorted current signals in case of iL = 100 A/m2
In Figure 4.10 the corrosion rates obtained by the two considered models and by voltage modulation of a process with both anodic and cathodic processes under mixed control are compared with those evaluated by weight loss and polarisation curves for carbon steel in deaerated simulated soil solution. It can be noticed that none of the models is able to describe the actual corrosion rate, neither for low AC densities (Figure 4.11). It can be concluded that if there were a faradaic rectification, it wouldnt be the principal or unique effect of AC on corrosion phenomena.
1.E+02 1.E+01 1.E+00 1.E-01 1.E-02 0 250 500 750 2 i AC (A/m ) 1000
mass loss test Bertocci Lalvani VM100 VM50 VM10
Figure 4.10 Corrosion rates as a function of AC density for carbon steel in deaerated soil simulated solution obtained by Bertocci and Lalvani models, by voltage modulation of a process with both anodic and cathodic processes under mixed control (VM10, VM50, VM100), and by mass loss test
144
vcorr (mm/year)
Discussion
1.E+00
mass loss test Bertocci
vcorr (mm/year)
Lalvani
1.E-01
VM100 VM50 VM10
1.E-02 0 25 50 75 2 i AC (A/m ) 100
Figure 4.11 Expanded scale of the graph of Figure 4.10
4.2.5
Proposed Mechanism
It is evident that more than one of the proposed theories has to be considered giving rise to a mixed mechanism. The effect of AC corrosion processes can be summarised as follows: reversibility of cathodic and anodic processes: the process occurring during the anodic half cycle of the AC interfering signal may not be completely reversed during the cathodic half cycle; this may cause a serious modification of the double layer composition. In addition oxide or hydroxide layers may be formed or destroyed on the metal surface. Such modifications occurring at the metal/solution interface may heavily influence the corrosion kinetics leading to changes on the overpotentials and corrosion (or equilibrium) potential; normally the principal anodic process is metal dissolution while the principal cathodic one is either oxygen reduction or hydrogen evolution. In fact during anodic half-cycles, the gas evolution reactions (O2 or Cl2) are less likely to take place than the metal dissolution reaction, because of potential considerations. O2 or Cl2 evolution will only take place under the conditions of concentration polarisation. Similarly, in the cathodic half-cycles, the H2 evolution is more likely than metal deposition. Thus the quantity of electricity expended for dissolution of metal in the anodic cycle must be greater than the quantity of electricity expended for metal deposition in the cathodic cycle; the amount of metal dissolved is related by the Faraday law to the amount of charge exchanged during the anodic half period; the AC current efficiency is very low (CE% < 2% for carbon steel in simulated soil solution). As for any process, also electrochemical reactions are characterised by an 145
Discussion
induction time, during which the current is mainly used for the electrical charging of the metal/solution interface. Furthermore, for current densities higher than 50-100 A/m2 the system would reasonably be under conditions of concentration polarisation, leading to a considerable increasing of the overpotentials.
4.3 CORROSION MORPHOLOGY IN THE PRESENCE OF AC

All the tested metallic samples were followed by visual inspection in order to investigate the morphology of AC-induced corrosion. Four carbon steel samples were analysed by SEM-EDS. It was confirmed that the appearance of the corrosion may vary, depending on the duration of the interference and on the environmental conditions, from small point-shaped attacks to large deep local attacks with smooth round corrosion morphology. Actually the enhanced corrosion due to the influence of AC voltages tends to be of a localised nature. The large local attacks that can be revealed after long exposition time are in fact several pits that had coalesced. It was also observed that the corrosion localised as the AC increased. Therefore the actual penetration rates would be higher than the average corrosion rates evaluated by weight loss tests. The nature of the layers of corrosion products formed on the metal surface is quite different than the case of non-interfered samples or samples interfered by the sole DC. The AC-induced layers are thick, but non-adherent. They tends to detach from the surface exposing a bare and active metal surface to the solution and then a new thick, non-adherent layer forms underneath.
4.4 CARBON STEEL IN ALKALINE SOLUTION

Localised corrosion on carbon steel in alkaline media occurs if the molar ratio [Cl]/[OH] exceeds 0.6[57]. Considering that the pH of the testing solution is close to 12.6, the critical chlorides concentration, i.e. the chlorides concentration above which localised corrosion may take place, is about 24 mmol/L. In Figure 4.12 the obtained critical chlorides threshold as a function of AC densities for carbon steel in alkaline solution are summarised. The grey area refers to the chlorides content related to the localised corrosion initiation for the control samples (AC = 0). For control samples, the evaluated critical chlorides content was in the range of 1730 mmol/L. The tests on sample interfered by AC, confirmed that the AC current leads to an appreciable reduction of the critical chloride content.
146
Discussion
30 25 [Cl-] (mmol/L) 20 15 10 5 0 1 10 iAC (A/m )

Figure 4.12 Critical chlorides threshold as a function of AC densities for carbon steel in alkaline solution (pH = 12.6)
2
No AC
100
1000
The results can be summarised as follows: for the samples non-interfered by AC the corrosion initiated in the range of 1730 mmol/L chlorides. 17 mmol/L is slightly lower than the one reported in literature. That could be explained considering the sudden pH decreased (10 hour long during night time) that occurred during the test; AC > 40 A/m2: the critical chlorides threshold is lower than 15 mmol/L; AC > 350 A/m2: the critical chlorides threshold is lower than 10 mmol/L If similar results were confirmed in concrete tests, it would mean that in the presence of AC current the minimum critical chlorides threshold may decrease from 0.4% - 1% with respect to cement weight. The value 0.4% is considered the minimum chlorides value above which localised corrosion may occur on reinforcing steel in concrete structures exposed to atmosphere[57]. Since carbon steel in reinforced-concrete structures is not coated, it is not actually possible to reach high AC current densities. Therefore AC would be rarely harmful to bare rebars in alkaline and chlorides free concrete. In the presence of chlorides AC may induce an early corrosion initiation even with chlorides content lower than 0.4% or worsen a already started corrosion. High AC densities may arise in case of fusion bonded epoxy coated reinforcement.
147
Discussion
4.5 CATHODIC PROTECTION MONITORING

The scope of the cathodic protection (CP) monitoring is to verify the protection level of the structure by checking that the potential matches the protection criteria. The potential measurement is easy to carry out, but its interpretation may present some concerns in the presence of DC or AC stray currents. Cathodic protection monitoring in the presence of simultaneous AC and DC interference could lead to erroneous measurements, since IR drop contribution could heavily affect potential readings. Therefore to know the true potential (or true polarisation level), the ohmic drop contribution has to be eliminated. In literature there is lack of agreement about the correct procedure to measure the true potential in the presence of AC. In this section the results (Par. 3.7, pag. 127) of laboratory tests on cathodically protected carbon steel in simulated soil conditions will be discussed.
4.5.1
Field Monitoring Approach
In CP conditions, the effect of AC current on carbon steel in simulated soil conditions is the changing of potential toward more positive values (Par. 3.7, pag. 127, Par. 3.181, pag. 81, Par. 3.2, pag. 84) which may lead to partial protection condition. Therefore a higher current density should be applied in order to guarantee the cathodic protection of the structure. In the presence of DC anodic interference due to the presence of direct anodic stray currents and in freely corroding samples (as for example an unprotected pipeline), the effect of AC is the changing of the potential toward less positive values. The experiments in 4 g/L sodium sulphate solution showed that the potential can shift down to about 0.85 V CSE in correspondence of AC densities higher than 100 A/m2. This situation is very dangerous, since at such negative potentials no significant corrosion rate is usually expected, instead an anodic current density as high as 1 A/m2 was applied, corresponding to a corrosion rate of 1 mm/y. The comparison of the true potential obtained by ON-OFF technique and by means of a commercial potential probe[63] showed the difficulty to eliminate all the ohmic drop contributions due to DC since coating defects which have different size and therefore different polarisation levels would exchange current even after current switch-off. It was confirmed that AC > 30 A/m2 has a depolarizing effect on both anodically and cathodically polarised carbon steel in simulated soil conditions, misleading traditional potential measurement. Reliable measurements are then mandatory. The potential measurements performed by means of Luggin capillary and potential probe were in good agreement: the use of potential probes is a reliable approach to evaluate the true potential in the presence of stray currents when AC interference is present.
148
Discussion
This results are of paramount importance for field measurements, where neither a capillary nor ON-OFF technique can be used, the former because of practical complication, the latter because of spikes. By using a proper potential probe in association with an AC filtered acquisition voltmeter, the true potential of the steel coupon is measured and directly interpreted on the basis of the immunity potential criterion. Concerns may arise on the problem of which potential criterion should be adopted. In the specific case of cathodic protection of coating defects in buried pipelines influenced by induced AC current, the CP evaluation becomes complicated, and the usual potential criteria are no longer necessarily valid. Currently the European standard EN12954[66] is under modification in order to define the proper protection criteria in the presence of AC interference (i.e. AC density threshold and true potential). More experiments are needed to elaborate new potential criteria in order to evaluate the corrosion risks in the presence of AC by means of true potential readings.
149
Discussion
150
CONCLUSIONS
The influence of AC on corrosion of carbon steel, galvanised steel, copper and zinc under different experimental conditions was studied. The AC signals were supplied to freely corroding, anodically and cathodically polarised samples. Anodic polarisation simulated corrosion conditions of buried structures in the presence of galvanic coupling, typically with bare copper grounding systems, or structures interfered by stray DC. Cathodic polarisation simulated buried structures under various cathodic protection levels. The environments considered were: sulphate and chloride aqueous solutions, aerated or de-aerated conditions, alkaline solution (pH = 12.6) simulating soils with different electrical resistivity, seawater and concrete respectively. Tests on metal samples in 1 M solutions of their ions were also performed because in such conditions the metals were in equilibrium with their ions and the cathodic process was the inverse of the anodic one. Tests performed included: potential monitoring, polarisation curves, potentiodynamic tests, immersion tests, weight loss tests and visual inspection. The experimental data were also compared with the models proposed in literature. The analysis of the experimental results allowed to draw the following conclusions.
AC density threshold
The AC densities is considered the most important parameter in order to estimate the risk of AC induced corrosion: the higher the AC density, the greater the risks. Weight loss tests showed that already 10 A/m2 may be armful for carbon steel in soil simulated solution increasing corrosion nearly two-fold relative to the non-interfered samples. Such value is lower than the 20 and 30 A/m2 threshold value currently suggested by standards and laboratory tests[34,35,36]. More experiments are needed to evaluate the AC density threshold for the different metals on field.
Corrosion rate and AC current efficiency (CE%)

It was confirmed that AC corrosion is only a small percentage of what it would be with an equivalent DC density. AC current efficiency (CE%) for carbon steel in simulated soil solution is lower than 2% and therefore in good agreement with the values reported in literature which vary between approximately 0.1% and 5%[39,53].
Conclusions
CE% decreased as the AC density increased. Such results can be explained considering that, as for any process, also electrochemical reactions are characterised by their induction time. During the induction time the current is mainly used for the electrical charging of the metal/solution interface. Furthermore, for current densities higher than 50-100 A/m2 the system would be reasonably under conditions of concentration polarisation, leading to a considerable increasing of the overpotential. It was also observed that the CE% did not depend on the cathodic process involved or on the Tafel slopes ratio r = a/c and that did not change significantly with time. The comparison of the corrosion rates obtained by weight loss tests and by polarisation curves showed that, while the two methods gave very close corrosion rates for tests on non-interfered samples, for the tests in the presence of AC, instead, the values obtained by Tafel plot were significantly lower than those obtained by weight loss tests. Therefore, Tafel extrapolation to calculate icorr is not applicable in the presence of AC interference. Reason of this has to be further investigated. The Tafel plots allows therefore the evaluation of the effects of AC on kinetics parameters as Tafel slopes of cathodic and anodic processes, but does not allow a correct estimation of the actual metal dissolution in the presence of AC.
Influence of AC on Corrosion Kinetics

The polarisation tests on carbon steel, galvanised steel, zinc and copper confirmed that AC current has a strong influence on corrosion kinetics and on corrosion and equilibrium potential. The effects of AC on parameters as Tafel slopes and exchange current depends on the system studied and on the AC density supplied. A general decrease of overpotentials and increase of exchange current density were observed for the different test conditions. Such overpotential decreases would most probably persist for a while even if the AC is turned off. With the only exception of the tests in simulated soil solution, the corrosion or equilibrium potential decreased.
Proposed mechanism
The experimental results suggested that more than one of the theories proposed in literature should be considered giving rise to a mixed mechanism. The effect of AC corrosion processes can be summarised as follows: reversibility of cathodic and anodic processes: the process occurring during the anodic half cycle of the AC interfering signal may not be completely reversed during the cathodic half cycle; this may cause a serious modification of the double layer composition. In addition oxide or hydroxide layers may be formed or destroyed on the metal surface. Such modifications occurring at the metal/solution interface may heavily influence the corrosion kinetics leading to changes on the overpotentials and corrosion (or equilibrium) potential; 152
Conclusions
normally the principal anodic process during anodic half-cycles is metal dissolution while the principal cathodic one during the cathodic half-cycles is either oxygen reduction or hydrogen evolution. Thus the quantity of electricity expended for dissolution of metal during the anodic cycle must be greater than the quantity of electricity expended for metal deposition during the cathodic cycle; the quantity of metal dissolved is related by the Faraday law to the quantity of charge exchanged during the anodic half period; because of the short time of the anodic half cycle the current efficiency is very low: the current is mainly used for the electrical charging of the metal/solution interface. Furthermore, for current densities higher than 50-100 A/m2 the system would reasonably be under conditions of concentration polarisation, leading to a considerable increasing of the overpotentials; if there were a faradaic rectification, that wouldnt be the principal or unique effect of AC on corrosion phenomena; AC leads to the growth of thick but non-adherent films of corrosion product on the metal surface The nature, thickness and adhesion of the film changes with the AC density, the metal and solution composition; AC enhances localised corrosion. Large localised attacks after long exposure seemed to be coalesced pits.
Carbon steel in alkaline solution

Tests on carbon steel in alkaline solution showed that the AC current leads to an appreciable reduction of the critical chloride content. If similar results were confirmed in concrete tests, it would mean that in the presence of AC current the minimum critical chlorides threshold may decrease from 0.4%-1% with respect to cement weight, where 0.4% is considered the minimum chlorides value above which localised corrosion may occur on reinforcing steel in concrete structures exposed to atmosphere[57]. Since steel in reinforced-concrete structures is not coated, it is not actually possible to reach such high AC current densities. Therefore AC would be rarely harmful to bare rebars in alkaline and chlorides free concrete. In the presence of chlorides AC may induce an early corrosion initiation or worsen a already started corrosion. High AC densities may arise in case of fusion bonded epoxy coated reinforcement.
Cathodic protection monitoring

The potential measurement is easy to carry out, but its interpretation may present some concerns in the presence of DC or AC stray currents. Cathodic protection monitoring in the presence of simultaneous AC and DC interference could lead to erroneous measurements, since IR drop contribution could heavily affect potential readings.
153
Conclusions It was confirmed that AC > 30 A/m2 has a depolarising effect on both anodically and cathodically polarised carbon steel in simulated soil conditions, misleading traditional potential measurement interpretation. Potential measurements performed by means of a Luggin capillary and potential probe were in very good agreement: the use of potential probes is a reliable approach to evaluate the true potential in the presence of stray currents when AC interference is present. By the use of a potential probe in association with an AC filtered acquisition voltmeter, the IR drop free potential is measured. Concerns may arise on which potential criterion should be adopted. More experiments are needed in order to elaborate new potential criteria to evaluate the corrosion risks in the presence of AC.
154
ACKNOWLEDGMENTS
Vorrei ringraziare prima di tutti Marco Ormellese per la sua disponibilit e pazienza nel supportarmi nel lavoro e per avermi insegnato, assieme a MariaPia, Luciano e Fabio ad affrontare con pi filosofia i piccoli e grandi ostacoli che giorno dopo giorno si incontrano nel lavoro. Un caloroso pensiero va sicuramente a tutti i giovani e meno giovani che gravitano intorno al gruppo Pedeferri - Lazzari - Bertolini. Lavorare con loro stato sicuramente stimolante sul piano scientifico, ma la cosa pi preziosa stata il lato umano: credo che difficilmente si possa incontrare un gruppo di persone cos straordinarie. Parte del merito di questo miracolo va sicuramente al nostro grande capo Pietro, che dallalto della sua cattedra non si dimentica mai dei suoi giovani, anzi cerca sempre un modo per stimolarli e farli crescere. Con la sua simpatia e i suoi piccoli scherzi ci ricorda inoltre che per lavorare bene non bisogna certo dimenticarsi di sorridere. Non posso certo dimenticare tutti i baldi giovani che hanno collaborato durante questi tre anni: Alessandra Bianchi, Andrea Valenti, Davide Cusumano, Francesco Ficco, Giuseppe Festa e Michele Nistrio e gli impareggiabili tecnici Franco Traisci, Giorgio Iovino e Mario Tarantino. Alberto Sarto e Francesco Morganti sono stati un indispensabile aiuto nellultimo anno di duro lavoro. Li ringrazio sicuramente per la loro bravura, ma soprattutto per la simpatia (fa sempre piacere lavorare in allegria!). Marco Manera vince il premio per la pazienza, non si sa infatti come abbia fatto a sopportarmi per questi due anni di ufficio in comune, pare che non si lamenti neanche! Poi ci sono i compagni del XVII ciclo con i quali ho avuto il piacere di dividere questa stimolante esperienza. Anche tra di loro ho trovato grande simpatia, disponibilit e soprattutto solidariet nei momenti difficili. Per non parlare poi della professoressa Chiara Castiglioni, alla quale tutti noi giovani dottorandi in Ingegneria dei Materiali dovremmo fare un monumento. Un particolare ringraziamento va anche ai professori Zaninelli e Ottoboni per il contributo dato nella messa a punto del circuito elettrico. Poi sarebbe doveroso spendere una parola per tutti i miei amati amici e parenti, ma non la finirei pi per cui mi limito a ringraziarli di cuore per essermi stati vicini, per avermi sopportata negli ultimi mesi e soprattutto per far parte della mia vita.
156
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L.Bertolini, F.Bolzoni, T.Pastore, P.Pedeferri, Stray Current Induced Corrosion in Reinforced Concrete Structures, Progress in the Understanding and Prevention of Corrosion, Eds. J.M.Costa, A.D.Mercer, Institute of Materials, London, 1993, pp. 658-664 H. Kaeshe, Metallic Corrosion Principles of Physical Chemistry and Current Problems, Published by National Association of Corrosion Engeneers, 1996 ASTM G1-03, Standard Practice for Preparing, Cleaning and Evaluating Corrosion Test Specimens, ASTM International, 2003 R.L Shreir, R.A Jarman, G.T. Burstein, Corrosion Metal/Environment Reactions, third edition, Butterworth Heinemann, 2000 L. Lazzari, M. Ormellese, MP. Pedeferri, New Probe for CP Potential Monitoring in Soil, CORROSION/02, NACE expo, Denver Colorado, Paper 105, 2002 P. Pedeferri: Corrosione e protezione dei materiali metallici, Edizioni Citt Studi, Milano 1978 G. Bianchi, F. Mazza: Corrosione e protezione dei metalli, Masson, Milano 1989 EN 12954: Cathodic Protection of Buried and Immersed Metallic Structures- General Principles and Applications for Pipelines
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Politecnico di Milano Dipartimento di Chimica, Materiali e Ingegneria Chimica, G.

INFLUENCE OF ALTERNATING CURRENT ON METALS CORROSION

Ph.D. Thesis in Materials Engineering XVII Course

1.2.1 1.2.2 1.3 1.4 1.5

1.8.1 1.8.2 1.8.3 1.8.4 1.8.5

Experimental Procedure ........................................................................................58

Experimental Procedure ........................................................................................ 60

2.5.1 2.5.2 2.5.3 2.6 2.7

2.7.1 2.7.2 2.7.3

2.8.1 2.8.2 2.9 3 3.1 3.2

3.2.1 3.2.2 3.2.3 3.3

0.4 g/L Sodium Sulphate Solution.................................................................................... 90 Simulated soil solution...................................................................................................... 92 III

3.7.1 3.7.2 3.8 4 4.1 4.2

4.2.1 4.2.2 4.2.3 4.2.4

Conductor Current lines

1.2 DIRECT CURRENT (DC) INTERFERENCE

Interfered Pipeline Groundbed Interference current

Corrosion attacks T/R

Figure 1.2 - Scheme of stationary interference between two crossing pipelines[11]

protection potential time

Rail I R rail Pipeline i R pipe

Figure 1.5 - Electrical scheme of non-stationary interference

Metallic Structures Interfered by DC

O2 + 2 H2O + 4e- = 4 OH2H2O + 4e- = H2 + 2OH-

Eq. 1.2 Eq. 1.3

Figure 1.6 - Interference on metallic structures[11]

or when the structures ohmic drop is ignored:

E C Iint erf L str

Iint erf C'

Maximum Allowable Interference

1.3 CASE HISTORIES OF AC-INDUCED CORROSION

Figure 1.8 - AC potential and defects distribution[19]

1.4 MORPHOLOGY CHARACTERISTICS OF AC CORROSION

Possibility of coating disbondment

Figure 1.10 - Specific characteristics of AC corrosion[12]

1.5 ALTERNATING CURRENT INTERFERENCE

60 AC Voltage (V) 50 40 30 20 10 0 0 5 10 15 20 25 30 Distance (km)

Magnetic induction (coupling)

Evaluation of induced peak voltage

Tab. 1.1 Values of the coefficients in Equation 1.11[27]

Double circuit vertical Like phasing Reversed phasing 0.10 0.015

Steady-State or Load Conditions

. Very low soil resistivity

1.6 CHARACTERISATION OF AC-INDUCED CORROSION

1.7 CORROSION RATE

Peak cell voltage (mV)

Test Category Low AC + No CP High AC + No CP

Actual CP shift (mV) 0 0 <150 >150 <150 >150

Relative (to control specimens) corrosion rate

600 500 400 300 200 100 0

Low AC + Low CP Low AC + High CP High AC + Low CP High AC + High CP

1.8 EVALUATION OF CORROSION RISKS AND CATHODIC PROTECTION MONITORING

DC Potential Measurements in the Presence of AC

Voltmeter E Reference electrode

Soil (or electrolyte)

Figure 1.16 - Potential measurement

Initial Vcorr Steady State Vcorr

AC Density/DC Density Ratio

Cathodic Protection Criteria Based on AC and DC Densities Measured by Coupons

25 10 25 1 DC Corrosion 0.1 0.01 0.1 1 10 20 100 Protection Overprotection

Size of the Coating Defects

d A insulating coating holiday h Rch Reh = Rh

Figure 1.20 Spread resistance or holiday resistance Rh to remote earth