Engineering and Material Science Faculty

German University in Cairo

Effect of demineralized water on

carbon steel and stainless steel

Bachelor Thesis

Author: Mostafa Yahia Elsehamy

Supervisor: Prof. Dr. Ahmed Abdelaziz
Reviewer: Prof. Dr. Ali Elwaraky
Submission Date: 15 May, 2016

i
This is to certify that:
(i) the thesis comprises only my original work towards the Bachelor Degree

(ii) due acknowledgement has been made in the text to all other material used

Mostafa Yahia Elsehamy

15 May 2016

ii
Acknowledgments
• I would like to thank Prof. Dr. Ahmed Abdel Aziz for his efforts and guidance

• I would like to thank my family and my colleague Aya Ashraf for their support and help.

• I would also like to thank Mohamed Othman and Mr. Mohsen from the GUC staff for their
help.

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Aim of Project
The aim of this project is to investigate the effect of water purity on carbon steel and stainless
steel. Two corrosion tests are used: electrochemical measurements and weight loss test.
Surface analysis was done using optical microscope in addition to scanning electron
microscope (SEM) and analyse the different surface content by using energy dispersive
X-ray (EDX).

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Abstract
Steel or stainless steel have reasonable corrosion behaviour in water, their corrosion
resistance is significantly dependent on the water purity. It was not expected that
demineralized water has an aggressive effect on steel alloys, in this study, the effect of water
with different purity on steel X52 and stainless steel 316L was investigated. Weight loss and
electrochemical measurements were employed to measure the corrosion behaviour. Samples
were microscopically investigated after test. It was observed that the higher the water purity
the more reactive it is. Comparative analysis of the potentiodynamic curves for different
water purity showed the aggressiveness of the demineralised water (conductivity of 0.05
S /cm) over the distilled water. Whereas, the corrosion rates of stainless steel 888.2 and
661.6 nm/y for demi and distilled water respectively. On the other hand the corrosion rates of
carbon steel x52 were estimated about 7.2 and 5.9 μm/y for demi and distilled water,
respectively. Open circuit potential (OCP) recorded more positive potentials in case of
stainless steel than carbon steel in different water purities. Generally, stainless steel
illustrated high pitting resistance than carbon steel alloy, the surface film was investigated by
scanning electron microscopy (SEM) and analyzed by energy dispersive X-ray spectroscopy
(EDX).This behaviour was explained based on that demi and distilled water might be
considered as "hungry water" in which it wants to be in equilibrium and will pull ions out of
the surrounding metals trying to satisfy its "hunger".

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Contents
Acknowledgments.................................................................................................................... iii
Aim of Project .......................................................................................................................... iv
Abstract ..................................................................................................................................... v
List of figures .......................................................................................................................... vii
List of Tables ........................................................................................................................... ix
Table of Abbreviations ............................................................................................................. x
Chapter 1 ................................................................................................................................... 1
Introduction: .......................................................................................................................... 1
1.1 Definition of corrosion: ............................................................................................... 1
1.2 Corrosion Mechanism in aqueous medium: ............................................................... 1
1.3 Common forms of corrosion: ...................................................................................... 2
1.4 Carbon steel: ............................................................................................................... 5
1.5 Stainless steel: ............................................................................................................. 7
1.6 Common types of purified water: ............................................................................. 10
1.7 Carbon dioxide effect on steels: ................................................................................ 11
Chapter 2 ................................................................................................................................. 13
Literature review: ................................................................................................................ 13
Chapter 3 ................................................................................................................................. 18
Experimental work: ............................................................................................................. 18
3.1 Material used:............................................................................................................ 18
3.2 Sample preparation ................................................................................................... 18
3.2 Storage of the samples: ............................................................................................. 20
3.3 Demi water preparation: ........................................................................................... 20
3.4 Weight loss technique: .............................................................................................. 21
3.5 Method of cleaning after testing: .............................................................................. 22
3.6 Electrochemical Measurements: ............................................................................... 22
Chapter 4 ................................................................................................................................. 29
Results and discussion: ....................................................................................................... 29
4.1 Weight loss measurements:....................................................................................... 29
4.2 Electron Microscope: ................................................................................................ 35
4.3 Electrochemical measurements:................................................................................ 43
4.4 Optical microscope: .................................................................................................. 61
Chapter 5 ................................................................................................................................. 62
Conclusion: ......................................................................................................................... 62
Bibliography ........................................................................................................................... 64

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List of figures
Figure 1: Common forms of corrosion…………………………………………….......5
Figure 2: Austenitic stainless steel families………………………………………….....9
Figure 3: Corrosion rate of steel versus time in aerated and deaerated DI water……...13
Figure 4: Corrosion potential time dependences for carbon steel……………………...14
Figure 5: DO concentration dependences of film thickness on carbon steel..................14
Figure 6: Film thickness time dependences for carbon steel………………………...…14
Figure 7: Anodic potentiodynamic curve for AISI 316L steel………………………....15
Figure 8: Pourbaix diagram of iron…………………………………………………..…16
Figure 9: stability region in Pourbaix diagram………………………………………....16
Figure 10: Grinding and polishing machine…………………………………………….19
Figure 12: Mounted sample…………………………………………………………..…19
Figure 13: PURELAB UHQ II………………………………………………………......20
Figure 14: Measurement of ECORR for a metal-solution system……………………....23
Figure 15: SCE and Auxiliary electrode………………………………………………....24
Figure 17: Tafel analysis………………………………………………………………....25
Figure 18: Zeiss optical microscope……………………………………………………...27
Figure 19: CS after weight loss test in demi water……………………………………….29
Figure 20: CS after weight loss test in distilled water………………………………...….31
Figure 21: SS after weight loss test in demi water.............................................................32
Figure 22: SS after weight loss test in distilled water………………………………….....34
Figure 23: CS in demi water 200X………………………………………………………..35
Figure 23: CS in demi water 3000X……………………………………………………....35
Figure 25: EDX of CS in demi water..................................................................................36
Figure 26: CS in distilled water 200X.................................................................................37
Figure 27: CS in distilled water 3000X...............................................................................37
Figure 28: EDX of CS in distilled water.............................................................................38
Figure 29: SS in demi water 200X......................................................................................39
Figure 30: SS in demi water 3000X....................................................................................39
Figure 31: EDX of SS in demi water...................................................................................40
Figure 32: SS in distilled water 200X..................................................................................41
Figure 33: SS in distilled water 3000X................................................................................41
Figure 34: EDX of SS in distilled water..............................................................................42
Figure 35: OCP of CS X52 in demi water...........................................................................43
Figure 36: OCP of CS X52 in distilled water......................................................................44
Figure 37: OCP comparison between CS in demi water and distilled water.......................45
Figure 38: OCP of SS 316L in demi water..........................................................................46
Figure 39: OCP of SS 316L in distilled water.....................................................................47
Figure 40: OCP comparison between SS 316L in demi water and distilled water..............48
Figure 41: OCP comparison between CS X52 and SS 316L in demi water........................49
Figure 42: PCV CS X52 in demi water................................................................................50
Figure 43: PCV CS X52 in distilled water...........................................................................51
Figure 44: PCV comparison of CS X52...............................................................................52
Figure 45: PCV of SS 316L in demi water...........................................................................53
Figure 46: PCV of SS 316 L in distilled water.....................................................................54

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Figure 47: PCV comparison between CS and SS in demi water and distilled......................55
Figure 48: Tafel curve of CS in demi water..........................................................................57
Figure 49: Tafel curve of CS in distilled water……………………………………………..57
Figure 50: Tafel comparison of CS.......................................................................................58
Figure 51: Tafel curve of SS in demi water...........................................................................59
Figure 51: Tafel curve of SS in distilled water......................................................................59
Figure 53: SS Tafel comparison.............................................................................................60
Figure 54: Carbon steel in demi water....................................................................................61
Figure 55: Carbon steel in distilled water...............................................................................61
Figure 56: Stainless steel in demi water..................................................................................61
Figure 57: Stainless steel in distilled water.............................................................................61

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List of Tables
Table 1: Carbon steel X52 chemical composition...................................................5
Table 2: Demi water specifications..........................................................................21
Table 3: variation of the constant of the corrosion rate............................................21
Table 4: Dimensions of CS sample in demi water....................................................29
Table 5: CS in demi water test data...........................................................................29
Table 6: Corrosion rate calculation of CS in demi water..........................................30
Table 7: Dimensions of CS sample in distilled water...............................................30
Table 8: CS in distilled water test data......................................................................31
Table 9: Corrosion rate calculation of CS in distilled water......................................31
Table 10: Dimensions of SS sample in demi water...................................................32
Table 11: SS in demi water test data..........................................................................32
Table 12: Corrosion rate calculation of SS in demi water..........................................33
Table 13: Dimensions of SS sample in distilled water...............................................33
Table 14: SS in distilled water test data......................................................................33
Table 15: Corrosion rate calculation of SS in distilled water.....................................34
Table 16: comparison between the corrosion..............................................................34
Table 17: EDX results of CS in demi..........................................................................36
Table 18: EDX results of CS in distilled.....................................................................38
Table 19: EDX results of SS in demi...........................................................................40
Table 20: EDX results of SS in distilled......................................................................42
Table 21: Pitting potential of all the samples...............................................................56
Table 22: corrosion rate of CS samples in both water purities.....................................58
Table 23: corrosion rate of SS samples in both water purities......................................60

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Table of Abbreviations
OCP Open circuit potential
PCV Potential cyclic voltammetry
°C Degree Celsius
Pt Platinum electrode “auxiliary “
SCE Saturated Calomel Electrode
CS Carbon steel
mm Millimetres
mV Millivolt
SEM scanning Electron Microscopy
Sat. Saturated
LPR Linear polarization resistance
SS Stainless steel
EDX Energy dispersive x-ray
Demi Demineralized water
SCC Stress corrosion cracking
DI Deionized
DO Dissolved oxygen
Icorr Corrosion current
Ecorr Corrosion potential
Ep Pitting potential
Eocp Open circuit potential

S Micro Siemens
SHE Standard hydrogen electrode
FCC Face centered cube
BCC Body centered cube
PPM Part per million

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Chapter 1
Introduction:

1.1 Definition of corrosion:

Perhaps the most common example of what is called corrosion is the reaction between
ordinary steel and its environment during which a voluminous and porous layer of rust is
formed. There are many well-known examples of this from perforation by rusting of silencers
and exhaust systems of cars, of car bodies and of various kinds of structural steelwork [1].
In fact rusting and corrosion are sometimes considered to be synonymous. Basically
corrosion is a destructive attack of the metals as a result of their reaction with the
environment. The extent of their reaction with time is termed corrosion rate. Some claim the
definition should be restricted to metals, but corrosion experts to solve a certain problem
must consider non-metals also, for example ceramics, plastics, rubber, and other non-metallic
materials. The term corrosion may refer either to the process or to the damage caused.

1.2 Corrosion Mechanism in aqueous medium:

Aqueous corrosion is the most prevalent type of corrosion as water is utilized for wide
Variety of purposes, like potable water, water for industrial tasks such as heat exchangers and
waste convey. Water has great effect on the efficiency of the materials so studying its effect
is paramount for system control. Steels and iron based alloys are the most prevalent material
exposed to water so they are a good model to study aqueous corrosion with a special fixates
on the reaction of iron (Fe) with the water (H2O). In the cases of iron-based alloys, the
following reaction conventionally takes place at anodic areas:
Fe → Fe+2 + 2e- (1.1)

This reaction is fast in most media, as appeared by the absence of pronounced polarization
when iron is made an anode utilizing an external current. At the point when iron consumes,
the rate is typically controlled by the cathodic reaction, which as a rule is much slower
(cathodic control). In deaerated solutions, the cathodic behaviour is

2H+ + 2e- → H2 (1.2)

This reaction proceeds rapidly in acids, but only slowly in alkaline or neutral aqueous media.
The corrosion rate of iron in deaerated neutral water at room temperature, for example, is less
than 5 µm/year. The rate of hydrogen evolution at a specific pH depends on the presence or
absence of low-hydrogen overvoltage impurities in the metal. For pure iron, the metal surface
itself provides sites for H2 evolution; hence, high-purity iron continues to corrode in acids,
but at a measurably lower rate than commercial iron.

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The cathodic reaction can be accelerated by the reduction of dissolved oxygen in accordance
with the following reaction, a process called depolarization:
4H++ O2 + 4e - → 2H2O (1.3)

Dissolved oxygen reacts with hydrogen atoms adsorbed at random on the iron surface,
independent of the presence or absence of impurities in the metal. The oxidation reaction
proceeds as rapidly as oxygen reaches the metal surface.
Adding (1.1) and (1.3), making use of the reaction H2O ↔ H+ + OH- , leads to reaction
(1.4),
2Fe + 2H2O + O2 → 2Fe(OH)2 (1.4)

Hydrous ferrous oxide (FeO_nH2O) or ferrous hydroxide [Fe (OH) 2] composes the
diffusion-barrier layer next to the iron surface through which O2 must diffuse. The pH of a
saturated Fe (OH) 2 solution is about 9.5, so that the surface of iron corroding in aerated pure
water is always alkaline. The colour of Fe (OH) 2, although white when the sub- stance is
pure, is normally green to greenish black because of incipient oxidation by air. At the outer
surface of the oxide film, access to dissolved oxygen converts ferrous oxide to hydrous ferric
oxide or ferric hydroxide, in accordance with
2Fe (OH) 2 + 2H2O + O2 → 4Fe(OH)3 (1.5)

Hydrous ferric oxide is orange to red-brown in colour and makes up most of ordinary rust. It
exists as nonmagnetic Fe2O3 (hematite) or as magnetic Fe2O3, the form having the greater
negative free energy of formation (greater thermodynamic stability). Saturated Fe(OH) 3 is
nearly neutral in pH. A magnetic hydrous ferrous ferrite, Fe3O4 _ nH2O, often forms a black
intermediate layer between hydrous Fe2O3 and FeO. Hence rust films normally consist of
three layers of iron oxides in different states of oxidation [2].

1.3 Common forms of corrosion:

Corrosion is the degradation of a material by electrochemical or chemical reaction with its

environment. Various forms of corrosion exist and they are classified as: 1- uniform, 2-
Galvanic, 3- Crevice, 4- Pitting, 5- Inter-granular, 6- Leaching, 7- Erosion-Corrosion,8-
Stress Corrosion Cracking, and 9- Hydrogen Attack (Embrittlement) [3].

1.3.1 Uniform corrosion:

Uniform corrosion is characterized by corrosive attack proceeding evenly over the entire
surface area, or a large fraction of the total area. General thinning takes place until failure.
On the basis of tonnage wasted, this is the most important form of corrosion.
However, uniform corrosion is relatively easily measured and predicted, making disastrous
failures relatively rare. In many cases, it is objectionable only from an appearance standpoint.
As corrosion occurs uniformly over the entire surface of the metal component, it can be
practically led control by cathodic protection, use of coatings or paints, or simply by
specifying a corrosion allowance. In other cases uniform corrosion adds colour and appeal to

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a surface. Two classics in this respect are the patina created by naturally tarnishing copper
roofs and the rust hues produced on weathering steels. (The breakdown of protective coating
systems on structures often leads to this form of corrosion. Dulling of a bright or polished
surface, etching by acid cleaners, or oxidation (discoloration) of steel are examples of surface
corrosion. Corrosion ant resist alloys and stainless steels can become tarnished or oxidized in
corrosive environments. Surface corrosion can indicate a breakdown in the protective coating
system, however, and should be examined closely for more advanced attack. If surface
corrosion is permitted to continue, the surface may become rough and surface corrosion can
lead to more serious types of corrosion.

1.3.2 Galvanic Corrosion:

Galvanic corrosion can result when a metal is in contact with another dissimilar metal. In
order for galvanic attack to take place, there must be four things present. First, there must be
an anode. This is the material which corrodes. Second, there also must be another electrode
called the cathode. Third, an electrical connection must exist between the anode and cathode
through which electrons can flow. Finally there must be an electrolyte through which
chemical ions can flow. The rate of galvanic attack depends on the relative anode-to-cathode
surface areas that are exposed to the electrolyte, and the rate is related directly to the
cathode–anode area ratio; that is, for a given cathode area, a smaller anode will corrode more
rapidly than a larger one. This is generally an aqueous solution yet even damp soil can make
an excellent electrical conductor. The arrangement of these four specific components is
always necessary for an electrochemical chemical cell to function. However in the case of
galvanic corrosion, the anode and cathode are clearly dissimilar metals, copper and zinc, iron
and brass, or mild steel and cast iron [3].

1.3.3 Crevice Corrosion:

Consider a sheet of stainless steel that has been immersed in the ocean for some time, years
perhaps. It has had a bolt with a washer on it to hold it in place. We notice that corrosion has
taken place underneath the washer. The reason for the corrosion is that a crevice had been
created under the washer. Stagnate water, an electrolyte, accumulated in the crevice. An
electrochemical, corrosion cell had been produced and corrosion resulted. This cell is called a
differential aeration, or oxygen concentration cell. The crevice must be wide enough for the
solution to penetrate, yet narrow enough for stagnancy; usually the width is several
thousandths of an inch. It results because there is a difference in the composition of the
electrolyte under the washer and that outside of the washer. There is a higher oxygen
concentration in the solution that surrounds than washer that there is under the washer. It may
surprise you to know that corrosion takes place at the lower oxygen concentration whenever
we have an oxygen concentration cell.

1.3.4 Pitting Corrosion:

Some materials are more subject to pitting than others. Pitting corrosion is a form of
corrosion that most of us see on almost a daily basis. This corrosion cell, the electrochemical
mechanism of the corrosion, is very similar to that of crevice corrosion. There is a stagnant
solution at the bottom of the pit; a lower oxygen concentration is outside of the pit than
inside, resulting in another oxygen concentration cell. Corrosion takes place at the bottom of
the pit. Generally, as the pit gets deeper, the solution at the bottom of the pit becomes more
stagnant creating more driving force to promote corrosion. A pit is said to be self-catalyzing.

3
1.3.5 Inter-granular Corrosion:

Consider a stainless sheet that has been welded to another. Along each side of the weld you
see a corrosion attack called weld decay. This attack takes place by inter-granular corrosion.
That is, the attack is into the boundaries of the metallic grains that make up the metal. As the
metal is heated during the weld, chromium is precipitated out of the heated grains and
deposits in the grain boundary, an area that separates the grains and is burdened with
impurities. Again, the components of a chemical corrosion cell are the result.

1.3. 6 Leaching Corrosion

Selective leaching corrosion is corrosion accelerated by the selective leaching of an alloying

element out of the alloy matrix. The most common form of this type of corrosion is
Dezincification, the selective leaching of zinc out of the brass matrix. Brass is made of zinc
and copper. Zinc is considerable more corrosive than is copper. In certain cases, e.g., when
brass is exposed to an aggressive environment, the zinc will corrode preferentially and
leaching zinc from the brass alloy leaving behind a weak network of copper. It may look
strong but is has been severely weakened.

1.3. 7 Erosion corrosion:

Erosion corrosion is the combined effect that occurs due to corrosion and erosion and is
caused by the rapid flow of any turbulent fluid on a metal surface. Pitting, which is often
found on the inner surfaces of pipes, is the main cause of turbulence. Erosion corrosion is
commonly found in piping, especially at bends, elbows, and abrupt changes in pipe diameter
and positions where the fluid changes direction or flow suddenly becomes turbulent. The rate
of erosion increases in turbulent conditions and can result in leakages in tubes and pipes.
Erosion corrosion can also result from poor workmanship. When burrs in the tubes are not
removed during installation, these inner burrs cause localized turbulence and hinder the
smooth flow of the fluid. This leads to high rates of pitting in the tubes. One of the best ways
to reduce erosion corrosion is to change the design to eliminate fluid turbulence and
impingement effects.

1.3.8 Stress corrosion cracking:

Stress corrosion cracking (SCC) is characterized by cracks propagating either trans-

granularly or inter-granularly (along grain boundaries). There are several types of stress
corrosion cracking (SCC), for example, chloride-induced SCC and H2S-induced SCC. Stress
corrosion cracking results from the conjoint action of three components: (1) a susceptible
material; (2) a specific chemical species (environment) and (3) tensile stress. For example,
copper and its alloys are susceptible to ammonia compounds, mild steels are susceptible to
alkalis and stainless steels are susceptible to chlorides. Probably the best measure to take in
reducing or totally eliminating stress corrosion is to lower the magnitude of the stress. This
may be accomplished by reducing the external load or increasing the cross-sectional area
perpendicular to the applied stress.

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1.3. 9 Hydrogen embrittlement:

Embrittlement corrosion is a corrosion that causes a ductile material to fail without localized
yielding or shearing. More specifically, hydrogen embrittlement assumes several different
forms with a general similarity. This damage takes place at the cathode, an area that we
normally think is safe from corrosion, but it does not in this case. Hydrogen ions are reduced
to hydrogen molecules at the cathode. Those atoms usually pair-up to become hydrogen
molecules. These molecules harmlessly bubble off as hydrogen gas. However, some metals
are very susceptible to letting hydrogen atoms permeate into the grains. This is done while
the hydrogen exists as an atom, before it becomes a molecule. Once inside the metal the
hydrogen atoms can do all sorts of mischief those results in hydrogen damage. High-strength
steels are susceptible to hydrogen embrittlement, and increasing strength tends to enhance the
material’s susceptibility. Martensitic steels are especially vulnerable to this type of failure;
bainitic, ferritic, and spheroiditic steels are more resilient. Some of the techniques commonly
used to reduce the likelihood of hydrogen embrittlement include reducing the tensile strength
of the alloy via a heat treatment, removal of the source of hydrogen, “baking” the alloy at an
elevated temperature to drive out any dissolved hydrogen, and substitution of a more
embrittlement-resistant alloy.
And the following figure illustrate most of these forms

Figure1: Common forms of corrosion

Carbon steel and stainless steel are two extremely popular grades of pipe and useful materials
for industrial pipe fabrications. Each type of material comes with its own particular sets of
pros and cons and likewise each material has different fabrication considerations. The main
difference between the two is in the components that are added to the steel to make it useful
for its intended purposes. So it is necessary to illustrate their different types and applications.

1.4 Carbon steel:

The term steel is used for many different alloys of iron. These alloys vary both in the way
they are made and in the proportions of the materials added to the iron. All steels, however,
contain small amounts of carbon and manganese. In other words, it can be said that steel is a
crystalline alloy of iron, carbon and several other elements, which hardens above its critical

5
temperature. Like stated above, there are several types of steels which are (among others)
plain carbon, stainless steel, alloyed steel and tool steel.

1.4.1 Plain carbon steel:

Carbon steel is by far the most widely used kind of steel. The properties of carbon steel
depend primarily on the amount of carbon it contains. Most carbon steel has a carbon content
of less than 1%. Carbon steel is made into a wide range of products, including structural
beams, car bodies, kitchen appliances, and cans. In fact, there are 3 types of plain carbon
steel and they are low carbon steel, medium carbon steel, high carbon steel, and as their
names suggests all these types of plain carbon steel differs in the amount of carbon they
contain. Indeed, it is good to precise that plain carbon steel is a type of steel having a
maximum carbon content of 1.5% along with small percentages of Silica, sulphur,
phosphorus and manganese.

General properties of plain carbon steel:

Generally, with an increase in the carbon content from 0.01 to 1.5% in the alloy, its strength
and hardness increases but still such an increase beyond 1.5% causes appreciable reduction in
the ductility and malleability of the steel. Low carbon steel or mild steel, containing carbon
up to 0.25% responds to heat treatment as improvement in the ductility is concerned but has
no effect in respect of its strength properties. Medium carbon steels, having carbon content
ranging from 0.25 to 0.70% improves in the machinability by heat treatment. It must also be
noted that this steel is especially adaptable for machining or forging and where surface
hardness is desirable.
One of the popular grades of plain carbon steel, which is used mainly in pipes, is carbon steel
X52. Carbon steel X52 (enhanced) high yield seamless pipes, modified to suit offshore
structural purposes. Intended for (but not limited to) use in fixed offshore structures,
designed to operate in the offshore sector.
It has the following chemical composition in percentage:

Table 1: Carbon steel X52 chemical composition

C Si Mn P V Nb Ti S
0.16 0.45 1.65 0.020 0.0.010 0.07 0.05 0.04

1.4.2 High carbon steels:

This type of steel contains carbon in the range of 0.70 to 1.05% and is especially classed as
high carbon steel. In the fully heat-treated condition it is very hard and it will withstand high
shear and wear and will thus be subjected to little deformation. Moreover, at maximum
hardness, the steel is brittle and if some toughness is desired it must be obtained at the
expense of hardness. Depth hardening ability (normally termed as hardenability) is poor,
limiting the use of this steel. Furthermore, as it has been seen that hardness, brittleness and
ductility are very important properties as they determine mainly the way these different
carbon content steels are used.). When the carbon content in the steel is increased, the
6
amount of pearlite increases until we get the fully pearlitic structure of 0.8% carbon.
Beyond 0.8%, high carbon steel contains proeutectoid cementide in addition to pearlite.
However, in slowly cooled carbon steels, the overall hardness and ductility of the steel are
determined by the relative proportions of the soft, ductile ferrite and the hard, brittle
cementite. The cementite content increases with increasing carbon content, resulting in an
increase of hardness and a decrease of ductility, as we go from low carbon to high carbon
steels .

1.5 Stainless steel:

Stainless steels are used for corrosion and heat resisting applications. Stainless steel is an
alloy of iron with a minimum of 10.5% chromium. Chromium produces a thin layer of oxide
on the surface of the steel known as the passive layer. This prevents any further corrosion of
the surface and heals itself in the presence of oxygen. This property is not evident in the low-
chromium structural steels previously discussed in the article on alloy steels and is apparent
only when the chromium content exceeds about 10 percent. Increasing the amount of
chromium gives an increased resistance to corrosion. Since stainless steels contain relatively
large amounts of chromium, the iron-chromium-carbon alloys belong to a ternary system.
Stainless steel also contains varying amounts of carbon, silicon and manganese. Other
elements such as nickel and molybdenum may be added to impart other useful properties
such as enhanced formability and increased corrosion resistance. Information about
classification of stainless steels and types of stainless steels is given in this article.

There are different types of stainless steel in terms of their applications, alloying elements or
their properties:
1. Ferritic stainless steel. 2. Austenitic stainless steel. 3. Duplex stainless steel. 4. Martensitic
stainless steel. 5. Precipitation Hardening.

1.5.1 Ferrite:

These types of stainless steels (series 4xx) are straight-chromium stainless steels containing
approximately 14 to 27 percent chromium with small amounts of carbon (usually less than
0.10%) The crystallographic structure of the steels is ferritic (BCC – body centered cubic
crystal structure) at room temperature. These alloys deliberately lack high nickel contents,
because nickel renders the steels austenitic.

Ferritic steels are best suited for general and high-temperature corrosion applications rather
than services requiring high strength. Ferritic steels are chosen for their resistance to stress
corrosion cracking. High chromium steels with additions of molybdenum can be used in
quite aggressive conditions such as sea water.

These types of steels are usually limited in use to relatively thin sections due to lack of
toughness in welds. However, where welding is not required they offer a wide range of
applications. Since the ferritic steels may be cold formed easily (they are not as formable as
austenitic stainless steels), they are used extensively for deep-drawn parts such as vessels for
chemical and food industries, hot water tanks and automotive trims and exhausting systems.

7
The ferritic stainless steels are the lower-cost stainless steels, because they contain less
alloys, and do not contain nickel (nickel is more expensive than chromium).

1.5.2 Austenitic:

These stainless steels have a microstructure of austenite (FCC – face centered cubic crystal
structure) at room temperature. Austenitic stainless steel (such as the popular type 304) has
been called 18/8 stainless steel, because it contains nominally 18% Cr and 8% Ni. There are
30 compositional variations in the standard austenitic stainless steels, and a summary of the
family relationships is shown in Figure (2).
All the austenitic stainless steels are essentially chromium-nickel alloys. The chromium
varies between 15 and 24% and the nickel between 3 and 22%. The total content of
chromium and nickel in these steels is at least 23%. The family is derived from two basic,
general-purpose alloys, types 302 and 202. The type 302 expands into 26 other types
(chromium-nickel stainless steels, series 3xx) with specific compositional variations to
impart particular properties, for example, better weldability, increased strength, increased
heat resistance, better corrosion resistance, and improved machinability (For example,
lowering the carbon content to 0.08% maximum led to type 304 with improved weldability
and decreased tendency towards carbide precipitation). The type 202 is limited to only three
types (chromium-nickel-manganese stainless steels, series 2xx) and was designed to replace
nickel, a rather expensive alloying element, with nitrogen and manganese.

One of the most common grades of austenitic stainless steel is 316 which is the standard
molybdenum-bearing grade, second in importance to 304 amongst the austenitic stainless
steels. The molybdenum gives 316 better overall corrosion resistant properties than Grade
304, particularly higher resistance to pitting and crevice corrosion in chloride environments.
Grade 316L, the low carbon version of 316 and is immune from sensitisation (grain boundary
carbide precipitation). Thus it is extensively used in heavy gauge welded components (over
about 6mm). There is commonly no appreciable price difference between 316 and 316L
stainless steel. The austenitic structure also gives these grades excellent toughness, even
down to cryogenic temperatures. The following table illustrates its chemical composition in
weight percentage:

8
 Figure 2: Austenitic stainless steel families

1.5.3 Martensitic:

These steels like ferritic steels are primarily straight chromium steels containing between
11.5 and 18 percent chromium but have higher carbon levels as compared to ferritic steels (as
high as 1%). This allows them to be hardened and tempered much like carbon and low-alloy
steels. The steels have austenitic structure (FCC) at high temperature, which transforms to
martensitic structure (BCC) as a result of quenching. Types 410 and 416 are the most popular
and are used for turbine blades and corrosion-resistant castings. They are used where high
strength and moderate corrosion resistance is required. They attain the best corrosion
resistance when hardened from the recommended temperature but are not as good as the
austenitic or ferritic stainless steels.
This type of stainless steel is magnetic, can be cold-worked without difficulty, especially
with low carbon content, can be machined satisfactorily, have good toughness and is easily

9
hot-worked. However, they have generally low weldability and formability. This type of steel
is used for turbine blades, knife blades, surgical instruments, shafts, pins, springs, etc.

1.5.4 Duplex:

Duplex stainless steels contain high amount of chromium (18% -28%) and moderate (as
compared to austenitic steels) amount of nickel (4.5% – 8%) as major alloying elements.
Molybdenum is used in some of duplex steels as additional alloying element. Since the
quantity of nickel is insufficient for formation of fully austenitic structure, the structure of
duplex steels is mixed. The duplex class is so named because it is a mixture of austenitic
(chromium-nickel stainless steel) and ferritic (plain chromium stainless steel) structures.
These steels have a microstructure which is approximately 50% ferritic and 50% austenitic.
This gives them a higher strength than either ferritic or austenitic steels, but poorer toughness
than austenitic stainless steels.
They are weldable but need care in selection of welding consumables and heat input. They
have moderate formability. They are magnetic but not as much as the ferritic, martensitic and
PH types due to the 50% austenitic structure. They are suitable for heat exchangers,
desalination plants, petrochemical plants and marine applications.

1.5.5 Precipitation Hardening (PH):

Precipitation hardening stainless steels contain chromium and nickel as major alloying
elements. These steels can develop very high strength by adding elements such as copper,
niobium and aluminium to the steel. These elements tend to form coherent alloy precipitates.
These steels can be machined to quite intricate shapes requiring good tolerances before the
final aging treatment as there is minimal distortion from the final treatment. This is in
contrast to conventional hardening and tempering in martensitic steels where distortion is
more of a problem. They have good weldability and their corrosion resistance is comparable
to standard austenitic steels grade like 304. They are magnetic. They are used for pump
shafts, valves, turbine blades, paper industry equipment, aerospace equipment, etc. [5].

1.6 Common types of purified water:

1.6.1 Demineralized water:

Demineralised water is uncommonly purified water that has had most or the majority of its
mineral and salt particles evacuated, for example, Calcium, Magnesium, Sodium, Chloride,
Sulfate, Nitrate and Bicarbonate. It is otherwise called Deionized water, DI or Demin water.
It is also known as Deionized water, DI or Demin water. Demineralised water and deionized
water are generally considered distinct from distilled water, which is purified in a still i.e. by
boiling and re-condensing, a. a procedure which likewise uproots salt particles the significant
contrasts are that demineralised water is usually free of mineral ions, depending on the
number of processes used to make it, and distilled water may have less organic contaminants,
as deionization does not remove uncharged molecules such as viruses or bacteria. However,
deionization also leaves behind less ‘scale’ than distillation, and so has a cleaner production
[6].

10
Demineralised water, in the attempt of compensating its ionic imbalance, are particularly
greedy for gases as O2 or CO2 and as a result of this absorption of CO2, which dissolves in
water as carbonic acid lowering its pH, causes a diffused corrosion whose gravity
progressively rises as pH diminishes.
Demineralised water is used for industrial and scientific purposes. Some of the major and
common uses are:
1. laboratory applications and testing e.g. autoclaves
2. wash water for computer chip manufacture, and other microelectronics
3. automotive uses e.g. lead-acid batteries and cooling systems
4. high pressure boiler feed
5. laser cutting
6. steam irons and steam raising applications
7. pharmaceutical manufacturing
8. cosmetics (‘aqua’ often refers to DI water)
9. aquariums
10. fire extinguishers

1.6.2 Distilled water:

Distilled water is water which has undergone a purification process to remove any
contaminants and natural minerals, through a process called distillation. Distilled water has
been around for a huge number of years and its initially recorded use was around 200AD by
Alexander of Aphrodisias who distilled sea water to drink. A significant disadvantage of
producing distilled water is that it is very costly because of the large amounts of electricity or
fuel required for the distillation process. Distillation is a process which involves heating
water to boiling point, then collecting the produced steam in another container and
condensing it back into water.
Various minerals and impurities have a lower boiling point than water. This means that by
the time the water has boiled at 100°C and turned into steam, the minerals and impurities
have already reached their lower boiling point and subsequently evaporated, as they are not
part of the steam catchment process. As the steam from the water cools down, it turns back
into water and what is collected is pure distilled water [7].

There are plenty of specific uses for distilled water though, including use in:

 Chemical and biological laboratories

 Lead acid batteries
 Automotive cooling systems
 Steam irons
 Household aquariums

1.7 Carbon dioxide effect on steels:

Carbon dioxide CO2 is a very common contaminant in hydrocarbon fluids, especially in

gases and gas condensate, and is a source of corrosion problems. CO2 in the gas phase
dissolves in any water present to form carbonic acid H2CO3 which I highly corrosive. Its
reaction with iron creates iron carbonate FeCO3:

11
 CO2 (w) + H2O → H2CO3 (1.6)

CO2 + H2O = H2CO3 (1.7)

H2CO3 partially dissociates in two steps to form bicarbonate (HCO3 -) ions (Reaction 1.8) and
carbonate (CO3 -) ions (Reaction 1.9).
H2CO3 → H+ + HCO3 – (1.8)

HCO3 → H+ + CO3 - (1.9)

Fe+ + CO3 → FeCO3 (1.10)

The corrosion rate of steel in carbonic acid is faster than in hydrochloric acid. Correlations
are available to the rate of steel corrosion for different partial pressures of CO2 and different
temperatures. At high temperatures the iron carbonate forms film of protective scale on the
steel’s surface, but this is easily washed away al lower temperatures.

The initial rates of corrosion are generally independent of the type of carbon steel, and
chrome alloy steels or duplex stainless steels (chrome and nickel alloy) are required to reduce
the rate of corrosion [8].

12
Chapter 2
Literature review:
N.Fredj,T.D.Burleigh,K.L. Heidersbach and B.R. Crowder were investigating the corrosion
rate of low carbon steel in water with different purity with and without aeration at different
velocities .Mild steel test coupons are used (UNS G10100) with composition 99.49 Fe – 0.09
C – 0.33 Mn – 0.01 Cu –0.02 Cr – 0.05 Al .The coupons were with one surface ground and
the other surface (acid etched to remove mill scale). The tests were conducted from 1 hour to
14 days at ambient temperature. The water was either aerated or deaerated. They concluded
that in case of stagnant water, aerated with oxygen, the corrosion rate was very high initially
but within half a day; it dropped to the similar level of deaerated DI water as illustrated in
Figure (3) . The coupons were uniformly covered by a reddish brown gelatinous ferric oxide
film. They also found that contaminated water with dissolved salts of chloride, sulphate or
carbonate showed a linear increase of the corrosion rate with the concentration, with chloride
being the most aggressive. They concluded that The RO water was found to be much more
aggressive than DI water [9].

Figure 3 : Corrosion rate of steel versus time in aerated and deaerated DI

water.

M. MATSUDAIRA, M. SUZUKI and Y. SATO investigated carbon steel passivation

behaviour in deionized water by ellipsometry. Ellipsometric measurements was adopted to
study the passivation of steel surface and the film thickness and its refractive index were
determined .The water was either aerated or deaerated. DI water was with specific
conductivity K < 1 µS/cm .Corrosion Potential was recorded vs saturated calomel electrode
(SCE) Figure (4).It was found that a 4 to 5 nm thick passive film, whose refractive index was
N2 = 3.0 - 0.4i, was formed on the surface of carbon steel in oxygen containing flowing
water Figure (5). The film thickness was smaller with higher DO concentration and larger
flowing velocity. In stagnant DO containing water, the passive film was not stable and small
corrosion pits occurred. In deaerated water, the passive film disappeared in a relatively short
time and another type of film grew. The characteristics of the film formed in deaerated
system were different from that of the passive film Figure (6). Its refractive index was N2 =
2.0 - 0.2i and the thickness was 15 to 30 nm or more. This film was considered to be a

13
 corrosion product film which grew as corrosion proceeded. The film thickness was especially
large in stagnant system [10].

Figure 4: Corrosion potential time dependences for carbon steel Figure 5: DO concentration dependences of film thickness on
carbon steel in stirred deionized water (3 hours immersion).
N2 = 3.0 - 0.4i.

Figure 6: Film thickness time dependences for carbon steel in

deaerated stagnant and stirred deionized water. N2 = 2.0 - 0.21.

M. Gojiæ, D. Marijan,S. KoÞuhand T. Soriæwere investigating the passivation behaviour of

austenitic stainless steel AISI 316L at the temperature of 80 °c. Potentiodynamic polarization
technique is used to test the effectiveness of various passivation media. They found that
demineralized water at 80 °C caused damage to the steel surface. Potentiodynamic
polarization was carried out in demineralized water before and after passivation treatment.
Comparative analysis of the effectiveness of the selected passivation solutions showed that

14
the HNO3 solution, j = 6.0 %, containing CuSO4_ 5H2O, w = 2.0 %, in which AISI 316L
steel was kept for t = 3600 seconds at J = 60 °C, was the most suitable solution for surface
protection by passivation. By passivation in that solution the effect of pitting corrosion was
reduced to a minimum. To assess the influence of the passivation solution on the general and
pitting corrosion parameters a potentiodynamic curve was recorded for AISI 316L steel
immersed in a HNO3 solution, j = 6.0 %,containing CuSO4_ 5H2O, w = 2.0 % (3600 s, 60
°C) Figure(7) [11].

Figure 7: Anodic potentiodynamic curve for AISI 316L steel in HNO3

solution, j = 6.0 %, containing CuSO4 _ 5H2O, j = 2.0 % (3600 s, 60 °C) at
a scan rate of n = 5 mV s–1

Many phenomena associated with corrosion damage to iron-based alloys in pure water can be
rationalized on the basis of iron-water E-pH diagrams. Potential-pH diagrams are also called
Pourbaix diagrams after the name of their originator, Pourbaix (1963), a Belgium
electrochemist and corrosion scientist. These diagrams represent the stability of a metal as a
function of potential and pH at a particular combination of pH and potential, a stable phase
can be determined from the Pourbaix diagram. In such diagrams, the redox potential of the
corroding system is plotted on a vertical axis and the pH on a horizontal axis. These diagrams
are constructed from calculations based on Nernst equations and solubility data for metal and
its species, such as Fe, Fe2O3, Fe(OH)2, Fe3O4 as illustrated in figure (8), etc. in equilibrium.
And we can identify the stability region (immunity, corrosion, and passivity) as shown in
figure (9), however these are only indications; actual rates cannot be derived from the
diagrams. The information in the diagrams can be beneficially used to control corrosion of
pure metals in the aqueous environment. By altering the pH and potential to the regions of
immunity and passivation, corrosion can be controlled [12].

15
 Figure 8: Pourbaix diagram of iron Figure 9: stability region in Pourbaix diagram

There are many characteristics of a Pourbaix diagram; some of them are:

1. pH is plotted on the horizontal axis and redox potential E vs. SHE on the horizontal axis.
2. The horizontal lines represent electron transfer reactions. They are pH -independent, but
potential-dependent.
3. The vertical lines are potential-independent but pH-dependent and not accompanied by
any electron transfer.
4. The sloping, straight lines give the redox potentials of a solution in equilibrium with
hydrogen and oxygen, respectively. This equilibrium indicates electron transfer as well as
pH.
5. The concentration of all metal ions is assumed to be 10- 6 mole/litre of solution. At lower
concentration, corrosion should not occur.
6. The diagram is computed for the equilibrium conditions at 25°C.
7. The upper end of the redox potential axis is the noble end and the lower end, the active
end, meaning that the oxidizing power increase with increasing potential.
8. The hydrogen and oxygen lines are indicated in Pourbaix diagrams by dotted line.

The validity of the diagrams is limited to reactions between pure metals, pure water and the
species that can be formed from these. Small amounts of impurities and alloying elements in
the metal and dissolved substances in the water do not necessarily influence strongly on the
diagram, but in some cases they do. These are some of Pourbaix diagram limitations:

1. These diagrams are purely based on thermodynamic data and do not provide any
information on the reactions.
2. Consideration is given only to equilibrium conditions in specified environment and
factors, such as temperature and velocity are not considered which may seriously affect
the corrosion rate.
3. The activity of species is arbitrarily selected as 10-6 g/mole which is not realistic.
4. Pourbaix diagrams deal with pure metals which are not of much interest to the engineers.

16
5. All insoluble products are assumed to be protective which is not true, as porosity,
thickness, and adherence to substrate are important factors

Although the above disadvantages appear to be substantial, the advantages offered by the
Pourbaix diagrams far outweigh their limitations

17
Chapter 3
Experimental work:

In the experimental part we aim to investigate the corrosion behaviour of carbon steel X52
and stainless steel 316L using two techniques : Electrochemical experiments and Weight loss
test .On the other hand, surface analysis is done using optical microscope, scanning electron
microscope (SEM)and energy dispersive X-ray (EDX).

3.1 Material used:

The material used in this research were carbon steel X52 and stainless steel 316L provided
by Enppi - Engineering For The Petroleum & Process Industries

3.2 Sample preparation:

3.2.1 Cutting:

The samples were provided as large rectangular cuboid blocks. They were cut down into
small samples using milling machine found in the GUC workshop. The material was water
cooled to preserve its metallurgical structure, the samples were clamped mechanically to
prevent surface distortions and provide a straight edge; after that they were manually sawed
while mounted on the vice clamp to create work-pieces with suitable dimensions, The carbon
steel samples’ dimensions were nearly 1×1×1 cm while the dimensions of stainless steel
samples were nearly 1×1×0.65 cm.Then the samples were grinded to remove of any the black
rust from it ; to be easily grinded in the lab with the LaboStrues grinding machine .

3.2.2 Grinding and polishing:

The aim of this process is to remove any scratches from the surfaces of the samples and the
scratches done by sawing during cutting the samples were grinded on LaboStrues grinding
machine Figure (10). All grinding papers were waterproof Silicon Carbide, starting with 60
to 180,320, 600, 800, 1000 and 1200 grits per square inch (roughness variation). The average
grinding speed was 300 rpm. Water was used as coolant and lubricant in the grinding process
avoiding any mechanical damage of the sample, also to avoid damage due to heat resulting
from the friction of the samples with the grinding papers.
For electrochemical tests; only one surface was grinded with all the grinding papers
mentioned above, whereas for weight loss test measurements were grinded from all the sides
as it will be exposed totally to the electrolyte solution.

After grinding, the samples’ dimensions were calculated using vernier caliper then the
samples were polished to make the samples surfaces clearer. Polishing was carried out using
polishing discs made of cloth and fine diamond particles. Three different particles grade were
used: Two coarse 6 & 3 micron polish are used to remove all the scratches from the samples’
surfaces; finally a fine 1 micron polish was used to produce a smooth surface.

18
 Figure 10: Grinding and polishing machine

3.2.3 Cold mounting:

The aim of this part is to cover all the surfaces of the samples of electrochemical tests except
one surface which will be exposed to the solution. A copper wire was attached to the samples
in order not to make any electrical resistance which may lead to further noise.The samples
were mounted using a Seri fix Resin and Seri fix hardener with ratio 50:1 by pouring the
mixture in cylindrical plastic cups where the samples were centered as shown in figure (11)
and figure (12), then leaving the mixture with the samples one day at room temperature
without moving to hold and stick together. Afterwards, the samples were polished using
polishing discs.

Figure 11: Mounting process Figure 12: Mounted sample

19
3.2 Storage of the samples:
In order to avoid formation of any oxide layer on the samples’ surfaces; the samples were
cleaned by ethyl alcohol then dried by a cool air or by napkin then placed in plastic small bag
and stored in a silica box.

3.3 Demi water preparation:

The demi water was prepared using a very special device

(PURELAB UHQ II) showing in the following figure which is a
unique system, combining the most efficient water purification
techniques in a compact, well styled unit, which is ideally suited
to the modern laboratory.

3.3.1 PURELAB built-in technologies include:

1. Reverse osmosis
A pre-treatment cartridge containing a highly efficient, low
pressure, thin-film composite membrane to deionize the
feedwater and remove colloidal and microbiological impurities.
Figure 13: PURELAB UHQ II
2. Adsorption
A cartridge of high quality adsorption media for removal of low molecular weight organic
compounds.
3. Deionization
A cartridge of specially conditioned nuclear grade ion exchange resin for absolute ionic
purity.
4. Microfiltration
A sub-micron membrane cartridge to provide enhanced security from any traces, colloidal
organics, micro-organisms and particles.
5. Photo-oxidation
A short wavelength ultra-violet photochemical reactor cell for destruction of micro-
organisms and cleavage of trace organic compounds, to assist in the reduction of (TOC).

3.3.2 Feedwater specification:

The PURELAB UHQ II is designed to operate automatically on raw potable feedwater but to
achieve the highest purity; we should use pre-purified water like distilled water.

20
3.3.3 Demi water specifications:
Table 2: Demi water specifications

Inorganics 18.2 MΩ-cm @ 25°C

Organics <0.0001AU @ 254nm
TOC <20 ppb
Micro-organisms <1 CFU/ml
Particles 0.05μm filtration

After water preparation, water is stored in cleaned plastic bottle with a nozzle then the nozzle
was covered with Parafilm to prevent any air contamination.

3.4 Weight loss technique:

The simplest way of measuring the corrosion rate of a metal is to expose the sample to the
test medium. The sample is then cleaned of all corrosion products using corrosion removal
solution and is reweighed to calculate the weight loss as a function of time. Although these
tests are simple, there is no simple way to extrapolate the results to predict the lifetime of the
system under investigation. Moreover, some corrosion processes occur with no significant
mass change (e.g. pitting corrosion) making them difficult to detect by gravimetric methods
[13].
The weight loss is converted to a corrosion rate (CR), as follows:

The constant can be varied to calculate the corrosion rate in various units:

Table 3: variation of the constant of the corrosion rate

Desired Corrosion Rate Unit Area Unit (A) K-Factor

(CR)

mils/year (mpy) In 5.34 x 105

mils/year (mpy) Cm 3.45 x 106

millimeters/year (mmy) Cm 8.75 x 104

Weight loss determination has a number of attractive features that account for its
sustained popularity:

1. Simple - No sophisticated instrumentation is required to obtain a result.

21
 2. Direct - A direct measurement is obtained, with no theoretical assumptions or
approximations.
3. Versatile - It is applicable to all corrosive environments, and gives information on all
forms of corrosion.

3.5 Method of cleaning after testing:

This process involves immersion of the corrosion test specimen in a specific solution that is
designed to remove any corrosion product with minimal dissolution of the base metal.
 For iron and steel the corrosion removal solution was prepared as follows:
A combination of (500 mL hydrochloric acid + 25 g stannous chloride + 10 g antimony
trioxide) is mixed at 70°C for 20 min to obtain homogeneous solution then covered with
Parafilm to avoid air contamination.
During cleaning process, the solution should be vigorously stirred or specimen should be
brushed.
 For stainless steel alloys the corrosion removal solution was as follow:
A combination of (100 mL Nitric acid HNO3+ 1000 mL reagent water) is mixed at 60°C for
20 minutes [14].

3.6 Electrochemical Measurements:

Since corrosion is actually a process involving electrochemical oxidation and reduction

reactions, it makes sense that electrochemical methods can be used to study and measure
corroding systems. More specifically, when a metal is immersed in a given solution,
electrochemical reactions characteristic of the metal-solution interface occur at the surface of
the metal, causing the metal to corrode. These reactions create an electrochemical potential,
called the corrosion potential or the open circuit potential (measured in volts), at the metal-
solution interface. Since the corrosion potential is determined by the specific chemistry of the
system, it is a characteristic of the specific metal-solution system.

There is an important practical point to consider when measuring the corrosion potential.
Simply stated, the corrosion potential (or ECORR) of the metal-solution interface cannot be
directly measured. Since all voltage measuring devices measure a potential energy
difference, ECORR can only be compared to the potential of a known reference system (EREF)
and can only be indirectly measured. Figure (14) shows how you can easily measure ECORR.
With a reference electrode placed in the same solution as the metal, you can record ECORR
with an electrometer (a voltage measuring device). As long as you use the same type of
reference electrode in each measurement, you should be able to consistently reproduce the
ECORR vs. EREF measurement in any given metal-solution system.

22
 Figure 14: Measurement of ECORR for a metal-solution system.

Only a few types of reference electrodes have been used for corrosion work and in recent
years most corrosion specialists have been using a single type – the Saturated Calomel
Electrode (SCE) which is used in our tests. Furthermore, if you measure ECORR using a
different type of reference electrode, you can easily convert the result of the measurement to
a SCE-related value, since the potential differences between various types of reference
electrodes are well documented.

3.6.1 Cell preparation:

The electrochemical cell used throughout this project Consists of 3 main components:

1. The electrolyte.
2. The working electrode.
3. The reference and auxiliary electrodes.

And the electrochemical cell is connected to an electronic instrument called a potentiostat.

23
Figure 15: SCE and Auxiliary electrode Figure 16: VoltaLab Radiometer Analytical, FRANCE

Three main techniques will be conducted throughout this experiment the open circuit
potential (OCP), Potential cyclic voltammetry (PCV) and Tafel analysis.

3.6.2 Open Circuit potential (OCP):

OCP is the process in which the potential of the working electrode is relative to the
potential of the reference electrode when no current is applied in the cell. The cell consists
of 3 electrode first the working electrode, After that comes the auxiliary electrodes (Pt)
which is not involved in the reaction, the third one is the standard calomel electrode (SCE)
which is the reference electrode based on the reaction between elemental mercury and
mercury I chloride filled with standard solution (potassium chloride in water). All these
electrodes were immersed one in demi water or distilled water. The working electrode’s
potential is measured relative to that of the reference electrode as variation of current as a
function of time until a steady state is reached.

3.6.3 Potential cyclic voltammetry (PCV):

A CV system consists of an electrolysis cell, a VoltaLab Radiometer Analytical, a current-to-

voltage converter, and a data acquisition system. The electrolysis cell consists of a working
electrode, counter electrode, reference electrode, and electrolytic solution. The working
electrode’s potential is varied linearly with time, while the reference electrode maintains a
constant potential. The counter electrode conducts electricity from the signal source to the
working electrode. The purpose of the electrolytic solution is to provide ions to the
electrodes during oxidation and reduction. A potentiostat is an electronic device which uses
a dc power source to produce a potential which can be maintained and accurately
determined, while allowing small currents to be drawn into the system without changing

24
the voltage. The current-to-voltage converter measures the resulting current, and the data
acquisition system produces the resulting voltammogram.

3.6.4 Tafel analysis:

In this experiment, a relation between the potential and log of the current density is
determined. After plotting a graph of the potential relative to log current density, two slopes
are done to the anodic and cathodic regions in the graph as shown in figure (17) . One way of
determining Icorr is to superimpose a straight line along the linear portion of the anodic or
cathodic curve and extrapolate it through ECORR. Under ideal conditions, the Tafel plot will
be linear over some rangeof potentials. For a cathodic Tafel plot, this occurs between -50 mV
and -250 mV vs. ECORR. For an anodic Tafel plot, this occurs between +50 mV and +250 mV
vs. ECORR. If a “best fit” straight line is extrapolated through ECORR, the point of intersection
at ECORR gives the Icorr value. Corrosion currents are directly related to corrosion rates.
Finally, after the corrosion current calculation, the corrosion rate of each sample can be
calculated from following equation:

CPR: Corrosion penetration rate (mm / year)

ICORR: Corrosion current (A/cm)
M: Atomic mass (gm)
P: Density (gm/cm³)
n: Valence number of the sample

Figure 17: Tafel analysis

25
3.6.5 VoltaMaster software:

Using this software we can control and monitor the two operations we are going to conduct
in this experiment first the OCP experiment and then the PCV experiment, finally further
analysis will be conducted to estimate the tafel curve and the corrosion rate.
3.6.5.1 Steps of the OCP experiment:

1. Creating a new file and entering the following data: operator, date, specification of the
test, working electrode, reference electrode (standard calomel electrode), auxiliary
electrode (platinum electrode) and comments if there are any.
2. From "Settings" click on "cell setup" and the following data is entered: area in (cm²),
atomic mass in (grams) and density in (gm/ cm³).
3. Clicking on sequence and choosing our desired type of test: open circuit potential and
settling the time to 90 minutes and check mark on "save points".
4. Operate the cell and click on "Start" to initiate the test.
3.6.5.2 Steps of the PCV experiment:

1. Creating a new file and entering the following data: operator, date, specification of the
test, working electrode reference electrode (standard calomel electrode), auxiliary
electrode (platinum electrode) and comments if there are any.
2. Click on "Sequence" and choose "potential cyclic voltammeter", double click this choice
and set the values of "potential 0"(-750) ,"potential 1"(-750) and "potential 2"(2000).The
scan rate to be 2 mV/second and the number of cycles to be 1.the value of "potential 0"
where it starts, "potential 1" where it ends and "potential 2" it’s the maximum value
wanted to be reached as its the peak of the curve.
3. Operate the cell and click on "Start" to initiate the test.

3.6.5.3 Steps of Tafel analysis:

1. Open the PCV curve

2. Click on “ Tafel “
3. Adjust the calculating zone , smoothing and segment
4. Click on “draw”
5. Collect the data (Ecorr, Icorr and corrosion rate)

3.6.6 Surface analysis:

3.6.6.1 Optical microscope:

The optical microscope is a type of microscope which uses visible light and a system of
lenses to magnify images of small samples. Optical microscopes are the oldest design of
microscope and were possibly designed in their present compound form in the 17 the

26
century. Basic optical microscopes can be very simple, although there are many complex
designs which aim to improve resolution and sample contrast. Historically optical
microscopes were easy to develop and are popular because they use visible light so the
sample can be directly observed by eye. The Zeiss Optical microscope shown in figure (18)
was used to observe the microstructure of every sample before and after testing. Pictures of
the samples were taken at 10X magnification.

Figure 18: Zeiss optical microscope

3.6.6.2 Scanning Electron Microscope:

The Scanning Electron Microscope (SEM) is a microscope that uses electrons rather than
light to form an image. There are many advantages to using the SEM instead of a light
microscope. The SEM has a large depth of field, which allows a large amount of the sample
to be in focus at one time. The SEM also produces images of high resolution, which means
that closely spaced features can be examined at a high magnification. Preparation of the
samples is relatively easy since most SEMs only require the sample to be conductive. The
combination of higher magnification, larger depth of focus, greater resolution, and ease of
sample observation makes the SEM one of the most heavily used instruments in research
areas today.

3.6.6.3 Energy-dispersive X-ray Spectroscopy:

It is an analytical technique used for the elemental analysis or chemical characterization of a

sample. As a type of spectroscopy, it relies on the investigation of a sample through
interactions between electromagnetic radiation and matter, analyzing x-rays emitted by the
matter in response to being hit with the electromagnetic radiation. Its characterization
capabilities are due in large part to the fundamental principle that each element has a unique
atomic structure allowing x-rays that are characteristic of an element’s atomic structure to be
identified uniquely from each other. EDX makes use of the X-ray spectrum emitted by a

27
solid sample bombarded with a focused beam of electrons to obtain a localized chemical
analysis. All elements from atomic number 4 (Be) to 92 (U) can be detected in principle.

28
Chapter 4
Results and discussion:

4.1 Weight loss measurements:

It is the simplest and long-established method of estimating corrosion losses. A weighed

sample of the metal or alloy under consideration is introduced into the process, and later
removed after a reasonable time interval. The sample is then cleaned of all corrosion
products and is reweighed.
1. Carbon steel (X52) in demi water:

The dimensions of the samples were calculated before the test and they were as follows:
Table 4: Dimensions of CS sample in demi water

Length (mm) Width(mm) Height(mm)

9.7 9.65 9.6

After that the exposed area was calculated using the following equation:
= 2*[length*width] + 2*[height*length] + 2*[width*height]
= 2*[9.7*9.65] +2*[9.6*9.7] +2*[9.6*9.65]
= 5.5878 cm2
The following Table illustrate all the data of this test:

Table 5: CS in demi water test data

Working Time (h) Weight Weight PH before PH after Weight

temperatu before(g) after(g) loss (g)
re
°C
25 24 6.6770 6.6756 7.27 4.54 0.0014

Figure of the sample after the test:

29

Figure 19: CS after weight loss test in demi water

It is clear from figure (19) that the sample is covered with black layer (black intermediate
layer between hydrous Fe2O3 and FeO) as expected.

Corrosion rate calculation:

Table 6: Corrosion rate calculation of CS in demi water

Weight K Density(g/cm3) Area(cm2) Time(hr)

loss(g)
1.4×10- 8.76×104 7.86 5.5878 24
3

Corrosion rate(mm/year)

0.1163

After weight loss test the solution colour was turned to orange or red-brown due to the
perception of small rust particles and using high magnetic field it was found that these
particles are hydrous ferric oxide which exists as nonmagnetic Fe2O3 (hematite)

2. Carbon steel (X52) in distilled water:

The dimensions of the samples were calculated before the test and they were as follows:

Table 7: Dimensions of CS sample in distilled water

Length (mm) Width(mm) Height(mm)

9.6 9.41 9.31

After that the exposed area was calculated using the following equation:

= 2*[length*width] + 2*[height*length] + 2*[width*height]

= 2*[9.6*9.41] +2*[9.31*9.6] +2*[9.41*9.31]
= 5.34638 cm2

30
The following Table illustrate all the data of this test:

Table 8: CS in distilled water test data

Working Time (h) Weight Weight PH before PH after Weight

temperatu before(g) after(g) loss (g)
re
°C

25 24 6.3728 6.3720 7.00 4.6 0.0008

And this was the figure of the sample after the test:

Figure 20: CS after weight loss test in distilled water

As illustrated in figure (20) the sample is covered with black intermediate layer between
hydrous Fe2O3 and FeO.

Corrosion rate calculation:

Table 9: Corrosion rate calculation of CS in distilled water

Weight K Density(g/cm3) Area(cm2) Time(hr.)

loss(g)
8×10-4 8.76×104 7.86 5.34638 24

Corrosion rate(mm/year)

0.0694

31
3. Stainless steel (316L) in demi water:

The dimensions of the samples were calculated before the test and they were as follows:
Table 10: Dimensions of SS sample in demi water

Length (mm) Width(mm) Height(mm)

9.7 9.7 6.2

After that the exposed area was calculated using the following equation:
= 2*[length*width] + 2*[height*length] + 2*[width*height]
= 2*[9.7*9.7] +2*[6.2*9.7] +2*[6.2*9.7]
= 4.874 cm2

The following Table illustrate all the data of this test:

Table 11: SS in demi water test data

Working Time (h) Weight Weight PH before PH after Weight

temperatu before(g) after(g) loss (g)
re
°C

25 24 4.3762 4.3755 7.27 4.69 0.0007

And this was the figure of the sample after the test:

Figure 21: SS after weight loss test in demi water

Figure (21) shows how the SS sample is not affected by the test and a asserts that SS has
higher corrosion resistance in demi water than CS

32
Corrosion rate calculation:

Table 12: Corrosion rate calculation of SS in demi water

Weight K Density(g/cm3) Area(cm2) Time(hr.)

loss(g)

7×10-4 8.76×104 7.86 5.34638 24

Corrosion rate(mm/year)

0.0608

4. Stainless steel (316L) in distilled water:

The dimensions of the samples were calculated before the test and they were as follows:

Table 13: Dimensions of SS sample in distilled water

Length (mm) Width(mm) Height(mm)

9.7 9.7 6.2

After that the exposed area was calculated using the following equation:

= 2*[length*width] + 2*[height*length] + 2*[width*height]

= 2*[9.7*9.7] +2*[6.2*9.7] +2*[6.2*9.7]
= 4.874 cm2

The following Table illustrate all the data of this test:

Table 14: SS in distilled water test data

Working Time (h) Weight Weight PH before PH after Weight

temperatu before(g) after(g) loss (g)
re
°C

25 24 4.4883 4.4878 7.27 4.29 0.0005

33
And this was the figure of the sample after the test:

Figure 22: SS after weight loss test in distilled water

As shown in figure (22): SS in distilled water has higher corrosion resistance than CS, we
can distinguish that the sample is very clear and there is not any corrosion product.

Corrosion rate calculation:

Table 15: Corrosion rate calculation of SS in distilled water

Weight K Density(g/cm3) Area(cm2) Time(hr.)

loss(g)
5×10-4 8.76×104 7.86 4.874 24

Corrosion rate(mm/year)

0.04763

The following table contains a comparison between the corrosion rates of our different
samples:
Table 16: comparison between the corrosion
rates
Sample Corrosion rate (mm/year)
CS in demi water 0.1163

CS in distilled 0.0694
water
SS in demi water 0.0608

SS in distilled 0.04763
water

It is clear that CS has higher tendency to corrode in both demi water and distilled water than
SS which has higher corrosion resistance.

34
4.2 Electron Microscope:

After finishing the weight loss measurements, the samples were dried and saved in small
bags. Surface analysis was done for the samples using Scanning Electron Microscope (SEM)
followed by Energy Dispersive X-ray (EDX) .For each sample, two photos are taken with
magnification 200X and 3000X and the results are as follows:

1- Carbon steel in demi water:

Figure 23: CS in demi water 200X

35

Figure 24: CS in demi water 3000X

 Figure 25: EDX of CS in demi water

Table17: EDX results of CS in demi

water
Elements Wt.% At. % K-ratio Z A F
CK 2.55 8.43 0.0053 1.1339 0.1831 1.0006
OK 12.63 31.31 0.0509 1.1177 0.3593 1.0041
Mn K 1.70 1.22 0.0162 0.9543 0.9997 1.0000
Fe K 83.12 59.04 0.8152 0.9742 1.0067 1.0000
Total 100.00 100.00

We can notice from figure (23) that CS in demi water is attacked vigorously by pitting
corrosion and the density of pits is very high. The EDX results show high Weight percentage
of oxygen and this supports the formation of iron oxides on the surface. Also the weight
percentage of carbon is high compared its percentage in the base metal so it is likely to be
due to formation of iron carbonate.

36
2- Carbon steel in distilled water:

Figure 26: CS in distilled water

200X

Figure 27: CS in distilled water

3000X
37
 Figure 28: EDX of CS in distilled water

Table 18: EDX results of CS in distilled

water
Elements Wt.% At. % K-ratio Z A F
CK 2.63 9.97 0.0053 1.1473 0.1758 1.0007
OK 5.17 14.73 0.0201 1.1308 0.345 1.0051
Mn K 1.91 1.59 0.0184 0.9661 0.9960 1.0000
Fe K 90.29 73.71 0.8939 0.9864 1.0036 1.0000
Total 100.00 100.00

It is clear from figure(26) that CS in distilled water is attacked by pitting corrosion but the
density of pits is much less than it was in demi water. The EDX results show high Weight
percentage of oxygen is high compared to the other elements and this supports the formation
of iron oxides on the surface. Also the weight percentage of carbon is high compared to its
percentage in the base metal so it is likely to be due to formation of iron carbonate.

38
3- SS in demi water:

Figure 29: SS in demi water 200X

Figure 30: SS in demi water 3000X

39
 Figure 31: EDX of SS on demi water

Table 19: EDX results of SS in demi

water
Elements Wt.% At. % K-ratio Z A F
CK 1.35 5.56 0.0027 1.1527 0.1710 1.0005
OK 2.32 7.16 0.0092 1.1361 0.3479 1.0038
Al K 0.49 0.89 0.0012 1.0631 0.2236 1.0013
Si K 0.81 1.42 0.0028 1.0949 0.3105 1.0022
Cr K 18.37 17.47 0.2119 0.9870 0.9834 1.1883
Mn K 2.19 1.97 0.0214 0.9709 0.9945 1.0119
Fe K 65.04 57.58 0.6181 0.9913 0.9443 1.0151
Ni K 9.43 7.94 0.0786 1.0113 0.8235 1.0000
Total 100.00 100.00

It is obvious from figure (29) that SS in demi water has high corrosion resistance. The EDX
results show high Weight percentage of oxygen is much lower than CS samples. Also the
weight percentage of carbon is low so it has higher resistance to form carbonate.

40
4- SS in distilled water:

Figure 32: SS in distilled water 200X

Figure 33: SS in distilled water

3000X
41
 Figure 34: EDX of SS on distilled water

Table 20: EDX results of SS in distilled

water
Elements Wt.% At. % K-ratio Z A F
CK 2.06 8.27 0.0041 1.1511 0.1718 1.0005
OK 2.33 7.03 0.0091 1.1346 0.3431 1.0037
Al K 0.43 0.77 0.0010 1.0617 0.2255 1.0014
Si K 0.94 1.62 0.0032 1.0934 0.3133 1.0022
Cr K 18.19 16.89 0.2095 0.9855 0.9839 1.1881
Mn K 2.23 1.96 0.0217 0.9795 0.9949 1.0117
Fe K 64.58 55.85 0.6133 0.9899 0.9453 1.0149
Ni K 9.25 7.61 0.0771 1.0098 0.8252 1.0000
Total 100.00 100.00

SS showed approximately the same results in both demi water and distilled water. And this
supports its high corrosion resistance in pure water.

42
 4.3 Electrochemical measurements:

4.3.1 Open circuit potential (OCP):

After the samples were subjected to the Open circuit potential mechanism, each sample had a
different behaviour regarding potential variation. Before discussing the curve and the
behaviour of each sample, it must be noted that if the potential decreases with time, no oxide
layer is being formed which means that the sample is actually corroding and if the potential
increases, then there is a passive layer that has formed on the sample, protecting it from
corrosion. All the potentials were calculated vs. Saturated Calomel Electrode (SCE).
1. OCP of CS X52 in demi water:

-400
CS in demi water
-420

-440
Potential (mV)

-460

-480

-500

-520

-540

0 20 40 60 80 100
Time (min)

Figure 35: OCP of CS X52 in demi water

The OCP curve of this sample in demi water shows the tendency of the carbon steel sample
to dissolve oxide layer formed on the surface of the carbon steel sample since the curve starts
from a more positive potential at -400 mV and ends at a more negative potential at -530 mV
which is an indication to low resistance and a high corrosion rate. The drop at the beginning
of the curve it means that the oxide layer formed from the air on the sample surface starts to
break down and the surface is exposed now to the solution in the cell and starts reacting with
it. Moreover the noises that appear on the curve show the tendency of the pitting corrosion.
The curve is stable around -530 mV which is the Eocp.

43
2. OCP of CS X52 in distilled water:

-320
CS in distilled water

-340

-360
Potential (mV)

-380

-400

-420

-440

-460

-480

-500

0 20 40 60 80 100
Time (min)

Figure 36: OCP of CS X52 in distilled water

The OCP curve of this sample in distilled water shows the tendency of the carbon steel to
dissolve oxide layer formed on the surface of the carbon steel sample since the curve starts
from a more positive potential at -332.5 mV and ends at a more negative potential at -493
mV. The drop at the beginning of the curve it means that the oxide layer formed from the air
on the sample surface starts to break down and the surface is exposed now to the solution in
the cell and starts reacting with it. The curve is stable around -493 mV which is the Eocp.

44
3. OCP comparison between CS in demi water and distilled water:

-320 CS in distilled water

-340 CS in demi water

-360

-380
Potential (mV)

-400

-420

-440

-460

-480

-500

-520

-540

0 20 40 60 80 100
Time (min)

Figure 37: OCP comparison between CS in demi water

and distilled water

This comparison illustrates the difference between the OCP of CS in demi water and
distilled. The more the curve tends to negative the lower the corrosion resistance and the
higher the corrosion rate. It is clear that, for CS in distilled the OCP potential is around -493
mV but for CS in demi water the OCP potential is around -530 mV so demi water affects CS
more aggressively than distilled water.

45
4. OCP of SS 316L in demi water:

0 SS in demi water

-50
Potential (mV)

-100

-150

-200

-250

-300
0 20 40 60 80 100 120
Time (min)

Figure 38: OCP of SS 316L in demi water

The OCP curve of this sample shows the tendency of the sample to form a protective oxide
layer on the surface as it goes to the more positive potential as the curve starts from -268 mV
and ends at -41.8 mV . The OCP potential at which the curve is stable and constant is around
-41.8 mV which is called Eocp.

46
4. OCP of SS 316L in distilled water:

-80
SS in distilled water

-100
Potential (mV)

-120

-140

-160

0 20 40 60 80 100
Time (min)

Figure 39: OCP of SS 316L in distilled water

The OCP curve shows the tendency of this stainless steel sample to dissolve the pre-formed
oxide film. Since the potential goes to more negative as it starts at -89.2 mV and
ends at -144.3 mV .The drop at the beginning of the curve it means that the oxide layer
formed from the air on the sample surface starts to break down and the surface is exposed
now to the solution in the cell and starts reacting with it.

47
5. OCP comparison between SS 316L in demi water and distilled water:

SS in demi water
0
SS in distilled water

-100
Potential (mV)

-200

-300
0 20 40 60 80 100 120
Time (min)

Figure 40: OCP comparison between SS 316L in demi water

and distilled water

This comparison illustrates the corrosion resistance of SS in demi water. As we can see from
the curves, SS in demi water tends to form protective film as the curve tends to more positive
potential while in distilled water, metal dissolution occurs as the curve tends to more
negative potential.

48
6. OCP comparison between CS X52 and SS 316L in demi water:

CS in demi water
0
SS in demi water

-100

-200
Potential (mV)

-300

-400

-500
0 20 40 60 80 100 120
Time (min)

Figure 41: OCP comparison between CS X52 and SS

316L in demi water

This comparison illustrates the different behaviours of CS X52 and SS 316L in demi water.
As mentioned before, the more the curve tends to go to more positive potential this is an
indication to higher resistance to corrosion therefore less corrosion rate ,and when it goes to
more negative potential it is an indication on lower resistance to corrosion so high corrosion
rate. So it is clear that SS has higher corrosion resistance and lower corrosion rate than CS as
it tends to form protective film; and the CS curve shows its lower corrosion resistance and
weakness to form protective film.

49
4.3.2 Potential cyclic voltammetry (PCV):

This technique measures the pitting tendencies of a specimen in a given metal-solution

system. We apply a potential scan beginning at ECORR (the open circuit potential) and
continuing in the positive (anodic) direction until a large increase in current occurs. When the
scan reaches a user programmed current density value, it reverses and begins scanning in a
negative (cathodic) direction. The scan rate is typically 2 mV/sec. The working potential
range is between -750 mV to 2000 mV.
1. PCV of CS X52 in demi water:

CS in demi water
150
2
Current density µA\cm

100

50

-1000 -500 0 500 1000 1500 2000 2500

Potential mV

Figure 42: PCV CS X52 in demi water

When the curve start to go above zero it means that this is the first potential at which the
first pit will be initiated. So it is clear that pitting starts early. The area of the curve is
small indicating very small numbers of pits formed.

50
2. PCV CS X52 in distilled water:

CS in distilled water

100
2
Current density µA\cm

µ
50

-1000 -500 0 500 1000 1500 2000 2500

Potential mV

Figure 43: PCV CS X52 in distilled water

When the curve start to go above zero it means that this is the first potential at which the first
pit will be initiated. So it is clear that pitting starts early. The area of the curve is small
indicating very small numbers of pits formed.

51
3. PCV comparison of CS X52:

( 1 ) CS in distilled water
( 2 ) CS in demi water
150
2
2
Current density /cm

100 1

50

-1000 -500 0 500 1000 1500 2000 2500

Potential mV

Figure 44: PCV comparison of CS X52

This figure shows that the curve of CS in demi water is shifted to more negative potential
than the curve of CS in distilled water so it is clear that distilled water has lower effect on
CS.

52
4. PCV of SS 316L in demi water:

SS in demi water

80
2
Current density \cm

40

-40

-1000 -500 0 500 1000 1500 2000 2500

Potential mv

Figure 45: PCV of SS 316L in demi water

The Figure above shows that, the current density is approximately constant from -750
mV to around 546 mV which indicates the oxidation and reduction reactions that happens
uniformly between the SS sample and the demi water. When the curve starts to go above
zero it means that pits start to initiate.

53
5. PCV of SS 316 L in distilled water:

SS in distilled water
60

40
2
Current density A\cm

20

-20

-1000 -500 0 500 1000 1500 2000 2500

Potential mV

Figure 46: PCV of SS 316 L in distilled water

The Figure above shows that, the current density is approximately constant from -750 mV to
around 726 mV which indicates the oxidation and reduction reactions that happens uniformly
between the SS sample and the demi water. When the curve starts to go above zero it means
that pits start to initiate.

54
6. PCV comparison between CS and SS in demi water and distilled:

( 1 ) CS in distilled water
( 2 ) CS in demi water
( 3 ) SS in demi water
150 ( 4 ) SS in distilled water
2
2

1
Current density A/cm

100

3
4
50

-50
-1000 -500 0 500 1000 1500 2000 2500
Potential mV

Figure 47: PCV comparison between CS and SS in demi

water and distilled

This figure shows all the PCV curves of the tested samples, and it makes a consequent series
related to the OCP curves. The more the curve is shifted towards the more positive potential
the more the pitting resistance is expected to be, and following this sense, the above figure
shows that stainless steel tends to have more pitting resistance ,in demi water and distilled
water, than carbon steel. It is clear also that carbon steel in distilled water has higher pitting
resistance than it has in demi water.

55
The following table illustrate the pitting potential of all samples in different water purity:

Table 21: Pitting potential of all the samples

Test Pitting potential (mV)

CS in demi water -345

CS in distilled water -330

SS in demi water 546

SS in distilled water 726

This table shows the difference between CS and SS in localized corrosion resistance i.e.
pitting, as mentioned above; the more positive Ep, the higher the resistance of steel to the
initiation of localized attack. So it is clear that SS has higher corrosion resistance than CS in
both demi and distilled water.

56
4.3.3 Tafel analysis:

After receiving the date from the potentiodynamic polarization curves, it is used in creating
another form of polarization, known as the tafel method. The tafel method in done by
applying the log function to the Y-axis (current density .The corrosion in length per year can
be calculated by estimating Icorr and Ecorr from the intersection of the slope in tafel region and
by substituting these values in the corrosion rate equation .
1. Tafel curves for carbon steel in both demi water and distilled water:

3
CS in demi water

1
log (A\cm )
2

-1

-2

-3
-900 -600 -300 0
Potential (mV)

Figure 48: Tafel curve of CS in demi water

CS in distilled water

2
log (A\cm )
2

-2

-900 -600 -300 0

Potential (mV)
Figure 49: Tafel curve of CS in distilled water

57
 ( 1 ) CS in demi water
1 ( 2 ) CS in distilled water

0
log (A\cm )
2

-1

-2

-3
-900 -600 -300 0
Potential (mV)

Figure 50: Tafel comparison of CS

Readings were taken from VoltaMaster program, after plotting curves using the tafel method,
which helped in collecting the data much faster and with an average accuracy too. The results
showed the corrosion rate of the samples in both water purities Table (22).

Table 22: corrosion rate of CS samples in both water purities

Water Icorr (A/cm2) Ecorr Corr. Rate

(m/year)

Distilled 0.5095 -486.9 5.9

Demi 0.6155 -470.9 7.2

It is obvious that CS in demi water has the higher corrosion rate and thus the lowest
corrosion resistance compared to distilled water

58
2. Tafel curves for stainless steel in both demi water and distilled water:

6
SS in demi water

4
log(nA\cm )
2

0
-900 -600 -300 0 300 600
Potential mV

Figure 51: Tafel curve of SS in demi water

6
SS in distilled water

4
log(nA\cm )
2

0
-900 -600 -300 0 300 600
Potential (mV)

Figure 52: Tafel curve of SS in distilled water

59
 (1) SS in demi water
4 (2) SS in distilled water
1

2
log(nA\cm )
2

0
-900 -600 -300 0 300 600
Potential (mV)
Figure 53: SS Tafel comparison

Readings were taken from VoltaMaster program, after plotting curves using the tafel method,
which helped in collecting the data much faster and with an average accuracy too. The results
showed the corrosion rate of the sample in both water purities.

Table 23: corrosion rate of SS samples in both water purities

Water Icorr (nA/cm2) Ecorr Corr. Rate

(nm/year)

Distilled 56.56 -235.4 661.6

Demi 75.9 -221 888.2

From the last table, we can notice that demi water has more aggressive effect on SS than
distilled water as the corrosion rate of SS in demi water is higher than in distilled water.

60
4.4 Optical microscope:

After electrochemical test, optical microscope was used to investigate the samples’ surfaces
and the corrosion mechanism. The following pictures illustrate the results:

Figure 54: Carbon steel in demi water Figure 55: Carbon steel in distilled water

Figure 56: Stainless steel in demi water Figure 57: Stainless steel in distilled water

It is obvious that carbon steel in demi water has high tendency to pitting corrosion but it has
higher resistance in distilled water. On the other hand, stainless steel showed very high
resistance in both demi water and distilled water

61
Chapter 5
Conclusion:

Two samples (Carbon steel X52 and Stainless steel 316L) were the focus of this study. The
samples were subjected to two different corrosion tests to observe their corrosion behaviour:

The electrochemical corrosion test (OCP and PCV) at room temperature and the weight loss
measurements in demi water and distilled water. The Tafel curve was obtained from the
results of the PCV stage and the corrosion rate of every sample. Surface analysis was
observed using the Optical & Scanning electron microscope (SEM) and the elemental
composition was identified using energy dispersive x-ray analysis (EDX)

In the light of the obtained results of this work to evaluate the corrosion behaviour, the
following conclusion can be drawn:

 Carbon steel X52

For the electrochemical tests, the results illustrated the relation between the water purity and
the corrosion rate. In the OCP tests for CS samples it was found that the Eocp decreased
gradually towards the more negative potential, which means that samples has the least
corrosion resistance. In demi water, the OCP curve tends to more negative potential so it is
clear that demi water affect CS more aggressively than distilled water. In the PCV tests, demi
water sample was shifted to the more negative potential, and then followed by distilled water
which was shifted towards the more positive potential as an indication that it has more pitting
corrosion resistance. The tafel curves were used to calculate the corrosion rates .It also
showed that there is a linear relation between corrosion rate value & Water purity

For weight loss tests, the measurements assisted the electrochemical results with comparable
corrosion rates in both demi water and distilled water. CS in demi water showed higher
corrosion rate than in distilled water. The microscopic analysis illustrated how demi water
attacks CS aggressively and the density of the pits was very high. On the other hand, distilled
water has lower effect on the carbon steel. It was noticed that the samples were covered by
black intermediated layer between hydrous Fe2O3 and FeO. The pH was measured and it
decreased significantly may be due to the formation of carbonic acid.

 Stainless steel 316L

For electrochemical test, The OCP curves showed the tendency of SS to form protective
oxide layer in demi water but in distilled water SS tends to metal dissolution which means
lower corrosion resistance. In the PCV tests, demi water sample was shifted to the more
negative potential, and then followed by distilled water which was shifted towards the more
positive potential as an indication that it has more pitting corrosion resistance. The tafel
curves were used to calculate the corrosion rates .It also showed that there is a linear relation
between corrosion rate value & Water purity but the corrosion rate was very low compared to
CS samples.
For weight loss tests, the results supported the electrochemical measurements with
comparable corrosion rates in both demi water and distilled water. In demi water SS has

62
higher corrosion rate than in distilled water. The microscopic analysis showed the high
corrosion resistance of SS in pure water, the surfaces were approximately clear and not
affected by any type of corrosion. The pH was measured and it decreased significantly may
be due to the formation of carbonic acid.
To sum up, Demi water is often referred to as "hungry water". The absence of ions from
demineralized water makes demineralized water more aggressive than any type of water. It
wants to be in equilibrium and will pull ions out of the surrounding metals trying to satisfy its
"hunger”. It does become slightly acidic due to dissolved CO2 from the air.
Stainless steel is preferable choice of material in demi water or distilled water as it has high
corrosion resistance than carbon steel.

63
Bibliography
1- Gellings, P. J. Introduction to Corrosion Prevention and Control for Engineers. Delft:
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