Chapter 7: Corrosion Test and Monitoring

7.1. Introduction
Physicochemical, electrochemical and biochemical principles and mechanisms behind
various types of corrosion and protection methods have already been discussed.
Experimental protocols to understand and demonstrate various principles as above are
also important. This chapter therefore devoted to illustrate laboratory experimental
procedures and research techniques pertaining to some important corrosion types,
electrochemical, biological and design aspects. This chapter will introduce students to
experimental techniques and corrosion evaluation methods. This chapter is so prepared
as to enable the students to undertake design of corrosion experiments based on
electrochemical and bio- chemical concepts. An understanding of both theoretical as
well as experimental aspects of corrosion principles and processes would provide the
synergy for a holistic knowledge of the subject matter. Only basic experimental
procedures dealing with fundamental aspects are covered. Students are encouraged to
prepare laboratory experimental plans and carry out as many experiments as possible
and feasible.
7.2. Objectives of Corrosion Testing
Typical main objectives of corrosion testing are:
i. Evaluation and selection of material or protection method for a specific
environment and a certain application.
ii. General information about the behavior of certain materials and groups of materials
in the main types of environment.
iii. Routine control of materials including coatings, e.g. for acceptance or reclamation
of deliveries.
iv. Investigation of corrosion mechanisms and fundamental effects of various
conditions, development of test methods, e.g. reliable model experiments for the
prediction of lifetime (see next section), and other studies in research laboratories.
This includes also contributions to the development of materials and coatings with
special corrosion properties.
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 7.3. Test Methods
To cover the objectives stated in the previous section, numerous test methods are available.
The methods can be arranged in the following groups:
i. Laboratory testing, comprising accelerated testing, model testing, and special tailor-
made investigations in research.
ii. Service (plant) and field testing, including exposure of coupons, test specimens or
components in process environments of industrial plants as well as in special natural
fields (in seawater, atmospheres, soils etc.)
iii. Testing in a pilot plant, which is a true model (up to half scale) of the actual industrial
plant.
7.4. Testing Procedures
A typical testing procedure includes most of the following items.
i. Selection and pre-treatment of materials and test specimens.
ii. Surface preparation.
iii. Measurement of surface area and possibly thickness. The accuracy of thickness
measurement must correspond to the expected reduction of thickness during the
test.
iv. Degreasing, e.g. by acetone.
v. Weighing. The accuracy of the weight must correspond to the expected weight loss
during the test.
vi. Masking. Surfaces that are not to be exposed, must be masked, by means of
materials such as wax, lacquer, paint, tape, glue or enamel.
vii. Exposure.
viii. Inspection of the specimens after exposure, including a preliminary visual
inspection (with the naked eye or a microscope), followed by surface cleaning
(mechanically, chemically or electrochemically), weighing and/or thickness
measurement, and finally metallographic investigation using an optical or electron
microscope.

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ix. Determination of corrosion rate, on the basis of weight loss or thickness reduction
measurements, or electrochemical measurements during the exposure.

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7.5. Specific laboratory corrosion tests

Atmospheric corrosion tests

Salt spray tests (Fog testing)

Neutral

Acetic Acid

Cyclic, acidified

Cyclic, seawater
acidified Cyclic SO2
Dilute electrolyte, Cyclic Fog.
Dry Copper-Accelerated Acetic
Acid

Immersion tests

Total immersion
Partial immersion
Intermittent immersion

Tests for a given type of corrosion

Stress corrosion (MgCl2, NaCl etc)

Intergranular corrosion (Huey, Strauss etc)

Pitting corrosion
Selective leaching (Dezincification
etc) Exfoliation
Galvanic corrosion etc.

Electrochemical tests
Polarization

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resistance Impedance
Cyclic potentiodynamic polarization

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 Galvanostatic
polarization Scratch –
repassivation
Pitting and repassivation potential

7.6. EMF and Galvanic series:

Study EMF and galvanic series.

a) Differentiate between EMF and Galvanic Series with respect to their

application in corrosion prediction.
b) With respect to Galvanic series, predict corrosion behavior (galvanic
corrosion) in different bimetallic contacts?
(i) For metals and alloys which are close together.
(ii) Metals and alloys farther apart.
c) Establish Galvanic Series in 3.5% wt. % NaCl and pH 2 sulfuric acid solution
for the following metals and alloys.
Mild Steel
Zinc
Copper
Aluminum
Platinum
Tin
Brass
Bronze
Aluminium – Mg alloy
18 – 8 Stainless steel
Nickel
Lead

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Cast-iron
Titanium

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Electrodes are made of the above metallic specimens. Saturated Calomel Electrode
(SCE) is used as reference. Take the electrolytes in a beaker and immerse the electrodes.
Measure steady state potentials using a pH meter. Arrange the various metals and alloys
in increasing or decreasing order of measured potentials.

7.7. In another series of tests, establish the potential difference for pair of
electrodes.

Measured potential differences between the half-cell potentials need be checked.

Potential difference = Ecathode - Eanode

The following combinations may be tried.
Copper – mild steel
Platinum – copper
Zinc – mild steel
Titanium – brass
Stainless steel – copper
For the above couples, discuss in electrochemical terms, corrosion behavior
Which one is anode? Which is cathode?

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7.8. Influence of surface area ratios in galvanic corrosion

Copper and mild steel sheet specimens of different areas can be prepared.

In an acid or chloride solution, different area combinations can be connected to a

milli (micro) ammeter device and measure current.

7.9. Demonstration of concentration cells

Salt concentration cells – Two beakers containing pH 2 sulfuric acid solutions,

separated by an agar bridge. Dip similar copper plates (same area) in the two
beakers and measure potential difference. Now add 1M CuSO4 in one beaker and
0.1M CuSO4 in another. Measure potential difference between the copper electrodes.

7.10. Differential aeration cell

In the system as above containing 3% NaCl in both beakers separated by an agar

bridge, dip the two copper plates. In one beaker bubble nitrogen gas continuously,
while bubbling oxygen (or air) in the other. Measure the potential differences as
function of time.

Write your observation clearly.

Which copper electrode is anode? Which is cathode? Why?

Write down probable anodic and cathodic reactions?

7.11. EMF Series

From standard thermodynamic data, calculate E0 (Standard Electrode Potentials) for

various metals in the EMF series and arrange them in a series.

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 To illustrate redox reactions involving displacement of ions in solution by a more
active metal, the following tests can be performed. Immerse the metallic strip in the
suggested solution and observe surface reactions.

Acidic copper sulfate solution - Strip of iron (carbon

steel) 10% hydrochloric acid - Strip of zinc

5% silver nitrate solution - Strip of copper

In all the above cases, discuss the electrochemistry of the reactions based on EMF
series.

Write down anodic, cathodic and net cell reactions.

7.12. Eh and pH Measurements and Standardisation

Use a pH meter and learn how to standardize and calibrate the meter for both pH and
Eh.

pH standardization is done using standard buffer solutions of pH in the range 2, 4, 9

and 11.

For redox potential measurements, ZoBell’s solution is used as a standard.

0.0033 M each of potassium ferro – and ferricyanide in 0.1 M of KCl (potassium

chloride).

Standard potential is +229 ± 5mV (Ag / AgCl)

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7.13. Measurement of redox potentials

The following couple can be used

Fe+++ + e = Fe++ E0 = +0.771V

Eh = 0.771 + 0.059 log

Prepare different concentrations of standard ferrous sulfate and ferric sulfate at acidic
pH of about 1.0. Using a platinum – SCE couple, measure the potentials for the
following after deaeration of solution using nitrogen

1M ferrous sulfate
alone 1M ferric sulfate
alone
Different ratios of ferric and ferrous sulfate solution mixed.

Plot a graph depicting measured potentials as a function of log at a constant

pH.

What is the slope of the line?

7.14. Laboratory Construction of Eh – pH diagrams

Can you experimentally construct an Eh – pH diagram for the iron-water-oxygen

system?

Try measurements of Eh and pH corresponding to different concentrations of ferrous

and ferric ions in the presence and absence of oxygen.

The following points may be considered.

a) Take distilled water in an electrolytic cell. Measure Eh and pH for different

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values of pH under oxygenated and deoxygenated conditions using platinum

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 – SCE couple. Plot Eh as a function of pH. Compare this experimental line
with the theoretically established line for the reaction.
O2 + 4H+ + 2e = 2H2O E0 = + 1.23V
b) Establish experimental Eh – pH curves for the following reactions.
1. Fe = Fe++ + 2e
2. Fe++ + 2H2O = Fe (OH)2 + 2H+
3. Fe+++ + e = Fe++
4. Fe+++ + 3H2O = Fe (OH)3 + 3H+
5. Fe + 2H2O = Fe(OH)2 + 2H+ + 2e
6. Fe (OH)2 + H2O = Fe (OH)3 + H+ + e
7. Fe++ + 3H2O = Fe(OH)3 + 3H+ + e

Comment on your experimental observations with respect to theoretical Eh – pH

diagram for iron based on the above reactions.

c) Prepare 1M solution of acidic ferrous sulfate at a pH of about 1.0. Under

changing pH in the presence of aeration, measure Eh as a function of pH.
Report only steady-state values. Plot a curve depicting ferrous and ferric ion
concentrations at different pH and time.

7.15. Use of zinc in corrosion protection of steels

Electrochemical principles governing corrosion of iron (mild steel) and zinc when
present alone and when in galvanic combination can be demonstrated. Establish
corrosion rate of zinc and iron (when present individually without contact) in dil.
Hydrochloric acid. This can be done through weight loss measurements as a
function of time. Then electrically join a sheet specimen of zinc and steel and
immerse in the same medium for different periods of time.

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 Tabulate your readings and comment?

Conditions Initial weight Final weight Change in weight

Steel
Zinc
Steel + Zinc

Zinc can be coated into steel through either electroplating or hot dipping.

Electroplating of zinc on a steel specimen can be experimentally demonstrated from an acid

zinc bath under specified experimental conditions. Scratch away some of the zinc coating from
the coated steel surface and study rusting of iron in salt water. Will steel corrode?

7.16. Electrochemical tests in a given environment

Polarization curves and Tafel plots for generalized corrosion.

Polarization resistance measurements.
Corrosion potential, pitting and repassivation
potential. Galvanic coupling – effect on polarization
curves.
Electrochemical impedance (to study behavior of coating, passivation).

Anodic polarization for establishing active-passive behavior of metals and alloys in

different environments – Anodic protection.
Impressed current cathodic protection.

In order to establish Tafel constants, corrosion potential, corrosion current and exchange
currents, extrapolated regions of anodic and cathodic curves have to be used.

Two types of approach

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a. Wide range of overpotentials with reference to rest potential (for example, -150mV to
+150mV), to facilitate determination of Tafel slopes through extrapolation to the
corrosion potential.
b. Narrow range of overpotentials (+20 mV to -20mV), facilitating determination of linear
polarization resistance (slow scan rate).

Description of cell and experimental arrangements are given in Fig 7.1 and 7.2.

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Fig. 7.1 Typical electrolytic cell with various electrodes for polarization measurements

Fig. 7.2 Automatic polarization measurement

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7.17. Measurement of pitting potentials

Cyclic polarization techniques can be used to evaluate pitting tendency of an active-passive

metal or alloy (Fig. 7.3). A potential scan starting from E corr in the anodic direction is applied till
significant current increase occurs. The final potential is negative with reference to repassivation
potential. The potential where the loop closes on the reverse scan is the protection potential,
which can also be estimated by extrapolating the reverse scan to zero current. Pitting potential
(Epit) corresponds to the potential at which current increases sharply. The larger the loop, the
higher the tendency for pitting. Pitting shows up as an increasing anodic current before
transpassive corrosion or evolution of oxygen.

Fig. 7.3 Cyclic polarization to determine pitting and protection potentials.

New pits can initiate only above pitting potential, and not between E pit and Eprot. No hysteresis is
exhibited by an alloy which is resistant to pitting. There will be potential and current
distributions around pits.

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7.18. Experiments for evaluation of sensitization in stainless steels.

Study chromium depletion and precipitation as carbides at the grain boundaries.

Oxalic acid test: Polished specimen is anodically etched at 1A/cm2 for a minute in 10% oxalic
acid at room temperature. Examine the specimen under the microscope to reveal step, dual or
ditch structures.

7.19. Determination of effect of alloy chemistry on passivation parameters:

For development of corrosion – resistant alloys with reference to active – passive behavior, the
following key parameters need to be optimized.

Epp – Primary passive potential

icrit – Critical anodic passivating current density.

1. Establish Anodic polarization curves for iron , nickel and chromium in 1N H2SO4. Comment
on the passivity curves with respect to passivity potential range, Epp and icrit.
2. Establish the effect of chromium (0 – 30%) in stainless steels on Epp and icrit in 1N H2SO4.
Plot your results with respect to
(a) Epp Vs percent chromium
(b) icrit Vs percent chromium
3. Determine pitting potentials for 18-8 stainless steel in different chloride concentrations.

7.20. Corrosion testing for metals and alloys

The following systems for corrosion testing are available, each covering different method of
corrosion evaluation
Humidity test chamber – Salt spray – Temperature and humidity control.
Test set-up for alternate immersion testing of metals and alloys in 3.5% NaCl solution for stress
corrosion testing.

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 Bimetallic corrosion testing in specific liquids under humidity control – current and potential
difference recorded.

7.21.Laboratory techniques for studying amenability to Microbially influenced

corrosion ( MIC) due to biofilms:

Evaluation of biofilms from deposit samples collected from various locations –organic
and inorganic content of biofilms.
Carbohydrate and protein analysis
(spectrophotometer) Presence of aerobes and
anaerobes in the deposits.
Redox potential measurements in liquid samples.

Corrosion potential measurements – Biofilm growth on metal surface influences anodic

and cathodic reactions – Shifting of corrosion potentials in positive or negative directions
to be monitored.
Examples: Stainless steels in aerated seawater
Mild steel in anaerobic seawater.
Distinguish between aerobic and anaerobic corrosion.

Polarization experiments in the presence and absence of biofilms on metals in the

presence and absence of microorganisms.
Monitoring and characterization procedures for different bacteria involved in MIC are listed in
Table 7.1. Various strains of different bacterial species can be procured from culture banks and
characterized as per recommended procedures.

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Table 7.1 Testing and Analyses of different bacteria relevant to MIC,

Type of Bacteria Monitoring and characterization

1. Acid producing Production of inorganic and organic acids –

attack on various metals and alloys.

2. Denitrifying Ammonia production – attack on copper

alloys.

3. Iron-related Ferrous oxidation and ferric-reduction-

plugging of water and oil pipelines- tubercle
formation.

4. Slime-forming Slime-sludge characterization.

5. Sulfate-reducing Sulfide production (H2S) – FeS production -

corrosion of metal surfaces.

Common media used for routine isolation of bacteria and fungi

Filamentous fungi - Potato Dextrose Agar

Aerobic and anaerobic bacteria - Nutrient Agar

Pseudomonas Sp - Select media from literature

Sulfate Reducing Bacteria (SRB) - Postgate media

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7.22. Microbially influenced corrosion of aluminium alloys

Choose desired aluminium alloys and make suitable specimens. Use naturally collected sea
water and fresh water samples from identified locations. A biofilm growth chamber (under
conditions of both stagnant and flowing liquid) can be constructed to expose the metallic
specimens for different periods of time.

Monitor biofilm growth by removing specimen frequently and characterize the biofilm with
respect to thickness, microbial assay, chemical and metallurgical analysis, surface roughness and
morphology. Isolate important bacterial species from the biofilm and carry out steady-state
potential and polarization measurements in the presence and absence of isolated bacteria.

7.23. Biofouling and MIC of stainless steels in sea water.

Experiments similar to the previous one for aluminium alloys.

7.24. Microbial diversity of pipelines and establishment of MIC

Locate a pipeline transporting water and petroleum products.

From the pipeline, collect aseptically, samples of water, oil and corrosion products (debris).

a) Visual, physical and chemical characterization of the water, oil and debris samples
for colour, chemical composition, pH.
b) Isolation and enumeration of different types of microorganisms through standard
microbiological procedures – characterization of isolated organisms with respect to
Autotrophs, Heterotrophs.
Bacteria, fungi
Aerobe, anaerobe
Iron oxidising, Manganese oxidising.
c) Based on the microbial assay and characterization and failure analysis of the
pipeline samples, predict nature of MIC (Microbially – influenced corrosion)

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7.25. Examination of biocorrosion of concrete in the laboratory simulating sewer
conditions
Samples of sewer pipes collected from sewerage processing stations can also be used.

Corrosion testing coupons

Fresh coupons from new sewer pipes.

Coupons prepared from corroded concrete slabs from sewer treatment plants.

Corrosion chambers for exposing the coupons to bacterial activity under simulated conditions
can be used.

Monitor conditions with respect to pH changes, H 2S generation, temperature and humidity.

Growth of Anaerobic Sulfate Reducing Bactria (SRB), aerobic sulfur oxidizers such as
Acidithiobaullus can be monitored and their role on concrete corrosion assessed.

7.26.Bacterial kinetics of sulfur oxidation of Acidithiobacillus thiooxidans and its

influence on concrete corrosion.

Experimental strategy:

Bacterial growth in recommended media.

Growth curve with respect to cell number, pH and sulfate concentration as a function of
time.
Establish bacterial growth kinetics.

Concrete corrosion tests in aqueous media at bacterial acidic pH under different

conditions of temperature, metal-ion concentrations, and types of reinforcement steels.

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7.27. Corrosion testing for medical implants
Compatibility

Tissue response
Dissolution rates
Toxicity

In vivo corrosion –

How susceptible is the implant metal to

corrosion?
Effect of corrosion on body response

Rest potential : Measurements over extended periods of time to predict metal

dissolution. Cyclic potentiodynamic polarization: Corrosion susceptibility of small
implant devices.
Galvanic corrosion: Coupled and uncoupled leach
rates. Fretting: Fretting corrosion in moving body
parts.
Various metal and alloy samples representative of implant materials can be shaped
into electrodes and tested in body fluids and simulated electrolytes.

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