Electrochemical Techniques for

Measuring Corrosion Rates in

Outline
Operating Oil and Gas Pipelines
• Introduction
Sankara Papavinasam • Electrochemical Measurements in the Field
CANMET Materials Technology Laboratory
183 Longwood Road South – Corrosion Potential Measurements
Hamilton, Ontario, Canada – General Corrosion Rates
Phone: 905-645-0742
Email: spapavin@nrcan.gc.ca – Pitting Corrosion Rates
• Summary
Presented at NACE 2011/097X Electrochemical Techniques
- Technical Information Exchange, March 13, 2011

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Introduction Cause - Pitting Corrosion

• Integrity Management
– Risk Assessment
– Risk Management
• Main Risk for Producing Pipelines
– Internal Pitting Corrosion
• Based on Estimation of Risk
– Corrosion Control Strategies
• Monitoring Corrosion - Important

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 Consequence – Oil
Leakage Corrosion Monitoring
Improved safety
Reduced downtime
Early warning before costly serious damage sets in
Reduced maintenance costs
Reduced pollution and contamination risks
Longer intervals between scheduled maintenance
Reduced operating costs and
Life extension

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Objectives Monitoring Internal Corrosion

• Monitoring Techniques • Direct Intrusive Measurement Techniques
– Access the Reliability • Direct Nonintrusive Measurement
– Real-Time Monitoring Techniques
– Standardize Analysis Procedure • Indirect On-line Measurement Techniques
• Indirect Off-line Measurement Techniques
NACE Report 3T199: Techniques for Monitoring
Corrosion Related Parameters in Field Applications.

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 Pipeline Integrity Internet Icon (PICon) - Survey
Monitoring Internal Corrosion (http//:www.nrcan.gc.ca/picon)

• Direct Intrusive Measurements Techniques

Electrochemical Techniques the Companies
– Physical techniques
Use for Pipeline Monitoring

Number of Responses
• Mass loss coupons
• Electrical resistance (ER) 25

• Visual Inspection 20

– Electrochemical Techniques 15

• DC techniques 10

– Linear polarization resistance 5

– Zero-Resistance Ammeter (ZRA) (Same or different alloy) 0

– Potentiodynamic/Galvanodynamic polarization

e
S

ic
se
R

ic

ila

m
EI
– Electrochemical noise

LP

on
m
oi

Sa
im
na
N

m
• AC techniques

A-
iss
dy

ar
ZR

H
-D
tio
– Electrochemical impedance spectroscopy (EIS)

ten

A
ZR
– Harmonic distortion analysis

Po
Electrochemical Techniques

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Main Differences in Using

Corrosion Monitoring Techniques Electrochemical Techniques in the
Laboratory and in the Field
Electrochemical Parameters Laboratory Field
• Time Averaged Corrosion Rates Counter electrode Platinum or graphite – two Normally made of the same
electrodes material as that of working
– Mass Loss electrode

• Instantaneous Corrosion Rates Reference electrode Standard reference electrode

(reversible)
Normally made of the same
material as that of working
electrode
– Linear Polarization Resistance
Tafel constants Determined by Tafel Normally assumed
– Electrochemical Impedance Spectroscopy extrapolation method

Luggin capillary Used Not used

• Continuous Monitoring Corrosion potential Measured and reported Only stable values are
against standard reference noted.
– Electrochemical Noise electrode

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 Equations to Convert Electrochemical Measurements
into Corrosion Rate

 V 
Rp   
 I  E corr

B
I corr 
Rp

a . c
B
2 .303 ( a   c )

1   a . c 
I corr   
RP  2. 303   a   c  

26
I corr 
Rp

Ref: ASTM Standard Guide for

On-line Monitoring of Corrosion
in Plant Equipment (Electrical and
Electrochemical Methods)
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Fig.6: Percentage Error in Calcuating icorr assuming a B value of 26

Values of Constant “B” for the Polarization Resistance Method
200

Corroding System βa, mV βc, B, mV

mV 150
30 30 6.5
30 60 9 100
30 120 10
30 180 11
Percentage Error

30 x 26 50
60 60 13
60 90 16
0
60 120 17
Theoretical
60 180 20
(Values of B calculated from arbitrary
60 x 26 -50
βa and βc values using formulae given
90 90 20
in Eqns. 9 and 10; βa and βc values can
90 120 22
be interchanged).
90 180 26 -100
90 x 39
120 120 26
-150
90 x 39
120 120 26
120 x 52 -200
180 180 39 0 20 40 60 80 100
180 x 78
Actual B Values
S.Papavinasam, Chapter 3: “Electrochemical Polarization Techniques”, in “Techniques for Corrosion
Monitoring”, Ed. L.Yang, Woodhead Publishing Limited, ISBN, 1-84569-187-3, p.47 to 85

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 Importance of Corrosion Field Measurements Corrosion
Potential Potentials - Conditions
Location Units Horizontal Horizontal Horizontal sour
• Fundamental parameter in the laboratory sweet sour (Pipe C)
(Pipe A) (Pipe B)
experiments Water M3 12.8 211 125
Oil M3 1.2 5.9 2.3
• All electrochemical knowledge developed based Gas 106 m3 46.6 1.4 -
on laboratory experiments Temperature oC 20 58 15
Pressure (total) psi 50 319 130
• Corrosion potential is a basic input units in many Partial pressure of psi 0 2 2
electrochemical models. H2S
Partial pressure of psi 0 4 4
CO2
Pipe OD in. 8 3 3
Pipe thickness in. 0.500 0.413 0.413

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Reference Electrode
Measurement of Pipe Internal
Potential
• Ag/AgCl reference electrode
– Retractable Reference Cell
– Operates up to 260oC (500oF)
– Pressure of 1500 psi.

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 Reference Element

reference electrode lead

reference electrode
assembly pipe lead

Photo showing internal potential measurement at CCN site.

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Corrosion Potential in Pipe A – 8 Inches Diameter –

power cord from Immediately after Introduction of the Reference Electrode
DC to AC inverter
-0.4
Potential vs Ag/AgCl (V)

-0.5

8 double or 16 single
channels board
-0.6

leads -0.7

-0.8
0 100 200 300 400 500 600
Time (sec)
Pipe potential measurement and acquisition setup

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Corrosion Potential in Pipe A – 8 Inches Diameter – Variation of Corrosion Potential due to Fouling
After 2 hours

-0.1
-0.20

Pipe potential vs Ag/AgCl (V)

-0.2
-0.28
Potential vs Ag/AgCl (V)

-0.3
-0.35

-0.4
-0.43

-0.5
-0.50

-0.6
-0.58
0 20 40 60 80 100 120 140 160
-0.7
0 100 200 300 400 500 600 Res ide nce time (min)

Time (sec)

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Solid junction was impregnated with potassium

Delrin prevents fouling chloride

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 Corrosion Potential in Pipe B – 3 Inches
-0.45
Measurement of Corrosion Potential in the
Field
-0.46
– Corrosion potential - important input for
electrochemical model.
Potential vs Ag/AgCl (V)

-0.47

– Laboratory measurement - Routine

-0.48 – Field measurement - Tedious

-0.49
Demoz, A.; Papavinasam, S.; Michaelian, K.; Revie, R.W., “Measurement of corrosion
potentials of the internal surface of high-pressure operating oil and gas pipelines”; Journal
of ASTM International, Vol.5, No.6., 2008 (June), Paper ID JAI 101244

-0.5
0 10 20 30 40 50 60 70
Time (min)

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Probe Insertion Process

Reliable Corrosion Measurement

Probe Location
Surface condition of sensor element
Metallurgy of the probe
Number of probes and monitoring
techniques
Correlation of monitoring data with pipeline
operating conditions. High Pressure access fitting Retrieval tool for removing
for insertion of corrosion probe corrosion probes under pressure
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 Schematic Diagram Indicating
Coupon Positions

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Photo of Coupons with Electrical Connections

Corrosion Coupons

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Schematic Diagram of a Typical Three-Electrode LPR Probe
LPR Probe

ASM Handbook Volume 13: Corrosion, Chapter: In-service Monitoring” Fig.5

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LINEAR POLARIZATION RESISTANCE

METHOD Field Operating Conditions
Conditions Gassy-Oil Field Oily-Gas Field Oil-Transmission Field
Gas composition 20% H2S + 2.5% CO 2, balance hydrocarbon Less than 0.5% H2S +
2.5% CO 2
Water Chemistry Similar Low water-cut, 0.5%
Temperature 60 55 55
Pressure, psi 250 250 Low
Replaceable
section diameter, 6 10 10
inches
Gas production 16.7 x103 122 x 103 Low
rate, m3/D
Oil production 48.5 27.96 High
rate, m3/D
Water production 170 31.3 Low
rate, m3/D
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 Inhibitors Schematic Diagram of Pipe Loop

Concentrations Tested
Inhibitor Inhibitor Inhibitor
Type Characteristics Gassy-Oil Field Oily-Gas Field Oil-Transmission
Field
#1 Continuous Water soluble 0, 50, 100, 200 Not Used Not Used
#2 Batcha Oil soluble, 0, 2000 Not Used 0, 2000
water
dispersible
Coupon Ladders
#3 Continuous Water soluble 0, 50, 100, 200 Not Used Not Used
#4 Batch Oil soluble 0, 2000 Not Used Not Used
#5 Continuous Not known Not Used 0, 100, 250, Not Used
500, and 1000
#6 Batch Not known Not Used 0, 5000 Not Used
a
Can Also Be Used as Continuous Inhibitor.

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 General Co rro sio n Rat e ( LP R T echnique) - 0 ppm
Measuring Techniques
150

120 Ladder A

Corrosion Rate, mpy

• Mass Loss 90
Ladder B
Ladder C
– Initial and Final Readings 60

• LPR and EIS 30

– Instantaneous Corrosion Rates 0

0 10 20 30 40 50
• Electrochemical Noise Duration, Days

– Corrosion Rates Based on Fixed Data Points

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Typical Electrochemical Noise Data, No Inhibitor

500 10
Mean Current, uA

General Corrosion Rate (LPR Technique) - 2000 ppm Std. Deviation of Current, 10e-6
Mean Potential, mV
150 Batch Inhibitor 250
Corr. Rate, mpy
8
Curren t m A or Po ten tial mV

120
C o r r o s io n R a te , m p y

Co rr. Rate, mp y

Ladder A
0 5
90 Ladder B
Ladder C
60
-250 3

30

0 -500 0
0 1 2 3 4 5 6 7 8 9
0 10 20Duration, Days30 40 50
Duration, Days

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 Variation of Corrosion Rate after Treating with Corrosion
Inhibitors as Determined by Electrochemical Noise Measurement

5
Corrosion Rates as Determined by EIS, No Inhibitor

4 60
C o rro s io n R ate , m p y

C o rro sio n R a te, m py

50
3 40
Ladder A

30 Ladder B

Ladder C

2 20
10
1 0
0 5 10 15 20 25 30 35 40
Duration, Days
0
0 5 10 15 20 25 30 35

Duration, Days
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Corrosion Rates on Individual Coupons as Measured by Various Techniques

EIS Issues in the Field 100

Oil Transmission Field

80
• Wide Frequency .
Corrosion Rate, mpy

wt.loss
Range 60 LPR,mean
EIS, mean
• Longer Duration Noise,mean
40
• Physical Models
• Data Analysis 20

0
l1 l1 l1 l1 l 2 al 2 al 2 al 2 A
h,
B D
ria ia ia ia ia i i i h, h,
,T Tr Tr Tr Tr , Tr , Tr , Tr tc tc tc
A B, , C, ,D, A,
B C D Ba Ba Ba
0, 0, 0 0 0, 0, 0, 0,
Inhibitor, Ladder Position
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Ranking of Measuring Techniques Based
on General Corrosion Rates
• Three Positions
– Top, Middle, Bottom
• Eight Coupons/Electrodes/Position
• Corrosion Rates Averaged per Position
• Variation of Corrosion Rate with Inhibitor
Concentration at Each Position
• Standard Trend = Most Repeated Trend
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Ranking of Measuring Techniques Based
on General Corrosion Rates
• Method 1
– 0 ppm > 50 ppm > 100 ppm > 200 ppm
• Method 2
– 0 ppm > 50 ppm > 100 ppm > 200 ppm
• Method 3
– 50 ppm > 0 ppm > 100 ppm > 200 ppm
• Most Repeated Trend
– 0 ppm > 50 ppm > 100 ppm > 200 ppm
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Ranking of Measuring Techniques Based Ranking of Measuring Techniques Based

on General Corrosion Rates on General Corrosion Rates
• The Trends Exhibited Techniques
• Electrochemical Noise (91 %)
Compared with the MRT
• Weight Loss (89 %)
• Technique with Closest Agreement with
MRT most Accurately Depicts Field • LPR (70 %)
Corrosion Rate • EIS (33 %)
• Example
S.Papavinasam, M.Attard, R.W.Revie, A.Demoz, and K.Michaelian, Comparison of Techniques for
– Method 1 and 2: 100 % Monitoring Corrosion Inhibitors in Oil and Gas Pipelines, NACE C orrosion, 59(12), p.1096 (2003).

– Method 3: 50 %
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 Photograph of Coupons After 15-
Measuring Techniques for Pitting
Day Field Exposure
Corrosion Rates

• Pit Measurements
– By Micrometer
– By EIS Analysis
– By Electrochemical Noise Analysis

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Typical Pit Distribution on Coupons

Photographs before & after cleaning 1.2

Working Electrode
After Cleaning 0.8
Pit Depths, mm

Counter Electrode

Reference Electrode
0.6

0.4

0.2
Before Cleaning

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 R2 Values for the Correlation Between Measured Pits
Vs. Pitting Corrosion as Indicated by Noise
Noise Pitting Analysis Measurements
1

• Pitting Index 0.8

Noise Pit Indicators

PI = dI/Imean 0.6

• Pitting Factor 0.4

Pit Indicator
Pitting Index
Pitting Factor
PF = [Δi(1) + ... + Δi(N)]/n . σi/Irms]
0.2
• Pit Indicator
0
Pit Indicator = STDnoise/Meannoise 0,
B
0,
A
0,
C
0,
A
0,
C
0,
A
0,
C
0,
A
0,
C
0,
A
0,
C
0,
A
0,
D
0,
B
0, ,10 ,10 20 ,20 05 ,05 10 ,10 20 ,20 200 200 200
1 1 1, 1 3, 3 3, 3 3, 3 2, 2, 4,
ASTM G199 Experimental Conditions

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Noise Response of Coupon in Ladder C in the Presence of

#3 Inhibitor at 200 ppm Concentration

Pit Indicator 20 1

• No Maximum Value 16 Pit Indicator 0.8

PF
Pit Indicator and Pitting Factor

– Unlike the Pitting Index Pitting Index

• Better Correlation with the Actual Pit 12 0.6

Pitting Index

Measurement
• Theoretical Correlation with the Events Occurring 8 0.4
No pits measured
during Pitting
4 0.2

0 0

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 Summary
• General Corrosion Rates
– Bottom > Middle > Top
– Weight Loss and EN Show Similar Trends
– LPR Measurements are Generally Reliable
– EIS Measurements Could not be Reliably
Obtained
• Pitting Corrosion Rates
– Pitting Index, Pitting Factor, and Pit Indicator
– Pit Indicator has the Best Correlation in Most
Cases
– Sometimes No Pits, but Noise Parameters Show
Pitting
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