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CORROSION MEASUREMENT

UNIT-5
CHE-545-172
DR IME B.OBOT

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Methods of Determining Corrosion Rates
• Weigh Loss
• Weight Gain
• Chemical Analysis of Solution
• Gasometric Techniques
• Thickness measurements
• Electrochemical techniques: Polarization
Resistance; Tafel Extrapolation; Potentiodynamic
Polarization and Electrochemical Impedance
Spectroscopy.

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Weigh Loss
• Metal samples are weighed.
• They are immersed into
aggressive corrosive medium.
• The previously weighed metal
samples are removed at
various time intervals.
• Metal samples are cleaned
before final weight are
determined.
• Weight Loss due to metallic
corrosion (per unit area) are
determined after final weight.

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Calculation of corrosion rate using
weight loss data
• The average corrosion
rate can be calculated as
follows:
• Corrosion rate = (K ×
W)/(A×T×D)
• Where K is a constant
• W is weight (mass)
loss(g)
• T is exposure time (h)
• D is density (g/cm3)
• A is area in cm2.
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EXAMPLE

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Coupons Types

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STANDARDS

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Weight Gain
• Not useful in aqueous corrosion.
• Suited for dry oxidation where oxide films or
products are more adherent than in the case
of aqueous corrosion.
• Gain in weight can be measured continuously
without removing corrosion products and the
specimens from the environment.
• Not very popular.

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Chemical Analysis of Solution
• A coupon is immersed in an electrolyte.
• The cation dissolves into the electrolyte.
• Solution becomes concentrated with the cation with time.
• Some aliquot are withdrawn with time for chemical analysis.
• Corrosion rate is then calculation.
• Calorimetric techniques, Atomic
Absorption spectrophotometry are used.

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Gasometric Techniques
• Coupons are immersed
in electrolyte.
• Hydrogen evolution is
measured.
• The volume of
hydrogen produced is
converted to corrosion
rate.

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Example
• If the rate of hydrogen evolution is 16.1 ml H2
(STP)/cm2/h in HCl, calculate the weight loss
of aluminum in g/m2/h.
• At STP, 1 mol of a gas occupies 22.4 L, Thus:

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Thickness measurements
• Measurement of thickness with time.
• Not a laboratory method of corrosion
measurement.
• Use in the industry to survey practical corrosion
in service.
• Use to track the progress of corrosion in rail road
hopper cars, storage tanks and pipelines.
• Based on the response of a metal specimen to
an ultrasonic or magnetic signal.

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Electrochemical techniques of
Corrosion measurements
• Electrochemical corrosion techniques are essential in
predicting the service life of metallic components used in
chemical and construction industries.
• They measure the corrosion rates, the oxidizing power of the
environment, and evaluate the effectiveness of corrosion
protection strategies.
• Direct current (dc) Techniques: Linear polarization
Resistance, Tafel Extrapolation and Open Circuit potential
(OCP vs Time).
• Alternating Current (ac) Techniques: This technique uses
alternating current to measure frequency-dependent
processes in corrosion and estimates the change of
polarization resistance. Example Electrochemical Impedance
Technique. 13
Electrochemical techniques of
Corrosion measurements
• LINEAR POLARIZATION
• In linear polarization measurements, the current is measured at potentials between 10 and
20 mV in cathodic and anodic direction from the equilibrium potential.
• The dependence of current vs. potential in this potential range is linear and the slope dE/dI
represents the polarization resistance.
• The corrosion current is calculated using the Stern-Geary equation for known values of the
anodic and cathodic Tafel slopes.
• TAFEL EXTRAPOLATION
• The Tafel extrapolation method provides a direct measurement of the corrosion rate and
the corrosion potential.
• It measures extremely low corrosion rates with an accuracy compared to that of weight
loss methods.
• Tafel technique is advantageous in evaluation of corrosion inhibitors and in comparison of
corrosion characteristics of alloys.
• This is a destructive technique due to a large polarization range required to complete the
polarization.
• Because the surface properties of the corroding metal change during polarization, it is
necessary to use new specimens to complete the corrosion evaluation studies.
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Electrochemical techniques of Corrosion measurements
• OCP vs TIME
• Measurement of the OCP as a function of time provides a qualitative method to
evaluate the stability of sacrificial coatings.
• The removal rate of a sacrificial coating in corroding solution is controlled by the
potential difference between the underlying metal and the sacrificial coating, the
severity of the corroding solution, and the thickness of the coating.
• The OCP reaches the value for the protected metal when the sacrificial coating is
completely removed from its surface.
• EIS TECHNIQUE
• Used in corrosion research to estimate the corrosion rates and to study the
passivation of metals, the corrosion protection provided by inhibitors, sacrificial and
barrier properties of electrodeposited coatings, and performance of polymer coatings
such as paints.
• Used to estimates the polarization resistance.
• As in the case of the linear polarization technique, the corrosion current is calculated
using the Stern-Geary equation for known values of anodic and cathodic Tafel
slopes.

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POLARIZATION METHODS

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Polarization Resistance

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Polarization Resistance
• Non-destructive method.
• For reactions under activation control, the
polarization resistance RP can be related to the
corrosion current by:
• Stern Geary Equation:
• Icorr = B/Rp
• B=babc/2.303(ba+ bc)

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Deriving the Stern Geary Equation
𝒊𝒄𝒐𝒓𝒓 = 𝒊𝑶,𝑴 = 𝒊𝑹,𝑯
 Rate of oxidation reaction equals rate of reduction reaction @ Ecorr
 When electrode is polarized, 𝒊𝒄𝒐𝒓𝒓 = 𝑬𝒂𝒑𝒑 − 𝑬𝒄𝒐𝒓𝒓

𝑖𝑂,𝑀
𝐴𝑛𝑜𝑑𝑖𝑐 𝑜𝑣𝑒𝑟𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑐𝑎𝑛 𝑏𝑒 𝑔𝑖𝑣𝑒𝑛 𝑎𝑠: 𝜂𝑎 = 𝑏𝑎 𝑙𝑜𝑔 ; 𝑏𝑎 is anodic Tafel
𝑖𝑐𝑜𝑟𝑟
slope (1)
𝑖𝑅,𝐻
𝐶𝑎𝑡ℎ𝑜𝑑𝑖𝑐 𝑜𝑣𝑒𝑟𝑝𝑜𝑡𝑒𝑛𝑡𝑖𝑎𝑙 𝑐𝑎𝑛 𝑏𝑒 𝑔𝑖𝑣𝑒𝑛 𝑎𝑠: 𝜂𝑐 = 𝑏𝑐 𝑙𝑜𝑔 ; 𝑏𝑎 is anodic Tafel
𝑖𝑐𝑜𝑟𝑟
slope (2)
Assigning a positive sign for anodic Tafel slope, ba, and negative sign for the
cathodic Tafel slope, bc, and rearranging

𝒊𝑶,𝑴 𝜼𝒂 𝒊𝑹,𝑯 𝜼𝒄
𝒍𝒐𝒈 = (3) and 𝒍𝒐𝒈 =– (4)
𝒊𝒄𝒐𝒓𝒓 𝒃𝒂 𝒊𝒄𝒐𝒓𝒓 𝒃𝒄

Rearranging (3) and (4), we obtain


𝜼𝒂
𝒊𝑶,𝑴 – 𝜼𝒃𝒄𝒄 𝒊𝑹,𝑯
𝟏𝟎 𝒃𝒂 = (5) and 𝟏𝟎 = (6)
𝒊𝒄𝒐𝒓𝒓 𝒊𝒄𝒐𝒓𝒓 19
Sum of anodic and cathodic currents equals the measured current, imeas, as
provided in (7)
𝜼𝒂 𝜼𝒄

𝒊𝒎𝒆𝒂𝒔 = 𝒊𝒄𝒐𝒓𝒓 (𝟏𝟎 𝒃𝒂 − 𝟏𝟎 𝒃𝒄 ) (7)

Solving the power series for small values of x (where x represents the power
of 10 in equation (7), we can derive:
𝜼𝒂
𝜼𝒂
𝟏𝟎 𝒃𝒂 = 𝟏 + 𝟐. 𝟑 (8)
𝒃𝒂
𝜼𝒄
– 𝜼
𝟏𝟎 𝒃𝒄 =𝟏− 𝟐. 𝟑 𝒂 (9)
𝒃𝒂
Substituting (8) and (9) into (7),
𝒃𝒂 + 𝒃𝒄
𝒊𝒎𝒆𝒂𝒔 = 𝟐. 𝟑 𝒊𝒄𝒐𝒓𝒓 𝜼 (10)
𝒃𝒂 𝒃𝒄
𝜼 𝒃𝒂 𝒃𝒄
= (11)
𝒊𝒎𝒆𝒂𝒔 𝟐.𝟑 𝒊𝒄𝒐𝒓𝒓 (𝒃𝒂 + 𝒃𝒄 )

𝜼 Δ𝑬
But 𝑹𝒑 =
𝒊𝒎𝒆𝒂𝒔 Δ𝑰

𝒃𝒂 𝒃𝒄 𝟏
𝒊𝒄𝒐𝒓𝒓 = (12) ----------------- The Stern Geary Equation
𝟐.𝟑 (𝒃𝒂 + 𝒃𝒄 ) 𝑹𝒑
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EXAMPLE

The polarization data for Ni in a solution, given in the above plot, were obtained
by scanning the coupon 20 mV from Ecorr. The area of the coupon is 1 cm2, bc and
ba are 0.1 V, and Ecorr - 0.218V vs. SCE. The polarization resistance obtained from
the plot is Rp = ΔE/Δi = 3.8797 mV/(μA/cm2). Using the equivalent weight and the
density for nickel of 8.9 g/cm3, calculate the corrosion rate for nickel in mpy by
using the Stern-Geary equation.
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Using the Stern Geary Equation

𝒖𝑨
𝒃𝒂 𝒃𝒄 Δ𝐢 𝟎.𝟎𝟏 𝑽 𝒄𝒎 𝒎𝑽 𝒖𝑨
𝒊𝒄𝒐𝒓𝒓 = = X 𝑿 𝟏𝟎𝟎𝟎 = 𝟓. 𝟔𝟎
𝟐.𝟑 (𝒃𝒂 + 𝒃𝒄 ) Δ𝑬 (𝟎.𝟒𝟔 𝑽) 𝟑.𝟖𝟕𝟗𝟕 𝒎𝑽 𝟏𝑽 𝒄𝒎

𝟎. 𝟏𝟑𝟏 𝑿 𝑰𝒄𝒐𝒓𝒓 𝑿 𝑬𝑾
𝑪𝑹 =
𝒅

𝒖𝑨 𝟔𝟗𝟑𝟒𝒈
𝟎. 𝟏𝟑𝟏 𝟓. 𝟔𝟎 𝑿 [𝟓𝟖. ]
𝑪𝑹 = 𝒄𝒎𝟐 𝒎𝒐𝒍 = 2.418 mpy
𝒈
𝟖. 𝟗
𝒄𝒎𝟑

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CORROSION POTENTIAL MEASUREMENTS AS A FUNCTION OF
TIME (OCP VS. TIME)
 Prior to corrosion monitoring, it is pertinent to perform an open circuit
potential (OCP measurement
 Necessary to stabilize the corrosion system and ensure an equilibrium status
wherein anodic and cathodic reaction rates are assumed to be constant
 More positive OCP value indicates more nobility of metal and less
susceptibility to corrosion

Open circuit potential vs. time of


various coatings on steel in 0.5 M
Na2SO4+0.5 M boric acid solution at
a pH of 7.0

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Tafel Extrapolation

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Deriving the TAFEL Equation
From Butler – Volmer equation,
𝜶𝒏𝑭 𝑬 −𝑬𝒐 𝟏−𝜶 𝒏𝑭 𝑬 −𝑬𝒐 𝜶𝒏𝑭 𝑬 −𝑬𝒐

𝒊𝒏𝒆𝒕 = 𝒊𝒄𝒐𝒓𝒓 𝒆 𝑹𝑻 −𝒆 𝑹𝑻 ; 𝒊𝒏𝒆𝒕 = 𝒊𝒄𝒐𝒓𝒓 𝒆 𝑹𝑻 (1)
𝟏−𝜶 𝒏𝑭 𝑬 −𝑬𝒐 𝜶𝒏𝑭 𝑬 −𝑬𝒐 𝟏−𝜶 𝒏𝑭 𝑬 −𝑬𝒐
− −
𝒆 𝑹𝑻
| 𝒊𝒏𝒆𝒕 | = 𝒊𝒄𝒐𝒓𝒓 𝒆 𝑹𝑻 −𝒆 𝑹𝑻 ; |𝒊𝒏𝒆𝒕 | = 𝒊𝒄𝒐𝒓𝒓 𝒆 (2)

Equation (1) with respect to anodic current while (2) with respect to cathodic current
Taking log of both sides for equation (1);
𝛼𝑛𝐹
log 𝑖 = log 𝑖𝑜 + 2.303 𝑅𝑇 𝐸 − 𝐸𝑜 (3)

𝜂𝑎 = 𝑏𝑎 𝑙𝑜𝑔 𝑖
𝑖
(4)  Cathodic current can be
𝑜 treated likewise so that
2.303 𝑅𝑇
𝑏𝑎 = (5) cathodic Tafel slope and
𝛼𝑛𝐹
cathodic overpotential can be
Equation (4) can be re-written as:
expressed in terms of
𝜂𝑎 = 𝑎 + 𝑏𝑎 log 𝑖 (6) cathodic current.
2.303 𝑅𝑇
Where 𝑎 = − log 𝑖𝑜 25
𝛼𝑛𝐹
Tafel Method We can only measure the net current across
the specimen electrode – at the corrosion potential there is no
net current (only local anode – cathode currents which constitute
the corrosion current). We cannot measure corrosion rate
directly, though we need icorr.
Measure potential and current at some distance on either side of
Ecorr – extrapolate E - log i curves (in same quadrant) back to Ecorr

Plot of the total current
(iT = io + ic) versus
potential showing the
extrapolation of the
Tafel regions to the
corrosion potential,
Ecorr, to yield the
corrosion current, icorr.
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Passivation
Under certain conditions of potential and pH, some
metals form protective films, i.e., they passivate
Pourbaix diagram for the
iron/water/dissolved
oxygen system showing
the effect of potential in
moving the system from a
corrosive (active) region
(point 1) to a passive
region (point 2)
We can exam the kinetics
using a potentiodynamic
scan and Evans diagram

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The polarization curve for the anodic reaction of a passivating
metal drawn for potentials more noble than the equilibrium
potential (Ee)a

Oxidative dissolution of oxide (e.g.,


Cr2O3  CrO42-)

(Ee)M/MO is the equilibrium potential


“Flade”
for oxide/hydroxide formation

Tafel region
(icrit is min. reaction rate required to
initiate film growth by precipitation
of Mn+)

The region attained by the metal in a given environment depends upon the
cathodic reaction i.e., where the cathodic curve cuts the above anodic curve.
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Tafel Extrapolation

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Tafel Extrapolation

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Tafel Extrapolation

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Calculating corrosion rate from the corrosion current
 Corrosion current can be used to determine the amount of corroded material
 Unit of corrosion current is usually A or A/m2
 There is a relationship between the corrosion current and the mass of material
corroded
𝐢 𝐗 𝐭 𝐄𝐖
𝐖=
𝐅

EW = Equivalent Weight of the material,


Q = product of total current passed in t sec.
EW = molar mass of material divided by number of electrons involved in
the redox reaction (n)

For material wit surface area (A) and density (d), corrosion penetration rate (CPR)
can be derived:
𝐜𝐦 𝐢𝐜𝐨𝐫𝐫 𝐗 𝐄𝐖
𝐂𝐏𝐑( ) =
𝐬 𝐝𝐧𝐅
Or simply corrosion rate (CR) in cm/s or in mils per year (mpy)
𝐜𝐦 𝐢𝐜𝐨𝐫𝐫 𝐗 𝐄𝐖 𝟎. 𝟏𝟐𝟗 𝐢𝐜𝐨𝐫𝐫 𝐗 𝐄𝐖
𝐂𝐏𝐑( ) = 𝐂𝐏𝐑(𝒎𝒑𝒚) =
𝐬 𝐝𝐅 𝐝 32
Table 1 Relationship Between Various Commonly Used Units of
Corrosion Rates and Their Expressions

Expression mA/cm2 mm/year mpy g/(m2 X day)


(mmpy)
mA/cm2 1 3.28 𝑀 129𝑀 8.95 𝑀
𝑛𝑑 𝑛𝑑 𝑛
mm/year 0.306 𝑛𝑑 1 39.4 2.74 𝑑
(mmpy) 𝑀

mpy 0.00777 𝑛𝑑 0.0254 1 0.0694 𝑑


𝑀
g/(m2 X day) 0.112 𝑛 0.365 14.4 1
𝑀 𝑑 𝑑

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Electrochemical Impedance Spectroscopy
• Similar to Ohm’s law

Et E0 sin t  sin t 


Z   Z0
It I 0 sin t    sin t   

• The important point to remember is that when an AC voltage


is applied to a pure capacitor the resulting AC current is
shifted in phase by 90o
• There is no phase shift for a pure resistor

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Electrochemical Impedance Spectroscopy
Current phase shift due to impedance. Through a
capacitor this phase shift is 90o

Applied
Voltage

Resulting
Current

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Electrochemical Impedance Spectroscopy
• Randles circuit for a simple corroding system

• Rs = the solution resistance


• Rct = the charger transfer (polarisation resistance)
• Cdl = the double layer capacitance

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Electrochemical Impedance Spectroscopy
• Nyquist plot for the Randels circuit

Capacitance
← Increasing Frequency

Charge transfer
resistance = Rtotal - Rs

Solution
Resistance
Resistance

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Electrochemical Impedance Spectroscopy
• Bode impedance plot

Impedance Rct
Solution
resistance

Frequency →
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Electrochemical Impedance Spectroscopy
• Bode Phase plot

Phase angle

Frequency →

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EIS (Summary)

We start here at the


high frequency

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EIS
• Diffusion or Mass Transfer controlled process
• Nyquist plot - Warburg Impedance

←Frequency

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EIS
• Diffusion or Mass Transfer controlled process
• Bode Impedance plot

Impedance

Frequency →

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EIS
• Diffusion or Mass Transfer controlled process
• Bode Phase plot

Phase Angle

Frequency →

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EIS – Mass Transfer Controlled Process (Summary)

Nyquist
Bode
Impedance

Bode
Phase

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EIS Equivalent Circuit for a Mixed Kinetic and Charge Transfer
Controlled Process

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EIS Bode Plots for the Mixed Controlled Reaction

Impedance

Phase

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EIS Equivalent Circuit for a Filmed Corroding
Surface (E.g. Failed Coating)

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EIS for a Filmed Corroding Surface (E.g. Failed Coating)

Bode
Impedance
(Magnitude

Nyquist

Bode Phase
Angle

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