Republic of Iraq

Ministry of Higher Education

and Scientific Research
University of Babylon
College of Materials Engineering
Department of Metallurgical Engineering

Effect of indium on wear and

corrosion resistance of α-brass alloy
A Thesis

Submitted to the Department of Metallurgical Engineering /

College of Materials Engineering / University of Babylon in
Partial Fulfillment of the Requirements for the Degree of Higher
Diploma in Materials Engineering / Metallurgical.

By

Ahmed Amer Ali

)B.Sc. Materials Engineering(
)2015(
Supervised by

Assist .Prof .Dr .Haydar Hassan Jaber

(2017) A.D
 ‫وزارة التعليم العالي والبحث الــــعـلمي‬
‫جــامـــــعــــــــــــــــة بـابـــــــــــــــــــــل‬
‫كليـــــــــــــة هنـــــــــــــــــــــدسة المواد‬
‫قســم هنــــــــــــــــــــــــدسـة المـعــادن‬

‫تأثير االنديوم على مقاومة البلى والتأكل‬

‫لسبيكة الفا‪-‬براص‬
‫رسالة‬
‫مقدمة إلى قسم هندسة المعادن في كلية هندسة المواد‪ /‬جامعة‬
‫بابل وهي جزء من متطلبات نيل درجة الدبلوم العالي في‬
‫هندسة المواد‪ /‬المعادن‬
‫من قبل‬
‫احمد عامر علي‬
‫(بكالوريوس هندسة مواد )‬
‫(‪)2015‬‬
‫بإشراف‬
‫أ‪.‬م‪.‬د‪ .‬حيدر حسن جابر‬

‫‪ 1027‬م‬
 Acknowledgments

Praise Be To Allah, Lord of the Creation

First of all, profusely all thanks be for )ALLAH ,the

most gracious) of all creations who enable me to achieve

this work. I would like to express my gratitude and

appreciation to my supervisor, (Assist. Prof Dr.

Haydar Hassan Jaber) for guidance , advice and

enthusiastic encouragement throughout my study.

I would also like to thank the staff of Materials

Engineering laboratories at the University of Babylon.
The support and understanding of my family is deeply
appreciated. Their love has been for me a powerful source
of inspiration and energy, support and encouragement
that have made all of this possible.

Ahmed
 ‫الر ِح ِيم‬
‫الر ْح َم ِن ه‬ ‫ِب ْس ِم ه ِ‬
‫َّللا ه‬
‫ح‬
‫الرو ُ‬ ‫الروحِ قُ ِل ُّ‬ ‫۞ َويَسألُونَ َك ع َِن ُّ‬
‫ِم ْن أ َ ْم ِر َر ِبّي َو َما أُو ِتيتُم ِ ّمن ا ْل ِع ْل ِم ِإالَّ‬
‫قَ ِليالً ۞‬

‫صدق هللا العظيم‬

‫{ سورة اإلسراء ‪ /‬آية ‪}58‬‬

 Dedication
To…. my merciful God
To…. my dear and respected father
To…. my beloved mother
To….my brothers and sisters .. Love,
respect and appreciation.
To…. All my friends who loved me and I
loved in my life. To all the lovers of
Engineering and seeking to the top
degrees.
I dedicate this work with love and

respect…

Ahmed Amer Ali

(2017)
 Supervisor Certification

I certify that this thesis entitled “Effect of indium on some properties of

brass alloy’’ was prepared by (Ahmed Amer Ali) under my supervision at
department Metallurgical Engineering / University of Babylon in a partial
fulfillment of the requirements for the degree of higher diploma of Science in
Materials Engineering / Metallurgical Engineering .

Signature:

Name:
Assist. Prof. Dr. Haydar Hassan Jaber

(Supervisor)

Date: / /
 Examining committee Certification
We certify that have read this thesis entitled '' Effect of indium on the
wear and corrosion properties of brass alloy'' and as an examining
committee, we have examined the student(Ahmed Amer Ali) in contents
and that is related to it, and that in our opinion it meets the standard of a
thesis for the degree of higher diploma of science in Materials
Engineering.
Signature:
Asist. Prof.Dr. Jassim Mohammed Salman
(Committee Chair)
Date: / /2018
Signature: Signature:
Asist. Prof. Dr. Ekbal Mohammed Saeed Asist. Prof.Dr. Haydar Hassan Jaber
(Committee Member) (Committee Member)
Date : / / 2016 Date : / / 2018

Approval of the Department of Approval of the Department of

Metallurgical Engineering Metallurgical Engineering
Head of metallurgy Engineering Head of metallurgy Engineering
Department Department

Signature Signature

Asist. Prof.Dr.Haydar Hassan Jaber prof.Dr.Kadhim F . Al Sultani

Date : / / 2018 Date : / / 2018

 List of Contents
Sequence Subject Page No.

Abstract I

List of Contents III

List of Figure VI

List of Tables X

Symbols and abbreviations XI

Chapter one:
Introduction
1.1 Introduction 1
Chapter Two:
Theoretical Part & Literature Review

2.1 Introduction 4
2.2 Properties and Uses of Copper 4
2.3 Base Alloys 5
2.4 Types of Brass Alloys 6
2.4.1 Alpha Brass (α) Alloys 6
2.4.2 Duplex brasses (α + β) 7
2.5 Microstructure of Brass Alloys 8
2.6 Corrosion 10
2.7 Type of Corrosion 10
2.7.1 General corrosion 10
2.7.2 Localized Corrosion 11
2.7.2.1 Pitting 11
2.7.2.2 Galvanic corrosion 13

III
2.7.2.3 Stress Corrosion Cracking 13
2.7.2.4 Intergranular Corrosion 14
2.8.1 Dealloying /Dezincification 15
2.8.2 Dezincification: Mechanism 17
2.9 Alloying Elements Commonly Added to Brass 17
Alloy
2.10 Heat Treatment for Brass Alloy 19
2.10.1 Full annealing 19
2.10.2 Annealing 20
2.10.3 Stress Relieving 21
2.10.4 Temper Annealing 21

2.11 Wear Mechanisms 22

2.12 Wear Theories 22
2.13 Hardness 24
2.14 Type of Hardness 24
2.14.1 Vickers Hardness 25
2.15 Literature Review 26
Chapter three:
Experimental Part
3.1 Introduction 30
3.2 Materials 30
3.3.3 Preparation of Sample 32
3.3.1 Melting and Casting Process for Material 32
3.3.2 Heat Treatments 33
3.3.3 Cutting Samples 34
3.3.4 Polishing 35
3.4 Testing of The Sample 35
3.4.1 Microstructure Test 35
3.4.2 Microhardness Test 36
3.4.3 Open circuit potential (OCP) 37
3.4.4 Potentiostatic Polarization 38
3.4.5 Dry Sliding Wear Test 39
3.4.6 X-Ray Diffraction Test 40
IV
3.4.7 X-Ray Fluorescent Analysis (XRF) 41

Chapter Four:
Results and Discussion
4.1 Introduction 42
4.2 Microstructure test 42
4.3 Microhardness Tests 44
4.4 Dry Sliding Wear Test 45
4.5 Electrochemical Tests 48
4.5.1 Open circuit potential (OCP)-time measurement 48
4.5.2 Potentiodynamic polarization 55
4.6 X-Ray Diffraction analysis 54
Chapter Five : Conclusions&
Recommendations
5.1 Conclusions 55
5.2 Recommendations 56

V
 List of Figure

Chapter Tow :
Theoretical Part & Literature Review
Figure(2-1): Some shape of brass 5
Figure (2-2) : Copper-Zinc partial phase diagram 7
Figure (2-3) : Diagram indicates the relationship between 8
composition and mechanical properties
Figure (2-4) : The crystal structure of brass. 9
Figure (2-5) : General corrosion. 11
Figure (2-6): Different shapes of corrosion pits 12
figure(2-7): Galvanic corrosion 13
Figure (2-8) Stress corrosion of metal 14
Figure (2-9) Intergranular corrosion of metal 15
Figure (2-10): Dezincification of brass 16
Figure (2-11) Effect of annealing temperature on brass strength 21
Figure (2-12): Hardness impression 24
Figure (2-13) : Vickers impression 25
Chapter Three :
Experimental Part
Figure (3-1): The experimental flowchart for the present work. 31

Figure (3-2): Electric furnace 32

Figure (3-3): Melting crucible 32
Figure(3-4): metallic mold 33
Figure(3-5): Rod samples α- brass after casting process 33
Figure (3-6): Electric heat treatment furnace 33
Figure (3-7): Horizontal turning machine 34
Figure(3-8): Microstructure & Hardness samples 34
Figure (3 -9): Grinding & polishing machine 35

VI
Figure(3- 10): Alight optical microscope(LOM). 36

Figure (3-11): Microhardness (HV) measuring 37

Figure (3-12) Schematic drawing of open circuit potential 38
measure
39
Figure (3-13): shows the electrochemical system

Figure (3-14): (A)Pin-on-disc wear instrument , (B) Pin-on- 39

disc concept

Figure (3.15) X- Ray Diffraction Analyzer 40

Figure (3-16) X-ray fluorescent (XRF) 41

Chapter Four :
Results and Discussions
Figure (4-1):Light optical microstructure for α- brass ( Cu 42
/Zn30) after heat treatment (A 100X, B 4 00X)
Figure(4-2):Light optical microstructure for (α- brass + 43
0.5wt %In) after heat treatment (A 100X, B 400X)
Figure(4-3): Light optical microstructure for (α- brass + 43
1wt %In) after heat treatment (A 100X, B 400X)
Figure(4-4): Light optical microstructure for (α- brass + 43
1.5wt %In) after heat treatment (A 100X, B 400X)
Figure(4-5): Light optical microstructure for (α- brass + 44
2wt %In) after heat treatment (A 100X, B 400X)
Figure(4-6):Effect of In content on microhardness for α- brass 44
without &with ( 0.5,1,1.5,and 2 wt % In)

Figure(4-7): Weight loose vs time for α-brass under (10, 15 and 45

20 N )load
Figure(4-8): Weight loose vs time for (α-brass+ 0.5wt%In) 45
under (10, 15 and 20 N )load under (5, 10 and 15 N )load

VII
Figure(4-9): Weight loose vs time for (α-brass+ 1wt% In) 46
under(10,15 and 20 N )load
Figure(4-10): Weight loose vs time for (α-brass+ 1.5wt% In) 46
under (10, 15 and 20 N )load
Figure(4-11): Weight loose vs time for (α-brass+ 2 wt% In) 47
under (10, 15 and 20 N )load
Figure(4.12): Wear rate vs In content for the samples under 48
(20 N )load (25 min)time
Figure (4-13) shows the OCP-time in NaCl solution at 37±1 C° 49
for all tested samples
Figure (4-14) The corrosion rate of α- brass 51
Fig (4-15) The effect of (0.5)wt% In on corrosion rate of α- 51
brass

Figure (4-16)The effect of(1)wt% In on corrosion rate of α- 52

brass
Figure (4-17) The effect of (1.5)wt% In on corrosion rate of α- 52
brass
Figure (4-18) The effect of (2)wt% In on corrosion rate of α- 53
brass
Figure(4.19): Corrosion rate vs In content for the samples in 53
NaCl solution
Figure(4.02): Result of X-ray diffraction analysis for(α- 54
brass)alloy specimen
Figure(4.02):Result of X-ray diffraction analysis for(α- 54
brass+2)wt% In alloy specimen

VIII
 List of Tables

Chapter Three :
Experimental Work
Table( 3-1) ) Detected chemical composition of α -brass alloy 30
without & with addition(0.5,1,1.5and2) wt% In
Chapter Four :
Results and Discussions
Table (4-1) Shows the corrosion current (Icorr.) , corrosion 50
potential (Ecorr.) and corrosion rate for all used samples in
NaCl Solution at 37 C°.

IX
 List of symbols and abbreviations

Symbols and
Description Unit
abbreviations

F.C.C Face center cubic

B.C.C Body center cubic
ASTM American Society for Testing and Material
Δw Weight change g
Q Volume of The Weariness

HV Vickers hardness Kg/mm2

F load applied of the sample g

OCP Open Circuit Potential

XRF X-ray fluorescence

SIER State Company for Inspection and Engineering
Rehabilitation
XRD X-Ray Diffraction

α alpha- phase
β beta- phase
Ecorr Corrosion Potential mV
Icorr Corrosion Current Density μA/cm²
LOM Light optical microscope
mV Millimeter Volt
Wt%. Weight percentage g

X
 Abstract

This study investigates the effect of indium as alloying element on

the corrosion, wear and hardness behavior of α- brass . The samples
prepared by casting method. The alloying element (In) was added with
percentage of (0.5, 1, 1.5 and 2) wt. %.The alloys were treated at a
temperature (550˚C) for 6 hours in order to homogenize the
composition. The alloys were cut using a turning machine to get
samples for inspections.

The goals of this research have been achieved through tests that
including: microstructure test , hardness test, corrosion resistance test,
wear test and X-Ray Diffraction (XRD) .

From results obtained in this study , it is found that the hardness

for (α- brass + 2wt % In ) increased by ( 49.8 %) , the corrosion
resistance of α- brass alloy improved after the addition of indium in
NaCl solution compared with the α- brass where the percentage of
improvement for (α- brass + 2wt % In ) was (99.4%), Wear
resistance increased in general with increasing the applied load . The
(α- brass+2 wt% In) has more wear resistance than (α- brass+1.5 wt%
In) , (α- brass+1 wt% In), (α- brass+0.5 wt% In) and α- brass alloys.

Optical images of (100X,400X) magnification showed the

microstructure was achieved of the α-brass alloy after addition
(0.5,1,1.5 and 2wt %) indium with compared to α- brass alloy. The
In has no effect on the microstructure of the α-brass alloy and this
due the very low content of In in this alloy.

I
 ‫الخالصة‬

‫ْذِ اندراست حب‪ ٍٛ‬حأث‪ٛ‬ز االَد‪ٕٚ‬و كعُصز سبك عهٗ خٕاص يقأيت انخأكم ‪ ,‬انسٕفاٌ‬
‫ٔانصالدة نسب‪ٛ‬كت انفا بزاص‪ .‬حى ححظ‪ٛ‬ز انع‪ُٛ‬اث بطزقت انسباكت ‪,‬حًج اضافت عُصز انسبك‬
‫(االَ‪ٕٛ‬و) بُسب ‪ . )2.5.1.1.5.0(wt%‬حى اجزاء يعايهت حزار‪ٚ‬ت نهسبائك عُد درجت حزارة‬
‫‪ 552˚C‬نًدة ‪ 6‬ساعاث يٍ اجم حجاَس انخزك‪ٛ‬ب‪ .‬حى قطع انسبائك بٕاسطت ياكُّ انقطع‬
‫نهحصٕل عهٗ ع‪ُٛ‬اث يٍ اجم انفحض‪.‬‬
‫انٓدف يٍ ْذا انفحض ْٕ انحصٕل عهٗ اخخباراث حخضًٍ ‪:‬اخخبار انبُ‪ٛ‬ت انًجٓز‪ٚ‬ت‪,‬‬
‫اخخبار انصالدة‪ ,‬يقأيت انخأكم‪ ,‬اخخبار انسٕفاٌ ٔح‪ٕٛ‬د االشعت انس‪ُٛٛ‬ت‪.‬‬
‫يٍ خالل انُخائج انخ‪ ٙ‬حى انحصٕل عه‪ٓٛ‬ا ف‪ْ ٙ‬ذِ اندراست‪ٔ ,‬جد اٌ انصالدة نم ( ‪α-‬‬
‫‪ )brass + 2wt % In‬اسدادث بحدٔد ‪ , 49.8%‬يقأيت انخأكم ف‪ ٙ‬يحهٕل كهٕر‪ٚ‬د‬
‫انصٕد‪ٕٚ‬و نسب‪ٛ‬كت انفا بزاص ححسُج بعد اضافت االَد‪ٕٚ‬و يقارَّ يع سب‪ٛ‬كت انفا بزاص‬
‫(بدٌٔ اضافت) ح‪ٛ‬ث كاَج َسبت انخحسٍ نم( ‪, 99.4% ْٙ (α- brass + 2wt % In‬‬
‫يقأيت انسٕفاٌ اسدادث بشكم عاو يع س‪ٚ‬ادة انحًم انًسهط ‪ ,‬ح‪ٛ‬ث اٌ ( ‪α- brass+2 wt%‬‬
‫‪ )In‬كاَج اقٕٖ يقأيت سٕفاٌ يٍ (‪(α- brass+1 wt% , (α- brass+1.5 wt% In‬‬
‫)‪ ٔ (α- brass+0.5 wt% In) ,In‬سب‪ٛ‬كت بزاص انفا (بدٌٔ اضافت)‪.‬‬
‫انفحض بانًجٓز انضٕئ‪ ٙ‬ححج قٕة حكب‪ٛ‬ز )‪ (100X,400X‬ب‪ ٍٛ‬انبُ‪ٛ‬ت انًجٓز‪ٚ‬ت انخ‪ ٙ‬حى‬
‫انحصٕل عه‪ٓٛ‬ا نسب‪ٛ‬كت انفا بزاص بعد اضافت)‪ (0.5,1,1.5 and 2wt %‬يٍ االَد‪ٕٚ‬و‬
‫يقارَت يع سب‪ٛ‬كت انفا بزاص (بدٌٔ اضافت)‪ .‬ح‪ٛ‬ث اٌ االَد‪ٕٚ‬و ال ‪ٚ‬ظٓز ا٘ حأث‪ٛ‬ز عهٗ انبُ‪ٛ‬ت‬
‫انًجٓز‪ٚ‬ت نسب‪ٛ‬كت انفا بزاص بسبب انكً‪ ّٛ‬انقه‪ٛ‬هت جدا يٍ االَد‪ٕٚ‬و انًضاف‪.‬‬

‫‪II‬‬
Chapter One Introduction

Chapter One
Introduction
1.1 Introduction

Copper is a pinkish-red metal, soft, easily workable, and has a good

corrosion resistance. It posses the second highest thermal and electrical
conductivity among metals. It can be easily machined, fabricated, welded,
brazed and soldered. The most important properties of copper are
electrical conductivity and corrosion resistance [1].

Nowadays, brasses are widely applied in technology, and they belong

to the most commonly used alloys in the group of non-ferrous metals .
Brass alloys are applied in various domains of industry, among others in
civil engineering, armaments industry, aircraft industry, machine
building, the production of car motors, electrical industry, ship building,
precision mechanics, chemical industry and many others, even in the
production of musical instruments. These alloys are characterized by a
considerable ductility and resistance to corrosion, particularly
atmospheric corrosion and corrosion in sea [2].

It has been reported that increasing the zinc content in brass alloys
above 45% increases their brittleness, and that the optimal mechanical
properties are displayed by brass containing about 30% zinc. Those are
characterized by considerable plastic properties together with high tensile
strength and hardness . Brasses can easily be cast to shape or fabricated
by extrusion, rolling, drawing, hot stamping and cold forming[3].

The correct choice of brass is important if manufacturing and

operating requirements are to be met in the most cost-effective way to

1
Chapter One Introduction

suit every need, there are over sixty standard compositions for brass with
copper contents ranging from 58% to 95%. Apart from the major alloying
element, zinc, small additions (less than 5%) of other alloying elements
are made to modify the properties so that the resulting material is fit for a
given purpose [4].

Properties of brasses depend upon the amount of zinc content in the

alloy. Strength of the brass increases with increasing the amount of zinc
content, and it attains a maximum value at about 40 percent zinc. On the
other hand corrosion resistance and ductility of brasses decrease with in-
crease in the amount of zinc. The best combination of strength and
ductility is obtained when the zinc content is about 30 percent. Brasses
are widely used in those applications which require high strength, good
corrosion resistance, and high thermal and electrical conductivity. Some
commonly used commercial brasses are red brass, cartridge brass, muntz
metal etc.
Brasses are generally used in harsh conditions, because they can be
easily rolled or extruded due to high plasticity of the material. Some
brasses are used in as-cast condition. The cast brasses should have high
castability and machinability, which are obtained by additions of lead and
tin[1].
A system containing copper -zinc on several phases that can be
summarized as follows:

1. (α - solid solution alpha)

Consists of soluble zinc in copper and reduce about 35% zinc, the
crystalline composition of the type f.c.c, this phase is characterized by
being malleable and ductile .

2
Chapter One Introduction

2. (β - solid solution)
The result of the interaction between the developed alpha(α) and
molten, the crystalline composition of the type which b.c.c phase, and
crisp hard.
3. ( - solid solution)
The result of the interaction between the developed solid beta phase
(β) and the remaining molten, the crystalline composition of the type
which b.c.c. phase and crisp hard [5].
Many elements may be added in small amounts to the( α- brass) in
order to improve mechanical and physical properties including:
(microstructure ,hardness , compression, tensile , and wear resistance )
.A number of researchers have studied the effects of adding elements
such as (Al ,Ni ,Ge, Cr ,…. etc ) on the ( α-brass) alloy properties[6].

The aim of this research

This work study the effects of indium addition (0.5,1,1.5 and 2) wt %

on some mechanical properties and physical properties including:
(microstructure ,hardness, corrosion resistance and wear resistance) of
( α-brass) alloys and discuss the results .

3
Chapter Two Theoretical Part & Literature Review

Chapter Two
Theoretical Part & Literature Review

2.1 Introduction
This chapter will cover a general view about copper and its alloys ,also
will pay a brief look at the phase diagram of copper and its alloys .There
have been focus on the brass alloys , their chemical compositions
,mechanical and chemical properties ,also there have been focus on the
heat treatment and applications of brass alloys , and there is some
attention to the wear properties and theories . Finally the end of this
chapter will cover some of the recent research and studies about brass
alloys in general .

2.2 Properties and Uses of Copper

Copper and its alloys are widely used in a variety of products that
enable and enhance our everyday lives. They have excellent electrical and
thermal conductivities, exhibit good strength and formability, have
outstanding resistance to corrosion and fatigue, and are generally
nonmagnetic [4]. They can be polished and buffed to almost any desired
texture and luster. Pure copper is used extensively for electrical wire and
cable, electrical contacts and various other parts that are required to pass
electrical current .Coppers and certain brasses, bronzes and copper
nickels are used extensively for automotive radiators, heat exchangers,
home heating systems, solar collectors, and various other applications
requiring rapid conduction of heat across or along a metal section.
Because of their outstanding ability to withstand corrosion, coppers,
brasses, bronzes and copper nickels are also used for pipes, valves and

3
Chapter Two Theoretical Part & Literature Review

fittings in systems carrying potable water, process water or other aqueous

fluids, and industrial gases [7].
2.3 Brass Alloys
Brass is the best material from which to manufacture many
components because of its unique combinations of properties. Good
strength and ductility are combined with excellent corrosion resistance
and super machinability. [8]. Figure (2.1) [4] shows some shapes of
brass.

Figure (2-1) Some shape of brass [4].

4
Chapter Two Theoretical Part & Literature Review

2.4 Types of Brass Alloys

Brass alloys can be divided in to two types :

2.4.1 Alpha Brass Alloys (α):

Alpha brasses(α) are malleable, can be cold worked, and are used in
pressing, forging, or similar applications. They contain only one phase,
with face-centered cubic crystal structure. With their high content of
copper, these brasses have a more golden hue than others ,it can be
divided to [9] :

1- Brass Alloy (70% Cu – 30% Cu )

The range of alloys, termed ‘alpha brasses’, or ‘cold working brasses’,
contain a minimum 63% of copper. They are characterized by their
ductility at room temperature, and can be extensively deformed by
rolling, drawing, bending, spinning and deep drawing. The best known
material in this group contains 30 wt % zinc and is often known as
‘70/30’ or ‘cartridge’ brass, CuZn30 - due to the ease with which the
alloy can be deep drawn for the manufacture of cartridge cases CuZn30
possesses the optimum combination of properties of strength, ductility
and minimal directionality which make it capable of being severely cold
drawn [5].

2- Gilding Metals and Cap Copper (80 to 90%Zn)

Alpha brasses with higher copper contents (80 to 90%), which closely
match gold in their color, are known as ‘gilding metals’ .They are used
for decorative metal ware and roll-formed sections for architectural
applications. Cap copper CW500L (CZ125) is a 95/5 brass, CuZn5, with
good ductility and corrosion resistance, only rarely used other than for
caps for ammunition [10].

5
Chapter Two Theoretical Part & Literature Review

3- Standard Brass Alloy (65%Cu / 35%Zn)

Alpha brasse with copper content (65wt%) Cu is considered the
cheapest alloys. These alloys forming on the cold to a large degree and
used for public purposes, such as industry (screws) , (rivet) ,and
condensate pipelines [10]. Figure (2.2) [4] shows Copper-Zinc partial
phase diagram.

Figure(2-2) Copper-Zinc partial phase diagram [4].

2.4.2 Duplex brasses (α + β):

The ‘alpha-beta brasses’, ‘duplex brasses’ or ‘hot working brasses’
usually contain between 38% and 42% zinc. In contrast to the alloys of
the first group, their ability to be deformed at room temperature is more
limited. They are, however, significantly more workable than the alpha
brasses at elevated temperatures and can be extruded into bars of complex
section, either solid or hollow, and hot forged in closed dies (hot

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Chapter Two Theoretical Part & Literature Review

stamped) to complex shapes. The ideal hot working temperature range is

whilst the brass is cooling, between 750˚C and 650˚C, during which the
alpha phase is being deposited .It is used in pipes and faucets and fixtures
industry pools radiation and industry hands of doors and furniture [11].
Figure (2-3)[6] shows diagram indicates the relationship between
composition and mechanical properties.

Figure(2-3) Diagram indicates the relationship between composition and

mechanical properties [6].

2.5 Microstructure of Brass Alloys

Brass commonly consists of two phases, the Cu rich α-phase and the
Zn rich β-phase. Their occurrence depends on the amount of Cu and Zn
in the material, as well as the temperature . Brass consists of several
phases, of which the α- phases and β-phases are of interest in this study.
The occurrence of the phases depends on the composition of the material
and the temperature. The more Cu brass contains, the more α-phase. For
materials with more than 70 % Cu, only α-phase is present. The α-phase
can be made de-zincification resistant through addition of As, a process

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which is not fully understood until this days. The β-phase cannot be made
dezincification resistant, and is therefore undesired in drinking water
applications, such as faucets. For brass with 32 to 38 % Zn weight, it is
possible to transform the β-phase to α-phase, by heat treatment of the
material at 500°C for about two hours, for brass with up to 38 % Zn,
the α-phase is stable at 500°C. The microstructure of brass consists of
grains. The grain boundaries are usually less ordered than the grain
centers, and impurities, such as Pb, tend to accumulate in these
boundaries, material is often supplied in the form of rods, produced by
extrusion, which means that the bulk material is pressed through a hole to
form the shape of a rod. This leads to deformations in the microstructure,
and the grains takes the form of strings. If β-phase is present, these β-
strings could act as paths for corrosion through the material, therefore it is
very important to heat treat the material to eliminate the β-phase [12].
Figure (2.4)[6] shows the crystal structure of brass.

Figure (2-4) The crystal structure of brass.

Atom 'Y' occupies a body- centered position in cube 'A', whilst atom Z occupies
a body centered position in cube 'B'. This is in fact the 'cesium chloride' type of
structure and not really BCC as it first appears[6]

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Chapter Two Theoretical Part & Literature Review

2.6 Corrosion:

Metals corrosion is considered as one of the most challenging and

serious problems worldwide. When metals contacts with various
environments, like water, air, pollutants, or chemical products they start
to degrade because of the interaction between the metal and its
environment [13].
Metallic materials corrosion is classified into three groups :
1. Wet corrosion: in which the corrosion environment is water or
electrolyte solution. The process is electrochemical.
2. Chemical Corrosion: happens in other fluids like molten metals and
fused salts.
3. Dry corrosion: in which the corrosive surrounding is a dry gas. Dry
corrosion is also named as high temperature metal gas corrosion[14].
Two main areas are noticed in the corrosion of alloys and metals. The
first one is where the alloy or metal is exposed to an electrolyte liquid,
mostly water, and thus typically called aqueous corrosion. Second one is
where corrosion happens in a gaseous environment, often called
oxidation, High- Temperature Oxidation, or High-Temperature
Corrosion, and here it is called as gaseous corrosion. Those two types
were (sometimes still are) referred to as dry corrosion and wet
corrosion[15].

2.7 Type of Corrosion:

2.7.1 General corrosion
The most common type of corrosion and it can be even or uneven as
shown in Fig. (2-5). It is described by a chemical or electrochemical
reactions that occur on the metals surfaces. The metal becomes thinner
and finally cause a failure. General corrosion can be prevented or

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Chapter Two Theoretical Part & Literature Review

decreased by the suitable choice of material or by use of cathodic

protection or corrosion inhibitor [16].

Figure (2-5) General corrosion [16].

2.7.2 Localized Corrosion

The attack is characterized by the formation of severely corroded
regions separated with sharp steps from neighboring areas with much less
attack. Localized attack develops when the surface is partly covered with
a protective film. The attack is usually associated with high flowrates.
However, experiments have shown that localized attack can also be
initiated and propagate under semi-stagnant conditions [17].

2.7.2.1 Pitting

Pitting corrosion is a localized form of corrosion by which cavities or

"holes" are produced in the material. Pitting is considered to be more
dangerous than uniform corrosion damage because it is more difficult to
detect, predict and design against. Pitting corrosion can produce pits with
their mouth open (uncovered) or covered with a semi-permeable
membrane of corrosion products. Pits can be either hemispherical or cup-
shaped [18], as shown Fig. (2-6).

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Chapter Two Theoretical Part & Literature Review

Pitting is considered to be autocatalytic in nature; once a pit starts to

grow, the conditions developed are such that further pit growth is
promoted. The anodic and cathodic electrochemical reactions that
comprise corrosion separate spatially during pitting. The local pit
environment becomes depleted in cathodic reactant (e.g., oxygen), which
shifts most of the cathodic reaction to the boldly exposed surface where
this reactant is more plentiful[19].
Localized corrosion of copper, at least in the form of the pitting of
copper water pipes, is a well-known phenomenon. Pit initiation involves
the local breakdown of a Cu2O film at grain boundaries or other surface
defects. The pit propagates because of the permanent separation of anodic
and cathodic sites, with the anodic reaction localized in the bottom half of
the pit under a porous Cu2O membrane and the cathodic reaction (the
reduction of Cu (II)) occurring in top half of the pit or (as the reduction of
O2) on the Cu surface around the periphery of the cap of corrosion
products [20].

Figure (2-6) Different shapes of corrosion pits [22]

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Chapter Two Theoretical Part & Literature Review

2.7.2.2 Galvanic corrosion

Galvanic corrosion tends to occur when dissimilar conducting

materials are connected electrically and exposed to an electrolyte, figure
(2-8). The following fundamental requirements therefore have to be met
for galvanic corrosion:
1. Dissimilar metals (or other conductors, such as graphite).
2. Electrical contact between the dissimilar conducting materials (can be
direct contact or a secondary connection).
3. Electrolyte (the corrosive medium) in contact with the dissimilar
conducting materials [23].

Figure (2-7) Galvanic corrosion [23].

2.7.2.3 Stress Corrosion Cracking

Stress corrosion cracking (SCC), or environmentally assisted

cracking, requires a specific corrosive environment and a simultaneous
stress for it to occur. There are several environments that can cause SCC
of copper and its alloys, of which the best known is ammonia (NH 3). The
stress to cause cracking can be an externally applied load due to service
conditions or an internal stress due, for instance, to welding or cold
working. The environment that caused the cracking was airborne

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Chapter Two Theoretical Part & Literature Review

ammonia, and the stress was the residual stress in the deep-drawn
cartridge cases [21], as shown Fig. (2-9).
The factors determining the mechanisms and the course of development
can be sorted into three main groups:
1. Environmental and electrochemical factors.
2. Metallurgical factors.
3. Mechanical stress and strain
The study of SCC is typically multidisciplinary, i.e. the description of the
three groups of factors and their effects belong to three different
technological disciplines, namely electrochemistry/corrosion, physical
metallurgy and fracture mechanics [14].

Figure (2-8) Stress corrosion of metal [23].

2.7.2.4 Intergranular Corrosion

Intergranular corrosion refers to preferential corrosion along the

grain boundaries. Grains are ‘crystals’ usually on a microscopic scale,
that constitute the microstructure of the metal and alloys. It has been
defined commonly as a form of localized attack on the grain boundaries
of a metal or alloy in corrosive media, which results in the loss of

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Chapter Two Theoretical Part & Literature Review

strength and ductility. The localized attack may lead to dislodgment of

the grain. It works inwards between the grains and causes more loss
of strength than the same total destruction of metal uniformly distributed
over the whole surface . The attack is distributed over all the grain
boundaries cutting the surface. Intergranular corrosion is less dangerous
than stress corrosion, which occurs when stress acts continuously or
cyclically, in a corrosive environment, producing cracks following mostly
intergranular paths[24]. This type of corrosion may have extreme effects
on mechanical properties, resulting in a loss of strength and ductility ,this
is shown in Fig.(2-9).

Figure (2-9) Intergranular corrosion of metal [23].

2.8.1 Dealloying /Dezincification

Dealloying, also known as selective leaching, is a rare corrosion form
in which one element extracted from a metal alloy and as a result the
structure is altered. Dezincification is the most known form of selective
leaching, in which zinc is taken out from brass alloys or from alloys that
have zinc [25] .Dezincification of brasses takes place in either localized
area on the metal surface, called plug type, or uniformly over the surface,
called layer type. A plug of dezincified brass may blow out leaving a
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Chapter Two Theoretical Part & Literature Review

hole, while a water pipe having layer type dezincification may split open
[26]. The most common example of selective corrosion is dezincification
of brass, in which zinc is removed from the alloy and copper remains.
After cleaning the surface, dezincification is easy to demonstrate because
the Zn–depleted regions have a characteristically red copper color in
contrast to the original yellow brass.
Dezincification occurs in two forms, see Figure (2-12).
a) Uniform (layer) dezincification, where the front of the selective
attack moves more or less uniformly through the material. This
form is favored by high Zn content and acidic solutions.
b) Localized (plug-type) dezincification, where the localization and
form of attack are determined more or less arbitrarily. This type occurs
more often in alloys with somewhat lower Zn content and in neutral,
alkaline and slightly acidic solutions.
The liability to dezincification increases with increasing Zn content
and temperature and is promoted by a stagnant solution, porous surface
layers and oxygen in the corrosive medium (but oxygen is not strictly
necessary) [14].

Figure (2-10) a) Uniform (layer) dezincification and b) localized (plug–

type) dezincification of brass [14].

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Chapter Two Theoretical Part & Literature Review

2.8.2 Dezincification Mechanism

The common mechanisms consist of three steps:

1- The zinc ions stay in solution, 2- the copper plates back on, and 3- the
brass dissolves. Zinc is quit reactive, whereas copper is more noble. Zinc
can corrode slowly in pure water by the cathodic ion reduction of H2O
into hydrogen gas and hydroxide ions. For this reason, dezincification can
proceed in the absence of oxygen. Oxygen also enters into the cathodic
reaction and hence increases the rate of attack when it is present. The
amount of copper oxide is related to oxygen content of the environment.
The porous nature of the deposit permits easy contact between the
solution and the brass [27].

2.9 Alloying Elements Commonly Added to Copper Alloy

 Aluminum
Aluminum added as the principal alloying element to copper forms a
series of high strength alloys called aluminum bronzes. Aluminum forms
solid solutions with copper up to about 9.5 wt%. High strength yellow
brasses contain aluminum in varying amounts [28].
 Arsenic and Antimony
Arsenic and antimony can be added in small quantities, up to about
0.05 wt%, to all brass alloys containing less than 80% copper to inhibit
the dezincification types of corrosion in yellow brass alloys [29].

 Manganese
Manganese is added as an alloying element in high strength brasses
where it forms compounds with other elements such as iron and
aluminum , manganese may also be used as a deoxidizer, although it is
not a common usage [29].

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 Chromium
Chromium addition to copper increased strength and corrosion
resistance and forms heat-treatable copper alloys [30].
 Lead
Lead is added to copper in amounts up to 40 wt%. Lead is insoluble
in copper-based alloys and because of its low melting point is found
distributed in the grain boundaries of the casting. Because lead imparts a
certain degree of brittleness to the structure, it enhances machining
operations by causing the alloy to break into chips as cutting tools are
thrust into the matrix. Additions of lead up to 1.5 wt% significantly
improve machinability without a serious decrease in tensile strength.
Lead concentrations of 5-25 wt% greatly increase machinability of the
alloy but with a resulting decrease in tensile strength. Alloys with lead
concentrations equal to or greater than the tin content are used for bearing
applications requiring resistance to both wear and friction. Lead addition
to copper in amounts of about 35-40 wt% forms a useful bearing alloy.
However, lead is considered undesirable in high strength manganese
bronze, silicon bronze, and silicon brass. It affects the surface of silicon
bronze and silicon brass, causing noticeable darkening [30].
 Beryllium
Beryllium addition to copper forms a series of age- or precipitation-
harden able alloys. These heat-treatable alloys are the strongest of all
known copper-base alloy [4].
 Indium
Indium is added as an alloying element to brasses where its increase
the corrosion and wear properties [31].

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Chapter Two Theoretical Part & Literature Review

 Phosphorus
Phosphorus is used principally as a deoxidizer in copper and high
copper alloys. The alloy should contain a minimum residual of 0.02 wt%
phosphorus to ensure complete deoxidization. Lesser amounts of residual
phosphorus can form an equilibrium system with copper and oxygen.
Phosphorus can be added in small quantities .So adding phosphorus to
play a big role in improving the viability of antioxidants[32].

2.10 Heat Treatment for Brass Alloy

Metals can be heat-treated to alter the properties of strength, ductility,
toughness, hardness and/or resistance to corrosion. Common heat
treatment processes include annealing, precipitation , quenching,
strengthening and tempering [33].

2.10.1 Full annealing

In order to fully soften most brasses, heat to( 500-550)˚C for 1⁄2 to 1
hour at temperature, then either air cool or, especially for alpha alloys,
ensure that excessive grain growth is prevented by a quench or rapid
furnace cool. ‘Flash’ annealing can be carried out at higher temperatures
for considerably shorter times, but care is needed to avoid excessive grain
growth. The use of a protective atmosphere reduces oxidation. Normally
this can be prepared from cracked or partly burnt ammonia to give an
atmosphere high in nitrogen and water vapor. Since zinc is volatile, care
needs to be taken to avoid overheating [34].

2.10.2 Annealing

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When cold worked brass is progressively heated, the first effect, at

about 250˚C, is for the internal stresses to be relieved . This prevents
stress corrosion cracking subsequently occurring and also minimizes the
amount of distortion which may occur during machining. This low
temperature heat treatment, which should be applied for 1⁄2 to 1 hour, is
known as ‘stress-relief annealing’ and has little, if any, measurable effect
on the mechanical properties of the material. The improved strength due
to the cold working is therefore retained. As the temperature is increased
further, a rather more fundamental change occurs at about 400˚C and
above and the material starts to ‘anneal’ or soften with time at that
temperature. The effect of cold working is progressively lost, until at
about 500˚C the alloy is in the fully annealed condition[4]. Restoration of
the cold work properties can then only be achieved by further cold work..
When designing components which will be exposed to temperatures of
400˚C or above during manufacture (e.g. pipe work with brazed or
welded flanges), strength calculations must be based on the properties of
the material in the annealed condition. Although initially it may be a cold
worked material, it will be locally annealed during fabrication or joining
operations that involve heating [35] . Fig(2-13) [51] showed the effect of
annealing temperature on brass strength.

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Chapter Two Theoretical Part & Literature Review

Figure(2-11) Effect of annealing temperature on brass strength[51]

2.10.3. Stress Relieving

In order to relieve internal stresses without loss of properties a
low-temperature anneal such as 1⁄2 to 1 hour at( 250-300)˚C should be
used, depending on section size[35]

2.10.4 Temper Annealing

Many brasses cold worked to hard temper can be partially softened to
produce intermediate tempers by carefully controlled heat treatment.
Time and temperatures need to be established by experiment, starting
from, say, 1⁄2 hour at 400˚C and altering time and/or temperature to
achieve the desired temper. Results are monitored by measuring hardness,
grain size, directionality or other relevant properties [34].

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2.11 Wear Mechanisms

In metals wear operations, small particles of the surface are removed

due to movement between the surfaces. Although the mechanism of wear
is not fully understood but there are processes occur unevenly may be
penetrating the surface of the metal and this depends on the nature of the
wear tool as it works to dig the surface of the metal or the occurrence of
local welding process because of the accurate contact and this depends on
the hardness of the metal. As the high hardness tends to prevent
penetration of the surface and distortion which increases the area of
contact. Small pieces of metal resulting from repeated impacts may be
distorted and then separated. High strength metals have good
resistancefor this type of wear. High temperature during wear reduces
wear resistance as it accelerates corrosion reactions and thus reduces
mechanical properties. Metals with high melting temperature show good
wear properties.[36]

2.12 Wear Theories

There are several theories found to explain the phenomenon of

adhesion wear . The simple adhesion wear theory . Archard assumed
that the contact occurs between a number of projections of diameter
(d) and the contact area will be (πr˚2). Thus this area will bear a load
of (P˚ πr˚2) where (P˚) is the yield stress of the material during the
sliding where it will pass though a sliding of length (2 r˚). Archard
also assumed that the fragment resulted will be of hemispherical
shape , and the volume will be (2/3* πr˚3) .Thus the volume of
weariness (Q) for the whole distance of sliding can be determined by
the following equation :

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Chapter Two Theoretical Part & Literature Review

…..….(2-1)

Where:(n˚) is the number of contact .As at every point of contact , the

projection is carrying a load of (P˚ πr˚2).Then the total applied load
will be :

W = pºπºrº²nº ….….(2-2)

Also the amount of volume of the weariness will be :

…….(2-3)

This equation depends on the theory that all projections are content by
the load which will produce fragments. It is proved that a projective of
these contacts will result particles of weariness , thus the equation
becomes :

…….(2-4)

Where is the possibility of producing these particles at the projections

contacts . This equation is known an (Archard Equation).

Row's was able to modify the simple adhesion wear theory to represent
the surface films after reconsideration Archard equation by adding some
new variations on it, which are (Km), a coefficient which represents the
particulars of the sliding metal upon each other and does not depend on
the particulars of the lubricant . Also (B), is the coefficient that represents
the lubricant or the surface films , and the equation which expresses the
volume (Q) of weariness becomes as equation:

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……..(2-5)

And this equation expresses "Row Modified Adhesion Theory"[37].

2.13 Hardness
Is a metal resistance against the plastic deformation. In some cases
hardness refers to the resistance against the material cutting, scratching
and bending. There are multiple devices to measure the hardness vary in
their use mismatch. Which is used in the workplace and is characterized
by its small size and the possibility of being transferred from one location
to another and use special types of these devices to measure the hardness
Products completed where after apparent damage exterior products[38].
Figure (2.14) [39] shows hardness impression.

Figure (2.12): Hardness impression[39].

2.14 Types of Hardness

1. Rockwell hardness.
2. Brinell hardness.
3. Vickers hardness.

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Chapter Two Theoretical Part & Literature Review

2.14.1 Vickers Hardness

It is a hierarchical tool stitches diamond square base levels intersect
at an angle (136˚) and measured after loading. The arithmetic average of
the diagonal polygon quadrilateral impact output (D) is calculated.
Vickers hardness number according to the formula below:
HV = 1.854 (F/D2)

HV: vickers hardness (kg/mm2).

F: is the applied load, kg.
D2: the area of the indentation (mm2).

The advantages of the vickers hardness test are that extremely

accurate readings can be taken, and just one type of indenter is used for
all types of metals and surface treatments. Vickers method is capable of
testing the softest and hardest materials, under varying loads. With
modern advances in technology, PCs and software development, it is now
possible to offer automatic indentation measurement. This has the benefit
of eliminating any operator influence over the result, reducing R&R
(repeatability and reproducibility) and uncertainty budgets[39]. Figure
(2.15) [52] shows vickers impression.

Figure (2.13) : Vickers impression [52].

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Chapter Two Theoretical Part & Literature Review

2.15 Literature Review

In(2001) the Researcher Mona K.A[40] studied the effect of

different percentage of aluminum addition (0.2%,0.5%,1%) to the Brass
alloy (70/30) .The improvement in mechanical properties of alpha brass
alloy, , attributed to the role of aluminum soften grained and then increase
the hardness and tensile strength.

In (2004) Rabab M.El-Sherif [41] research, the electrochemical

behavior of brasses with various Zn content (5.5–38 mass%wt) and brass
(Cu–38Zn) with different Pb contents (1–3.4 mass%wt) in 0.6 M NaCl
was investigated. The effects of temperature, immersion time, and
concentration of chloride ions on the behavior of the different alloys were
studied. The pitting corrosion behavior of Cu–Zn alloys and leaded–brass
alloys in 0.6 M NaCl solution was also investigated. Open-circuit
potential measurements (OCP), polarization techniques and
electrochemical impedance spectroscopy (EIS) were used. The results
show that the increase in the Zn content increases the corrosion rate of the
brass alloys in chloride solutions, while the increase of Pb content in Cu–
38Zn–Pb decreases the corrosion rate of the alloy. The electrochemical
behavior of the different alloys was discussed in view of the fitting results

In(2005) K. M. Ismail[42] research the corrosion behavior of Cu-Zn

alloys in sulfuric acid (H2SO4) solutions was investigated using open-
circuit potential measurements, potentiodynamic techniques, and
electrochemical impedance spectroscopy. The influence of alloy
composition, H2SO4concentration, and temperature on the corrosion
response of the alloys was discussed. The thickness and resistance of the
surface film, formed on the alloy, increase as the Zn content is increased
up to 31.1%, before they start to decrease again. The addition of Pb, as a

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Chapter Two Theoretical Part & Literature Review

minor alloying element, to the brass alloy (Cu-38Zn) led to a significant

decline in the corrosion rate of the alloy due to the formation of an
insoluble lead sulfate (PbSO4) layer. Prolonged immersion of the alloys
in H2SO4 solutions improves their corrosion resistance. The influence of
the alloy composition and H2SO4 concentration on the equivalent circuit
parameters.
In (2009), Dr.. Mona Khudair Abbas and etal [43] studied dry
sliding wear of α–Brass (70/30) with addition of lead and tin(3%wt) for
each alloy. The results showed that the wear rate increases with
increasing applied loads and with increasing sliding time at constant
sliding speed (2.7m/s), while hardness of steel disc was 35 HRC , the
results also show that the brass alloy containing 3% tin has higher wear
resistance than that of other brass alloys.
In( 2009) J.A. Omotoyinbo and etal [44] research, the effects of
stress relief annealing and homogenizing annealing on the microstructure
and mechanical properties of cast brass were studied. The test samples
were heated to 200⁰C, 230⁰C, and 260⁰C for stress relief annealing. Other
sets of samples were heated to 650⁰C, 680⁰C, 700⁰C, 750⁰C, and 800⁰C,
respectively, for homogenizing annealing. It was observed that stress
relief annealing has little or no effect on the microstructure and
mechanical properties of each cast brass while homogenizing annealing
increases the impact strength but reduces the tensile strength, yield
strength, and hardness as a result of elimination of the brittle phase, or
intercrystalline segregation, present in the cast brass.

In (2010) W. Ozgowicz and etal [3] determined the influence of the

recrystallization temperature on the microstructure and mechanical
properties of the brass CuZn30 subjected to cold deformation in the
process of rolling at various degrees of strain. The brass CuZn30 was

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Chapter Two Theoretical Part & Literature Review

recrystallization annealed within the temperature range of 300-650°C

after cold rolling with the strain of 15.8-70.2%.The results of the
investigation revealed the occurrence of the phenomenon of
heterogeneous plastic deformation in the recrystallized alloy.

In(2011), Ali H. Haleem & Alaa A. Ateia & Nawal Mohammed

[45] studied the addition of Al to alpha brass alloy. Yielded a
significant improvement in the oxidation resistance. In this work, pure
aluminum (1- 2wt%) added to alpha brass alloy. These alloys were
prepared by melting and casting in a metallic mold. Cyclic oxidation tests
were conducted on the alpha brass alloy with and without aluminum
addition at a wide range of temperatures (500- 900 °C) in still air for 52
hrs. at 4 hrs. cycle .The oxidation kinetics followed breakaway behavior
for alpha brass alloy at 800 and 900 °C. This indicated that the oxidation
behavior of this alloy is non-protective. The phases presents on the cyclic
oxidation of alpha brass alloy with out aluminum addition as revealed by
XRD analysis are: ZnO, CuO and Cu2O. Alpha brass alloys containing Al
demonstrated high oxidation resistance. This was attributed to the
formation of protective alumina. Oxide morphology was examined using
light optical microscope.

In(2017), the Researcher Eman Solaiman Obaid[46] studied the

effect of different percentages of silver addition (1, 3 and 5) wt% to α-
brass alloy (CuZn30) produced by casting (with using electric mixer) ,
on some mechanical and physical properties. The mechanical and
physical properties included microstructure, hardness, compression,
tensile, and wear .Achieving the goals of this research was through tests
that include: microstructure test , hardness test, compression test , tensile
test, wear test , X-Ray Diffraction (XRD) analysis ,and Scanning
Electron Microscope (SEM) & (EDS) test. From results obtained in this

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study , it was found that hardness for (α- brass+5wt % Ag ) increased

by ( 10 %) , compressive strength for (α- brass+5wt % Ag) increased by
(23%) . While tensile strength for (α- brass+ 3wt % Ag) increased by
(12%) . Wear resistance is increased in general with increasing the
applied load.
In(2017), the Researcher asia Mishaal Salim[47] attempted to use an
effective, available, not toxic, and almost cost free, organic material to
protect brass tubes used in heat exchangers.. The corrosion currents
observed by the addition of Al, Sn, Y2O3, in the samples {B,C,D} were
reduced to,0.34, 0.31 ,0.24 respectively compared to that observed with
bar brass (reference sample) {A}. The great improvement was
introduced by the use of the cost free organic inhibitor. The corrosion
current obtained by Potentiostatic polarization was only (≈0.1) of the
corresponding value of the reference sample. However, the weight losses
of these samples conducted at room temperature (B, C, and D) In wear
tests were {(3, 1, and 2) x 10 -4 g} respectively compared that observed
with the reference sample (16x 10-4 g). A great improvement was
observed in corrosion/ erosion test caused by the inhibitor. The weight
loss was almost zero compared to the corresponding values of the costly
alloys (B, C and D). Their weight losses were (0.6 ,0.4, and 0.2)
respectively at room temperature with respect to the reference sample.
These weight losses in corrosion/erosion test remained about zero even
at higher temperatures of 50 to 55 ℃.

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 Chapter Three Experimental part

Chapter Three
Experimental Part

3.1 Introduction

In this chapter materials and equipment's that used in specimens

preparation process are illustrated. Several tests done such as hardness,
corrosion resistance, and wear resistance. Furthermore, phase
identification by X- ray diffraction and microstructure imaging are also
explained.

3.2 Materials
Three types of metals (copper, zinc, Indium) had been used to obtain
the required alloys through casting in a metal mold. Table(3-1) shows
chemical composition of α- brass alloy purchased from market without
& with(0.5,1,1.5and2) wt% In additions. This inspection has been
performed in State Company for Inspection and Engineering
Rehabilitation (SIER) by using a computerized spectrometer. Figure (3-1)
the experimental flowchart for the present work
Table( 3-1) shows chemical composition of α -brass alloy without & with
(0.5,1,1.5and2) wt% In additions.
CHEMICAL COMPOSITION[%]
Zn Pb Sn P In Mn Fe Si Sb As Cu
M 33.21 2.15 0.524 0.018 .......... 0.0254 0.35 0.157 0.006 0.064 Bal.

A1 33.38 2.09 0.584 0.017 0.005 0.0244 0.37 0.153 0.006 0.053 Bal.
A2 32.81 2.14 0.736 0.017 0.01 0.0231 0.375 0.149 0.0061 0.025 Bal.
A3 32.96 2.32 0.736 0.016 0.015 0.0215 0.381 0.149 0.004 0.02 Bal.
A4 33.61 2.38 0.762 0.016 0.02 0.0206 0.487 0.145 0.0044 0.0104 Bal

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Chapter Three Experimental part

Cutting α- brass form into small pieces

Melting & casting of α- brass in metallic mould

without and with ( 0.5,1,1.5,and 2 wt %) In

Heat treatment(550˚c) for 6 hour and cooling inside

the furnace

Tests

Microstructure Mechanical Electrochemical

charcterization tests Test

Optical Vickers Open Circuit

microscope hardness test potential

XRF Wear Polarization

inspection Test Tests

XRD
inspection

Figure (3-1): The experimental flowchart for the present work

03
Chapter Three Experimental part

3.3 Preparation of Specimen

3.3.1 Melting and Casting
Gas furnace showed in Figure (3-2)was used to give enough heat
for melting and pouring in melting crucible shown in Figure (3-3 ).
Addition (0.5,1,1.5 and 2 wt%) of indium to the α-brass(Cu/Zn30)
,this alloy melting in 902˚C While the melting point of Zn is 419.6˚C
and the boiling point is 907 ˚C. Added 5wt % from zinc to
compensate with lost zinc ratio during melting . Mixed molten by
graphite rod to homogenous the melting alloy.
The metal is poured into the cylindrical metallic mold (inner
diameter 10.5 mm and height 65mm) show in Figure(3-4) ,the casting
process conducted in room temperature . Figure (3-5) Showed rod
specimens of α- brass without and with ( 0.5 ,1 ,1.5 ,and 2 wt % In)
after casting process.

Figure(3-2): Gas furnace Figure (3-3): Melting crucible

03
Chapter Three Experimental part

Figure(3-4): Metallic mold alloys Figure (3-5):Ingots of brass

3.3.2 Heat Treatments

The process of treatment was conducted at a temperature (550˚C) for 6
hours then the furnace cooled in order to homogenize the composition, to
ensure the distribution of the elements of foundries and impurities on a
regular basis in the alloy. This leads to give the alloy homogeneous,
hardness and mechanical properties in electrical furnace. Figure (3-6)
shows electric heat treatment furnace.

Figure (3-6): Electric heat treatment furnace.

00
Chapter Three Experimental part

3.3.3 Cutting Specimens

Turning machine shown in Figure (3-7) had been used to achive the
favorable dimensions of the test specimens. It is to produce five
specimens with dimensions(3-4mm thickness) for the purpose of
microstructure and hardness and five specimens with dimensions (5-6mm
thickness, 10.5 mm diameter) for the wear test. It has also been arranged
to produce 5 specimens (5mm Thickness, 10.5 mm diameter) for the
corrosion test, the machine and specimens are shown in Figure ((3-8) and
(3-9))

Figure (3-7): Horizontal turning machine

Figure(3-8): Microstructure & Hardness specimens

03
Chapter Three Experimental part

3.3.4 Polishing
Polishing stage is highly required to ultimately produce a scratch-free,
highly polished and flat surface ready for subsequent etching and
microstructure examination , by using cloth polishing and diamond paste
type (nature diamond, with size 0.1 micron).

Figure (3-9 ): Grinding & polishing machine

3.4 Testing of The Specimens

3.4.1 Microstructure Test
Microstructure of specimens was investigated by using the optical
microscope shown in Figure (3-10). The specimens were imaged after
grinding of up to (3000) grit and finally polished by 0.25μm diamond
paste.To study the microstructure of the specimens, they were etched
using (FeCl3 5gm+alcohol.95mml)[53].

03
Chapter Three Experimental part

Figure(3- 10): Alight optical microscope(LOM).

3.4.2 Microhardness Test

Microhardness test was used to measure hardness values by
microhardness Vickers (HV) device using a load of (500 g for 10 sec )
with a square-base diamond pyramid, the hardness was recorded as an
average of three hardness readings for each specimen . It is necessary to
determine the hardness over small positions on the surface . Figure (3 -11
) shows microhardness (HV) measuring device [38].
HV = 1.854 (F/D2)
HV: vickers hardness (kg/mm2).
F: is the applied load, kg.
D2: the area of the indentation (mm2)

03
Chapter Three Experimental part

Figure (3-11): Microhardness (HV) measuring

3.4.3 Open circuit potential (OCP)

The experimental arrangement for the measurement of open circuit

potential is shown in figure (3-12)with a schematic drawing describes the
experimental situation. A 500 ml capacity glass electrolytic cell is used.
The tests were carried out with the specimens immersed in a NaCl
solution. The potential of the working electrode is measured with respect
to a Saturated Calomel electrode (SCE).A voltmeter is connected between
the working electrode and the reference electrode. For each specimen,
three hours open circuit potential measurement was performed.
The first record was taken immediately after immersion then the voltage
was monitored for the intire period of test at an interval of (5min).

03
Chapter Three Experimental part

Figure (3-12) Schematic drawing of open circuit potential measurement

3.4.4 Potentiostatic Polarization

Potentiostatic technique is another corrosion measurement technique

used to observe the anodic and cathodic behaviors (i.e. monitoring the
corrosion reactions on specimen of desired metal). Polarization tests were
performed by Potentiostatic device of type (winking M lab 200,
Germany), using standard electrochemical cell with open necks for
working electrode (brass alloys), auxiliary electrode (Pt. electrode) and
saturated calomel electrode SEC reference electrode. The corrosion
resistance of the specimens (M, A1, A2, A3 and A4) were studied in
NaCl solution at room temperature. Corrosion current density
measurement is obtained by using the following equation [54]:

2
where: icor = corrosion current density, μA/cm ,
Icor = total corrosion current, μA, and
2
A = exposed specimen area, cm .
The used electrochemical system is shown in Figure (3-13).

03
Chapter Three Experimental part

Fig. (3-13): shows the electrochemical system

3.4.5 Dry Sliding Wear Test
The dry sliding wear were studied by using pin-on-disc concept using
(400 rpm) and constant radius 5.25mm and the loads (10,15and 20)N.
The specimen was weighted before test using (0.0001) accuracy electric
balance . After a period of time (5,10,15,20,and 25 min) the test specimen
was weight again. The wear instrument that was used in this work is
shown in Figure (3 – 14) .

(A) (B)
Figure (3 – 14): (A)Pin-on-disc wear instrument , (B) Pin-on-disc
concept

03
Chapter Three Experimental part

3.4.6 X-Ray Diffraction Analysis

X-ray diffraction analysis have been conducted for the alloys using
XRD instrument. The brass alloy was examined to determine the
crystalline phase. The XRD generator with Cu target at 40 KV, 30 mA
and scanning speed 6° per minute was used. The scanning rate was (200 –
900).

Figure (3.15) X-ray Diffraction Analyzer

33
Chapter Three Experimental part

3.4.7 X-Ray Fluorescent Analysis (XRF)

Handheld (XRF) analyzer type (DS-2000) American, is used to

explain the chemical composition for powders and alloys. Figure (3-16)
shows images of machine and the results which clearly specifies the
chemical composition of brass alloy.

Fig (3-16) X-ray fluorescent (XRF)

33
 Chapter Four Results and
Discussion

Chapter Four
Results and Discussion
4.1 Introduction
This chapter discusses the results obtained from several tests
conducted throughout this work. It includes microstructure examination,
mechanical properties tests which involved(hardness and dry sliding wear
tests),electrochemical test which include Potentiostatic Polarization test .
4.2 Microstructure Examination
Light optical microscope was used to examine the microstructure of
etched specimens. The specimens have been etched to reveal the grain
boundaries in the microstructure . The most common types of features in
the microstructure in metallic materials are the boundaries between
crystalline grains and /or the boundaries between different solid phases
in multiphase alloys . Optical images of (100X,400X) magnification
showed the microstructure was achieved of the α-brass alloy after
addition (0.5,1,1.5 and 2wt %) indium with compared to α- brass alloy.
The In has no effect on the microstructure of the α-brass alloy and this
due the very low content of In in this alloy.

(100X) (400X)
Figure(4-1) : Light optical microstructure for α- brass ( Cu /Zn30) after
heat treatment ( 100X, 4 00X)
24
 Chapter Four Results and
Discussion

(100X) (400X)
Figure(4-2):Light optical microstructure for (α- brass + 0.5wt %In) after
heat treatment ( 100X, 400X)

(100X) (400X)
Figure(4-3): Light optical microstructure for (α- brass + 1wt %In) after
heat treatment ( 100X, 400X)

(100X) (400X)
Figure(4-4): Light optical microstructure for (α- brass + 1.5 wt %In)
after heat treatment ( 100X, 400X)

24
 Chapter Four Results and
Discussion

Figure(4-5): Light optical microstructure for (α- brass + 2wt %In) after heat
treatment ( 100X, 400X)

4.3 Microhardness Tests

In the current study the hardness of the specimens of all alloys
was measured by using Vickers hardness test. From figure (4-6), it
can be observed that (CuZn30) with In presented higher hardness
values in comparison with (CuZn30). And, the hardness increased as
the In content increases. The increase in hardness values of the α-
brass alloys with the increase in indium addition is attributable to
indium atoms, which located at the grain boundary.

Figure(4-6):Effect of In content on microhardness for α- brass

without &with ( 0.5,1,1.5,and 2) wt % In.

22
 Chapter Four Results and
Discussion
4.4 Dry Sliding Wear Test

A specimens of (10.5) mm in diameter subjected to wear test

under different loads (10, 15 and 20)N and for different times (5,
10,15, 20 and 25)min at room temperature. The results have been
presented in Figures((4-7)-(4-11)).

Figure(4-7): Weight loose vs time for α-brass under

(10, 15 and 20 N)load

Figure(4-8): Weight loose vs time for (α-brass+ 0.5) wt%In under

(10, 15 and 20 N) load

24
 Chapter Four Results and
Discussion

Figure(4-9): Weight loose vs time for (α-brass+ 1) wt% In under

(10, 15 and 20 N)load

Figure(4-10): Weight loose vs time for (α-brass+ 1.5) wt% In under

(10, 15 and 20 N)load

24
 Chapter Four Results and
Discussion

Figure(4-11): Weight loose vs time for (α-brass+ 2) wt% In under

(10, 15 and 20 N)load
From the above figures, it can be noted that the wear rate of all tested
specimens under 20N load is higher than that of 15N and 10N.Also 15N
is higher than that for 10N. The reason behind this variation is very clear.
This is due to increase in friction at the surface as the load on the material
increases [48].
In addition, the wear rate increase as the time increase for all tested
specimen. This is certainly because more time of friction tend to remove
more material from the surface. This increase in wear rate has been
attributed to the increase in plastic deformation of the material on the
surface , particles of the material pulled out [49] .
In order to study the effect of In addition on the wear rate of (CuZn30)
used alloy , the wear rate with In content under 20N load at 25 min time
plotted in the following figure (4-12).

24
 Chapter Four Results and
Discussion

Figure(4.12): Wear rate vs In content for the specimens under

(20 N )load (25 min)time.
It can be noted from figure (4-12), that the wear rate decrease as the In
content increases. The reason behind these reduces in wear rate might be
simple since the In addition increase the hardness then the wear rate will
be reduced.

4.5 Electrochemical Tests

4.5.1 Open circuit potential (OCP)-time measurement

The OCP-time was measured with respect to SCE. NaCl solution was
used for all tested alloys. Figure (4-13) shows the evolution of corrosion
potential of the alloys throughout time. A time period from (0 to 180)
minutes with interval of 5 minutes were potentially reported. The mean
values of the OCP were recorded for each specimen.

24
 Chapter Four Results and
Discussion

Figure (4-13) shows the OCP-time in NaCl solution was used for all tested specimens.

The above figure show the variation of open circuit potential (OCP)
with time from which several deduction can be made. The first is that
during the first 30 minutes, the corrosion potential increases at a greatest
speed in this period in most case study. This initial increase generally
seems to be related to the formation and thickening of the oxide film on
the metallic surface, improving its corrosion protection ability.
Afterwards the OCP increases slowly because of the growth of the film
onto the metallic surface. The second is that the corrosion potential
reaches a level at which corrosion potential tends to stabilize. The
constant OCP means that there is equilibrium between dissolution and
deposition. The (α- brass + 2wt % In ) is the best, The closer get to the
positive side, the alloy becomes more noble [50].
4.5.2 Potentiodynamic polarization

The corrosion behavior of all used specimens in NaCl solution has

been studied. In addition, the effect of corrosion on the microstructure has
been illustrated in NaCl solution using Potentiodynamic polarization to
give estimation about the corrosion behavior of alloys. The corrosion

24
 Chapter Four Results and
Discussion
parameters are corrosion current (Icorr.), corrosion potential (Ecorr.) and
(corrosion rate) resulted from corrosion test for the specimens in
mentioned solutions were illustrated in table (4-1).
From Table (4-1) it can be seen that there is a significant improvement in
corrosion resistance of the alloy with different additives of indium. Icorr.
for the specimens were graded from 5.595 ( μA/cm²) for A1 alloy to
0.0734 (μA/cm²) for A4 alloy which were lower than Icorr. For M alloy
which was 6.27 (μA/cm²). However, the Ecorr.values are graded from
-199.1mV for A1 to -147.1mV for A4 which are higher than Ecorr.for M
alloy which is -207mV. This improvement in corrosion resistance can be
attributed to the behavior of In element as noble element which enhanced
the corrosion resistance of α- brass alloy. Finally the corrosion rates were
calculated based on following equation[55]:

Corrosion rate = … (4-1)

Where:
E.W= equivalent weight (g/eq.)
𝜌= density (g/cm³)
0.13 = metric and time conversion factor
icorr.= current density (μA/cm²).
mpy = Corrosion rate (mils per year)

Table (4-1) Shows the corrosion current (Icorr.) , corrosion potential

(Ecorr.) and corrosion rate for all used samples in NaCl Solution.
Sample code Icorr. Ecorr. Corrosion Improvement
(μA/cm²) (mV) Rate(mpy) percentage%

M 6.27 -207 0.0321 ____

A1 5.595 -199.1 0.023 28.3
A2 1.53 -160.7 0.00539 83.2
A3 0.435 -152.4 0.00122 96.1
A4 0.0734 -147.1 0.000179 99.4

45
 Chapter Four Results and
Discussion

Figure (4-14) The corrosion rate of α- brass

Figure (4-15) The effect of (0.5)wt% In on corrosion rate of α- brass

45
 Chapter Four Results and
Discussion

Figure (4-16) The effect of (1)wt% In on corrosion rate of α- brass

Figure (4-17) The effect of (1.5)wt% In on corrosion rate of α- brass

44
 Chapter Four Results and
Discussion

Figure (4-18) The effect of (2)wt% In on corrosion rate of α- brass

Figure(4.19): Corrosion rate vs In content for the specimens in NaCl solution.

44
 Chapter Four Results and
Discussion
4.6 X-Ray Diffraction analysis
Alloys were examined by X-Ray device based on the principle of
diffraction,where the planned statement shown in Figures
((4.20)-(4.21)) .
The X-rays test of α- brass alloy showed X-ray diffraction for the
α- phase in alloy , Figure (4.21) doesn't indicate any peak belong to
indium. This is due to the very low content of indium that cannot be
indicated by this analysis

Figure(4.45): Result of X-ray diffraction analysis for(α-brass)alloy specimen

Figure(4.45):Result of X-ray diffraction analysis for(α-brass+2)wt% In alloy

specimen
42
Chapter Five Conclusions and Recommendations

Chapter Five
Conclusions and Recommendations

5.1 Conclusions

The improvements in mechanical and corrosion properties and

adding indium particles to CuZn30 alloy can be concluded as following:

 The addition of In with (0.5-2) wt% causes an increase in

hardness of CuZn30 alloys.
 Indium addition led to improve corrosion resistance of α- brass in
NaCl solution up to 99.4% for 2wt% In .

 Indium addition led to improve wear resistance and the highest

wear resistance is for 2wt%In .

55
Chapter Five Conclusions and Recommendations

5.2 Recommendations

 Use Other ratios of indium to the α- brass alloy and study the
properties.
 Add other alloying elements like Ni, Cr and study the effect of
these elements on the corrosion resistance of α- brass alloy.
 Use other tests to detect the effect of adding indium to α- brass
alloy and study more properties for alloys.

55
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