STUDY OF THE AGE HARDENING BEHAVIOR OF

Al - 4.5Cu/ZrSiO4 COMPOSITE IN DIFFERENT

QUENCHING MEDIA

Thesis submitted in partial fulfillment of the requirement for

The award of the degree of
Master in Technology
In
MATERIALS SCIENCE AND ENGINEERING

Submitted by

ASHUTOSH
Roll No.6050501

Under
the able guidance of
Dr. Sanjeev Das
School of Physics and Material Science
Thapar University, Patiala

School of Physics & Material Sciences

Thapar University, Patiala
Patiala - 147001
June-2007
 Dedicated

To
My Grand Parents
CERTIFICATE

This is to certify that Mr. ASHUTOSH, Roll No. 6050501 has worked on
this thesis report as a final fulfillment for award of the degree of MASTERS
IN TECHNOLGY in Material Science and Engineering. I certify that the
matter embodied in this report is of the candidate’s own record and not
submitted to any other university in any part or full form for the award of
such kind of a degree.

(Dr. Sanjeev Das)

Supervisor
SPMS, Thapar University
Patiala

Countersigned by:

Dr.O.P.Pandey Dr. R.K.Sharma

(Prof. & Head) Dean of academic Affairs
School of Physics and Materials Science Thapar University
Thapar University, Patiala Patiala
 ACKNOWLEDGEMENT

No matter how much enterprising and entrepreneurial one’s thinking is, yet nobody can
do everything all by himself without some help and guidance. It is inhumane if the
concerned person’s assistance goes without appreciation and thanks.

My first and foremost offering of thanks goes to the architect who shaped my dreams into
reality, my guide and mentor Dr. Sanjeev Das. Perseverance, exuberance, positive
approaches are just some of the traits he imprinted on my personality. He steered me
through his journey through his invaluable advice, positive criticism, stimulating
discussion and consistent encouragement. His meticulous attention towards my
proceedings, his devoted time and his ideas has enabled me to make the project a success.
His faith in me has always made me more confident. If I will stand proud my
achievements then undoubtedly he is the main creator. It had been my privilege to work
under his guidance.

My greatest thanks are to Dr. O.P.Pandey, Prof. and Head, School of Physics and
Material Science, Thapar University, Patiala. He has been very helpful in improving
dissertation. I am grateful to him for sharing his time and expertise. His comments and
views were very insightful and helpful.

I would like to give many thanks to Dr K.K.Raina, Dean of faculty affairs, School of
Physics and Material Sciences allowing me to use the facilities in Materials Research
Lab and, for his support, assistance, encouragement, advice, and overall guidance
throughout this study.

I would like to thank Dr. Kulvir Singh, Assistant Professor, School of Physics and
Materials Science for his full motivation and appreciation to my work
My special thanks to P G Lab incharge Mr. Purushottam. His assistance and
partnership were of great pleasure. His comments and views were very insightful and
helpful. I would also like to thank Mr. Jant Singh, for providing all kind of assistance in
PG Lab for creating a healthy research environment.

I would also like to give many thanks to Research Scholar Pankaj Kumar and Vishal
Kumar for any kind of help and valuable suggestions whenever I needed out of their
busy schedule.

All the faculties, my friend Sachin Tyagi, and my colleagues at the Materials Science &
Engineering program and the School of Physics and Material Sciences are acknowledged
for providing me a friendly atmosphere and encouraging me throughout this research.

Ashutosh
Roll No.6050501
ABSTRACT

This report deals with a comparative study based on the age hardening behavior of Al-
4.5%Cu metal matrix composite reinforced with zircon sand particulates in different
quenching media viz, water, oil, and salt brine solution (7%). All the samples were
solutionised; quenched in water, oil, and salt solution, and aged in a vacuum oven.
Vicker’s microhardness test is conducted on all samples for ageing. Optical micrographs
of the as cast alloy composite indicates that the matrix of the composite has the cellular
structure. Segregation of copper rich phase (CuAl2) has been found in the vicinity of
particle matrix interface. Scanning electron micrographs at low magnification show
uniformly distributed zircon particles throughout the matrix. Scanning electron
micrographs at higher magnification shows the presence of uniformly distributed
secondary phase in the alloy matrix indicating a strong continuous bond between zircon
particle and the alloy matrix. Results of ageing kinetics demonstrate that the
microhardness of age hardenable Al-Cu alloys depend on the rate on which the alloy is
cooled after solution heat treatment. The peak hardness in oil quenched sample is attained
at an early stage while water quenched sample show peak hardness at a later stage. Salt
brine quenched sample shows the maximum hardness but peak hardness is in between
water and oil quenched samples. Thermal cycling of the composite has been studied in
different quenching media. A maximum of different heat treatment cycles are taken and
microhardness of the matrix is discussed and an interesting hardness result were observed
while varying quenching media.
LIST OF FIGURES

Page No.

1 The binary phase diagram for Aluminium-Copper alloy [33]. 7

2 The effect of ageing time on the yield stress of an aluminum-copper 8

alloy, aged at 180°C, showing the age hardening strengthening effects
[34].
3 Hypothetical phase diagram for a precipitation hardenable alloy of 16
composition x1
4 Schematic temperature versus time plot showing both solution & 17
precipitation heat treatments for age hardening [67]
5 Schematic ageing curve for an Al-Cu alloy composite [33] 18

6 (a) Decomposition Products created by ageing the supersaturated 19

solution [33] 19
(b) Precipitation sequence in Al-Cu alloy
7 (a) Coherency of the precipitates, (b) Geometry of Guinier Preston Zones 20
[33]
8 (a) Hardening of different zones [71], 21
(b) Al-Cu phase diagram along with metastable phase boundaries for 21
GP zones, θ’ and θ”, together with the equilibrium solvus line for the θ
phase.[33,68], 23
(c) Example of hardening behavior in Al-Cu alloy [69]
9 Experimental Techniques followed 27

10 29
Scanning electron micrographs of the composite showing uniform
distribution of zircon sand particles
11 Scanning electron micrographs showing good particle matrix bonding 29

12 Typical X-Ray diffraction pattern for as cast composite 30

13 Optical microstructures of as cast composite 31

14 Age hardening behavior of the composite in different quenching media 33

15 Schematic diagram to show dislocations around the interparticle matrix 34

interface
16 Thermal cycling of the composite in different quenching media 37
LIST OF TABLES

Page No.

Designation of Wrought Aluminium alloys

1 4

2 Designation of Cast Aluminium alloys 4

3 Temper Designation System 4

4 Composition of materials 26
Ageing data of the composite in Water
5 32

6 Ageing data of the composite in Oil 32

7 Ageing data of the composite in Salt brine solution 32

8 Ageing Conditions 33
Thermal cycling data of the composite in Water
9 36

10 Thermal cycling data of the composite in Oil 36

Thermal cycling data of the composite in Salt brine solution
11 36
LIST OF ABBREVIATIONS

AAA Aluminium Association of America

AMC Aluminium Matrix Composites

BCT Body Centered Tetragonal

EDS Energy Dispersive X-ray Spectroscopy

CTE Coefficient of Thermal Expansion

Hv Vicker’s hardness

IADS International Alloy Development System

GP Zones Guinier Preston Zones

MMC Metal Matrix Composites

PRMMC Particulate Reinforced Metal Matrix Composites

SEM Scanning Electron Microscope

SSSS Super Saturated Solid Solution

UTS Ultimate Tensile Strength

YS Yield Strength
CONTENTS
Page No.

Certificate i
Acknowledgement ii
Abstract iv
LIST OF FIGURES v
LIST OF TABLES vi
LIST OF ABBREVIATIONS

vii

Chapter -1 Introduction 1

Chapter -2 Literature Review 3

2.1 Aluminium and its alloys 3
2.1.1 Casting alloys 3
2.1.2 Wrought Aluminium alloys 3
2.1.3 Heat Treatable Aluminium alloys 5
2.1.4 Non Heat Treatable Aluminium alloys 5
2.2 Age Hardening of Aluminium alloys 6
2.3 Effect of Ageing on microstructure and strength 7
2.4 Applications of Aluminium alloys 9
2.5 Metal Matrix Composites 10
2.5.1 Reinforcements 10
2.5.2 Matrix 11
2.6 Al-MMC’s 11
2.7 Age Hardening in Al-MMC’s 12
2.8 Basic requirements for Ageing 15
2.9 Ageing curve 18
2.9.1 Effect of Ageing time and Temperature 18
2.9.2 Hardening of GP zones 21
2.9.3 Effect of Quenching Media 24

Chapter -3 Experimental Details 26

3.1 Materials 26
3.2 X-Ray diffraction and microscopy 27
 3.3 Ageing studies 27

Chapter -4 Results and Discussion 29

4.1 Characterization of zircon sand particles 29
4.2 Microstructural examination of composite 31
4.3 Ageing behavior of composite 32
4.4 Thermal cycling of composite 36

Chapter -6 Summary and Conclusions 39

References 40
 Chapter 1
INTRODUCTION

Aluminium alloys are widely used in aerospace and automobile industries due to their
low density and good mechanical properties, better corrosion resistance and wear, low
thermal coefficient of expansion as compared to conventional metals and alloys. The
excellent mechanical properties of these materials and relatively low production cost
make them a very attractive candidate for a variety of applications both from scientific
and technological Viewpoints. Recently, Aluminium metal matrix composites with
Al2O3, SiC whisker and Ceramic fiber used to substitutes steel [1]. Some of these
materials have been used to manufacture automotive components for trial but its
commercialization was limited due to the difficulties in manufacturing and also the high
production cost. On the other hand particulate reinforced composites have been reported
to have a better plastic forming capability than whisker & fiber reinforced composites [2],
and thus have an advantage to lower the manufacturing cost. Also they exhibit excellent
heat and wear resistances of due to the superior hardness and heat resistance
characteristics of the particle distributed in the matrix [3-5]. Moreover they are easily
available and synthesized via a variety of manufacturing routes. There are several
fabrication techniques are available for the in manufacturing of MMC materials.
According to the type of reinforcement, the fabrication techniques can vary considerably.
These techniques include stir casting [6-8], liquid metal infiltration [9], squeeze casting
[10], and spray co deposition [11]. Stir casting route is generally practiced commercially
[12-13]. Its advantage lies in its simplicity, flexibility and applicability to large quantity
production. Numerous research work have been reported on Aluminium reinforced with
various particulates such as SiC, B, TiC, Si3N4, Silica Sand, MgO, mica glass beads, B4C,
Al2O3 [5,14,15]. Limited work has been reported on fabrication and Characterization of
zircon sand reinforcement in Aluminium matrix alloys. Zircon sand possesses high
hardness, high modulus of elasticity, and excellent thermal stability. Banerji et al. found
improvement in hardness, abrasive and wear resistance, elastic modulus, 0.2% proof
stress, and UTS of cast Al-3wt%Mg alloy due to dispersions of zircon sand particles [16],
which makes zircon sand reinforced composite an important material for industries like
aerospace, military, automobiles etc. Also the thermal coefficient of expansion of zircon
sand is comparable to that of SiC. Hence the influence of zircon sand reinforcement in
ageing behavior of Al-4.5%Cu matrix is really interesting.

Cast Al-Si-Mg alloys have been widely used in automotive and aircraft industries for
their good properties and high strength-to-weight ratio [17,18]. Intensive studies of this
cast aluminum family have been found in the literature in terms of enhancing the
mechanical properties [18, 20-24]. It is well known that the heat treatment is one of the
important methods for improving the mechanical properties of aluminum alloys [21]. The
heat treatment of agehardenable aluminum alloys involves solutionzing the alloys,
quenching, and then either aging at room temperature (natural aging) or at an elevated
temperature (artificial aging) [18].

Quenching is a crucial step to suppress the precipitation to retain the supersaturation of

solid solution, control the distortion, and minimize the residual stress in aluminum alloys.
Quenching media commonly used for aluminum alloys include brine solution, water, and
polymer solutions [25-26]. The physical properties of polymer quench bath directly affect
the cooling rate of a quenched part. These properties include the type of quenchant, its
temperature, concentration, and agitation level [25-27]. These parameters must be
controlled to optimize the quenching process in terms of alloy microstructure, properties,
and performance. People have used polymer quenchants and oils to still maintain similar
quenching performance [25-28].

The present investigation has been done to study the age hardening behavior of Al-
4.5%Cu alloy reinforced with zircon sand particles, synthesized by stir casting route in
different quenching media water, oil and salt brine solution (7%). Current researches
indicate an accelerated ageing behavior with Aluminium reinforced with zircon sand
when quenched in water [29-30]. However, limited work has been done when the
hardening behavior of Al-Cu alloy composites are characterized in different quenching
media other than water. In present case effect of age hardening effect in oil and salt brine
solution has been examined along with thermal cycling of composites.
 Chapter 2.
LITERATURE REVIEW

2.1 Aluminium and its alloys

The three main alloys of importance in engineering and aerospace applications are the
aluminium alloys, steels and nickel alloys. Titanium, magnesium and copper alloys are
also significant. Aluminium alloys with great durability and high strength, some with a
tensile strength as good as that of constructional steels, are available to the designer in the
form of extruded profiles, rolled sheet and plate, castings and forgings. The majority of
these alloys consist of aluminium with carefully controlled additions of copper,
magnesium, silicon, manganese, zinc and more recently lithium.

Aluminium alloys are the dominant materials for airframe structures. There are three
main classes of aluminium alloys used in aerospace applications, though only the
wrought heat-treated alloys have sufficient strength for structural components. [31]

2.1.1 Casting Alloys: Aluminium and its alloys are used in a variety of cast and
wrought form and conditions of heat treatment. Forgings, sections, extrusions, sheets,
plate, strip, foils and wire are some of the examples of wrought form while castings are
available as sand, pressure and gravity die-castings. e.g. Al-Si and Al-Mg alloys

2.1.2 Wrought Aluminium Alloys: to meet various requirements, aluminium is

alloyed with copper, manganese, magnesium, zinc, nickel and silicon as major alloying
elements. These alloying additions improve the properties of aluminium when added in
desired percentages. The AAA (Aluminium Association of America) has classified the
wrought aluminium alloys according to a four-digit system. The classification is adopted
by the International Alloy Development System (IADS) and by most of the countries in
the world. Table 1-3[70] gives the basis of designation of wrought and cast aluminum
alloys in the four-digit system. The first digit identifies the alloy type the second digit
shows the specific alloy modification. The last two digits indicate the specific aluminium
alloy or the purity level in case of pure aluminium.
Table 1- Designation of Wrought Aluminium alloys

Alloy Designation Detail

1XXX 99% pure Aluminium
2XXX Cu containing alloy
3XXX Mn containing alloy
4XXX Si containing alloy
5XXX Mg containing alloy
6XXX Mg and Si containing alloy
7XXX Zn containing alloy
8XXX Other alloys
9XXX Unassigned

Table 2- Designation of Cast Aluminium alloys

Alloy Designation Detail

1XX.X 99% pure Aluminium
2XX.X Cu containing alloy
3XX.X Si, Cu/Mg containing alloy
4XX.X Si containing alloy
5XX.X Mg containing alloy
7XX.X Zn containing alloy
8XX.X Sn containing alloy
9XX.X Other alloys
6XX.X Unassigned

The condition of temper of Aluminium alloys be denoted by specific letters as shown

below

Table 3- Temper Designation System

Letter Condition of alloy

F As–fabricated
O Annealed
H Strain hardened (Wrought
products only)
W Solution heat treated
T Thermally treated to produce
tempers other than F, O, H
T4 Solution treated
T6 Solution treated and aged
 Numeric additions indicate specific variations

2.1.3 Heat Treatable Aluminium Alloys: Heat treating in its broadest sense, refers to
any of the heating and cooling operations are performed for the purpose of changing the
mechanical properties, the metallurgical structure, or the residual stress state of a metal
product.

When the term is applied to aluminum alloys, however, its use frequently is restricted to
the specific operations employed to increase strength and hardness of the precipitation-
hardenable wrought and cast alloys. These usually are referred to as the "heat-treatable"
alloys to distinguish them from those alloys in which no significant strengthening can be
achieved by heating and cooling [31-32].

The Aluminium alloys of this class belong to systems with limited solubility in solid
state. These are precipitation hardenable alloys. The main characteristic of these alloys
system is temperature dependent equilibrium solid solubility, which increases with rise in
temperature. In addition the other requirements are possibility of retaining single phase
supersaturated solid solution by quenching, and precipitation of coherent/partially
coherent phase by decomposition of the super saturated solid solution. The examples of
this group are:

1. Aluminum-copper systems with strengthening from CuAl2

2. Aluminum-copper-magnesium systems (magnesium intensifies precipitation)
3. Aluminum-magnesium-silicon systems with strengthening from Mg2Si
4. Aluminum-zinc-magnesium systems with strengthening from MgZn2

2.1.4 Non-Heat treatable Aluminium alloys: These alloys do not respond to heat
treatment, because they consist of a homogeneous solid solution with or without non-
coherent precipitate(s) and show low strength and high ductility. These alloys may be
stress hardened. Commercially pure Aluminium (1100), Al-Mn (3003), Al-Mn-Mg, and
Al-Si alloys are examples of this class [31]. These alloys are used as sheet, bar, plates,
wire, extrusion and so on. They are readily bent, formed and welded and possess
excellent resistance to corrosion.

2.2 Age-hardening of aluminium alloys.

Hardening and strengthening of a metal alloy by extremely small and uniformly

distributed dispersed particles that precipitates from a supersaturated solid solution. The
alloy becomes harder with time or as it ages it develops hardness and strength. The
hardness of the quenched alloy increases as a function of ageing time. Ageing of the
quenched alloy at room temperature is known as natural ageing while at elevated
temperatures is known as artificial ageing. Precipitation in solid solution occurs when the
solubility of solute decreases with decreasing temperature. The precipitate of the second
phase should be coherent in nature. The object of age hardening is to create in a heat
treated alloy a dense of fine dispersions of precipitated particles in a matrix of deformable
metal. The precipitate particles act as obstacles to dislocation motion and thereby
strengthen the heat-treated alloy.

The strengthening mechanisms in wrought, heat-treated Aluminium alloys can be

demonstrated using the Al-Cu alloy as shown in Fig.1
Precipitation hardenable aluminum alloys are heat treated in three-step process: solution
heat treatment, quenching and age hardening. The solution treatment aims to dissolve the
soluble phases. Quenching aims to preserve the solid solution formed by rapidly cooling
to some lower temperature, usually room temperature. Age hardening aims to precipitate
out the strengthening phases. Overheating above or under heating below a specfied range
of temperatures in the solution treatment and age hardening steps as well as inadequate
quenching may cause degradation of mechanical properties [31].

Hardening is achieved by the controlled rejection of copper from a supersaturated solid

solution. The solubility of copper in α-Aluminium increases with increasing temperature
up to the eutectic temperature of about 540°C. The equilibrium microstructure below the
eutectic temperature is a two-phase mixture of α-Aluminium and the Al2Cu intermetallic
phase. Rapid quenching from the solution temperature prevents the kinetically slow
precipitation of θ, forming a highly supersaturated solid solution of copper.

Fig.1 - The binary phase diagram for Aluminium-Copper alloy [33].

.

2.3 The Effect of Ageing on Microstructure and Strength.

Ageing may occur at room temperature (Natural Ageing) or above (Artificial Ageing),
and takes place via a sequence of precipitation reactions. The precipitation sequence is
driven by the super saturation of copper in solution.
During ageing, copper atoms segregate by diffusion to form copper-rich zones called
Guinier-Preston GP(1) zones. The difference in atomic size of copper and aluminium
strains the lattice. Hardening is due to the increased work required to move dislocations
through the strained lattice (coherency stress) and work required for dislocations to cut
though the GP(1) zones (cutting stress). Above around 100°C, further copper segregation
produces GP(2) zones, sometimes known as θ" phase.
Hardening occurs by the same mechanisms as the GP(1) zones, though GP(2) zones have
a stronger effect. A high number density of GP(2) zones or θ" gives the maximum
strengthening effect.

Fig. 2 - The effect of ageing time on the yield stress of an aluminum-copper alloy,
aged at 180°C, showing the age hardening strengthening effects [34].

Further growth of the GP(2) zones leads to the formation of the θ' phase. θ” is the
dominant phase at the peak hardness, where strengthening is due to a combination of
lattice coherency strain (coherency stress), precipitate cutting by dislocations (cutting
stress) and dislocation bowing between precipitates (bowing stress). With further ageing,
the precipitate distribution changes as large, widely dispersed precipitates grow at the
expense of finely dispersed small precipitates. This process is known as "Ostwald
ripening". Dislocation bowing between precipitates becomes easy and the strengthening
contribution from coherency strain and precipitate cutting is lost. Over-ageing develops
the equilibrium tetragonal θ phase (Al2Cu), which does not have a strong strengthening
effect.

2.4 Applications of aluminium alloys: aluminum is a strong, durable and lightweight

metal. In today's energy-conscious society, these three basic properties combine to make
the metal the preferred material of construction for transport applications, where weight
reduction to reduce fuel consumption and to increase load carrying capacity is vital.
Products like motorcars, aircraft, ships, conductors, lorries and trains are all obvious
examples[35].

Electrical Conductors
Conductors in either the 1000 or 6000 series alloys are sensible technical alternatives to
copper for all electrical conductors, even in domestic wiring.

Transport
Aluminium and its alloys have been the prime material of construction for the aircraft
industry throughout most of its history. Even today, when titanium and composites are
growing in use, 70% of commercial civil aircraft airframes are made from aluminium
alloys, and without aluminium civil aviation would not be economically viable.

Packaging

The successful use of the 1000 series alloys as foil for food wrapping and for containers
utilizes their good corrosion resistance and barrier properties against UV light, moisture
and odour. Foil can be readily formed, attractively decorated and can be usefully
combined with paper and plastic if required.

Building and Architecture

Aluminium is used in buildings for a wide spectrum of applications. These include
roofing for factories which incorporate foil vapour barriers, windows and pre formed
sheet cladding features, doors, canopies and fronts for shops and prestigious buildings,
architectural hardware and fittings, rainwater goods and replacement windows.
In composites, Particle reinforced AMCs are in use as recreational products including
golf club shaft and head, skating shoe, baseball shafts, horseshoes and bicycle frames.
AMCs containing high volume fraction ceramic particles are being used as
microprocessor lids and integrated heat sinks in electronic packaging. They are also in
use as carrier plates and microwave housing.

2.5 Metal Matrix Composites: An alternative to conventional alloys are metal matrix
composites (MMC’s), which have a high specific modulus, good wear resistance and a
tailorable coefficient of thermal expansion. A major drawback to these MMC’s is high
cost.
A metal matrix composite (MMC) combines into a single material a metallic base with a
reinforcing constituent, which is usually non-metallic and is commonly a ceramic. By
definition, MMC’s are produced by means of processes other than conventional metal
alloying. Like their polymer matrix counterparts, these composites are often produced by
combining two pre-existing constituents (e.g. a metal and a ceramic fibre). Processes
commonly used include powder metallurgy, diffusion bonding, liquid phase sintering,
and squeeze-infiltration and stir casting. [9-11]

Major Phases: The major phases in a metal matrix composite are one or several
reinforcements (strengthening phases) and a matrix, which transfers external load to the
reinforcement(s). In AMCs, these can be briefly described as follows.

2.5.1 Reinforcement
The most common reinforcements are silicon carbide (SiC), alumina (Al2O3), and
graphite. Other carbides such as TiC and B4C as well as aluminum nitride (AlN) can be
used. SiC is of interest because of its relatively high modulus, low density, and its
availability in different reinforcement shapes and sizes [36]. Three different
reinforcement shapes are considered: particulates, whiskers or discontinuous fibers, and
continuous fibers. AMCs with particulates offer low cost, isotropic properties, and
significant stiffness improvement, but the strength, strain to failure, and fracture
toughness are low com-pared to the matrix material. AMCs with discontinuous
polycrystalline fibers or flakes offer higher strength. Monocrystalline whiskers have
much higher strength, but their cost is higher. Composites with continuous fibers offer
the best combination of strength and stiffness, but their cost is relatively very high. Fibers
such as boron (as Borsic), carbon (as Pitch), alumina (as Safill and Safi- max), and SiC
are considered for strengthening AMCs[36-40].

2.5.2 Matrix

According to the aluminum association system, the matrix materials generally employed
include pure Al (AA 1000), AlCu (AA 2000), AlMg (AA 5000), AlMgSi (AA 6000),
AlZn (AA 7000), and AlLi (AA 8000) [41]. In particular, aluminum alloys in the Al–Si
and Al–Cu systems are successful matrices for AMCs. Heat-treatable Al alloys are
interesting because with post processing, additional improvement in mechanical
properties can be obtained. .

2.6 Al-MMC’s: Aluminium alloys are widely used in aerospace and automobile
industries due to their low density and good mechanical properties, better corrosion
resistance and wear, low thermal coefficient of expansion as compared to conventional
metals and alloys. Of all the AMCs, particle reinforced AMCs constitutes largest quantity
of composites produced and utilized on volume and weight basis. PAMCs are produced
by PM stir cast/melt infiltration/spraying/in situ processing techniques at industrial level.
Particulates of SiC, Al2O3, TiC, TiB2, B4C have been used as reinforcements [5,15,42]. In
general, PRMMCs are at least approximately isotropic. They are produced using both
solid state (powder metallurgy)[43] and liquid metal techniques (stir casting etc,)[30].
Their mechanical properties, while often inferior to those of fibre-reinforced metals, are
more or less isotropic and often represent, at moderate cost, significant improvements
over those of corresponding unreinforced metals. Their novelties, and their interesting
mechanical behavior (at both micro- and macroscopic levels), have led to many
publications, exploring many features of their microstructure, deformation, and fracture
behavior. Many mechanisms responsible for their mechanical characteristics are now
well understood, including the roles of damage development, internal stresses,
reinforcement clustering, interfacial bond strength and the effects of the presence of the
reinforcements on ageing of the matrix.

A major difficulty when studying the literature data on Aluminium based metal matrix
composites is the wide range of information that is available. This is mainly due to the
facts above that the materials are a combination of two or more components. This chapter
presents a review of the literature data available on the effect of various reinforcement
types, their size and volume fraction, ageing behavior with Al based MMC’s. Metal
matrix composites are a combination of two phases, matrix and the reinforcement.
Matrices can be selected from a number of Aluminium alloys e.g. 2000, 6000, 7000, and
many reinforcement types SiC, B4C, Al2O3, AlN, and C etc. are available in different
sizes, morphologies (particulates, short fibers, long fibers and platelets) and volume
fractions. These reinforcements can be combined with the different matrices, resulting in
large composite systems. Furthermore, several different processing routes, such as
powder metallurgy, square casting, rheocasting etc, can also process a specific MMC. An
additional factor for a number of MMC’s is also that their mechanical properties depend
upon the age hardening behavior of the matrix alloy.

2.7 Age Hardening in Al-MMC’s

Age hardening in Al-MMC has been of great interest of present research. The nature of
change in kinetics and magnitude of hardening has been investigated by the authors for a
various type of reinforcements in Al-MMC. Authors have shown that the ageing
characteristic accelerates with the reinforcement as compared to the unreinforced alloy.
The effects of artificial ageing on wear properties of AA6063 Aluminium alloy reported
that ageing treatments improved the wear behavior of the matrix alloy as compared to the
as cast samples. The artificial ageing produces the harder structure that is attributable to
acceleration of precipitation of Mg2Si and other phases as CuAl2 and AlFeSi[44].
In the case of Al-Mg-Si Alloy (6xxx series) based composites it has been shown that the
presence of ceramic reinforcements such as SiC/Al2O3 (whisker, short fibers or particles)
lead to acceleration in ageing kinetics when compared to unreinforced alloy [45,46].
However in contrast different rules have been reported in the case of hardening behavior
of ceramic reinforced Al-Cu alloy composites. Suresh et al [47] reported rapid age
hardening of Al-3.5Cu composites during the ageing at 190°C as compared to
unreinforced alloy. On the contrary, Kim et al [48] reported significant retardation in the
kinetics of hardening (i.e. increased time to peak hardness) during ageing of Al-4 Cu-SiC
whisker composites (1992).
However, Harris et al [49] have shown that SiCp additions have no influence on room
temperature ageing kinetics of Al-4Cu-SiCp Composites as compared to the unreinforced
alloy. Further more they also reported that, in case of high temperature ageing (ageing at
135°C, 170°C & 190°C), the composites attain peak hardness much earlier as compared
to unreinforced alloy. Dutta et al [50] observed the same behavior on the cast and
extruded Al-3.2Cu-5vol%SiCp composites exhibited accelerated hardening during the
natural and high temperature ageing. While there have been many papers examining the
abrasive wear properties of MMC’s only some authors have studied the effect of thermal
ageing on wear resistance. W.Qsong et at [51] examined the behavior of thermal ageing
on the abrasive wear resistance of 2014 Al-SiC and 6061Al-SiC composites. They found
that raising the ageing temperature from the underaged to peakaged condition improved
the wear resistance of the composite with decreasing the size of particulates.
M.Gupta et al [42], examined an Al-Based MMC Al-2%Cu reinforced with graphite and
SiC using conventional casting techniques. They demonstrated accelerated ageing
kinetics in samples of Al-Cu/SiC when compared to Al-Cu/C samples, this is attributed to
the enhanced Cu-enrichment in the interfacial region when compared to C-reinforced
samples, which favors the hardening behavior. Similar behavior is observed by M.Gupta
and M.K Sarappa [52] in 1995,that if the varying SiC volume fraction is reinforced in an
Al-based alloy (6061/SiC) ageing kinetics increase with increasing volume fraction of
SiC particles and decreasing their sizes. L.Salvo et al [53], studied the various types of
reinforcements including SiC of different sizes and volume fraction (up to 50%), chopped
nicalon and safill in 6061 and reported the same lines.

Vijay K. Sharma et al [54] has also reported the behavior of Al-Cu-Mg alloy composite
with SiC reinforcements with varying sizes and got the similar results. N V Ravi Kumar
et al [55] chosen the alloy Al-Zn Mg/SiCp and examined the matrix strength on
mechanical properties of composite and showed that the strengthening was found to be
dependent on the damage that is occurring during strain (with different heat treatments).
Similar behavior is observed by stir cast 6061/SiCp composite [52]. Compared to control
alloy the UTS values had decreased in peak and overage condition whereas in
solutionised condition different trends were observed in compositions having higher yield
strength than in tension. The fracture was found to be a combination of particle fracture
and particle pull out.

An accelerated ageing response has also been reported with SiC particulate whisker
reinforcements in SiCp/8090[56,45], SiCw/Al-Li[46], and SiCw/Al-Li-Cu[57], SiCw/Al-
Li-Cu-Mg-Zr composites [58]. Authors have also reinforced Al-4%Cu with Al2O3 fibers
produced by squeeze casting. The Cu precipitation in al-4Cu alloy is different from that
of the unreinforced alloy [43]. The formation of GP zones have been find to be inhibited
by the presence of fibers while the precipitation of θ’ phase is accelerated in composites.
The elastic moduli of the composites have been confirmed to be higher than that of the
unreinforced alloy, and sensitive to age hardening. S.Arakawa et al [43] investigated the
effect of heterogeneous precipitation of Al-4Cu/Al2O3 produced by mechanical alloying.
The authors have found that the age hardening response is significantly decreases, and
that considerable θ-phases are formed at a very short ageing time, as compared to those
by powder or ingot method. This is attributed to the preferential precipitation of the stable
θ-phases on grain boundaries occurs in earlier stages of ageing, and extends to fair
amount due to very fine grains, which reduces the concentration of Cu atoms in matrix to
form GP Zones and intermediates. There is a remarkable ageing kinetics in mechanically
alloyed composite, which is ascribed to the precipitation of intermediates assisted by the
higher dislocation density.

Mandal et al [59] reported the effect of TiB2 particles in Al-4Cu alloy. They also showed
a significant enhancement in ageing kinetics of the alloy in presence of TiB2 particles in
both as cast and peak aged conditions. However with higher additions of TiB2 particles’
strengthening is marginally reduced and the formation of Al3Ti phase is completely
suppressed. In contrast, strengthening contribution from TiB2 particles increases in
amount of these particles as expected.

In all such type of investigations, the authors have selected the various ceramic
reinforcements, in the current research has been constricted to few reinforcement types
such ac Al2O3, SiC, B4C. Limited work has been reported on fabrication and
characterization of Aluminium zircon composite. Banerji et al observed that the abrasive
wear rate of the Al-Si-Mg alloy decreases with in volume fraction (>0.09) of zircon
particles [16].

Current researches shows that the ageing behavior of Al-4.5%Cu matrix alloy reinforced
with zircon sand particles of varying sizes accelerated ageing response as compared to
the matrix alloy [29,30]. However it was found that Al2O3 reinforced composites show
higher acceleration in age hardening as compared to zircon sand particles, which is due to
the breakage of Al2O3 particles during melting and stirring processes. We se in all the
research here on Aluminium metal matrix composites the age hardening is better age
compared to the monolithic alloy due the enhanced dislocation density of the matrix as a
result of the difference of CTE between matrix and the reinforcement. Dislocations
generated due to the CTE mismatch act as heterogeneous nucleation sites for the
precipitates. If we go through the literature we see little research on zircon sand though it
possess high hardness, high modulus of elasticity and excellent thermal stability. Banerji
et al [16] found improvement in hardness, abrasive wear resistance, elastic modulus,
0.2% Proof stress and UTS of cast Al-3wt%Mg alloy due to dispersions of zircon sand
particles, which make zircon sand reinforced composite an important material for
industries like aerospace, military, automobiles etc. Also, the coefficient of thermal
expansion of zircon sand is comparable to that of SiC. Hence the influence of zircon sand
in ageing behavior of Al-4.5%Cumatrix alloy composite seems to be interesting. Also
limited work has been done to investigate ageing behavior of Al- alloys in oil and salt
brine quenching media.[25-28]
2.8 Basic Requirements for Age Hardening: Two basic requirements are:
• The main basic requirement of age hardening alloy system is that the solid solubility
limit should decrease with decrease in temperature, i.e. the phase diagram should
show a solvus as illustrated in Fig 3

• The precipitate of the of the second phase should be coherent in nature.

Fig. 3 - Hypothetical phase diagram for a precipitation hardenable alloy of

composition x1

Consider the precipitation hardening of an alloy of the composition x1 (since there is a

large decrease in solid solubility of solid solution in decreasing temperature) from T2
to T3, the hardening involves three basic steps: ---
1. Solution heat treatment: the alloy sample is heated to a temperature between solvus
and solidus temperature and soaked there until a uniform solid solution structure is
produced.
2. Quenching: the sample is rapidly cooled to a lower temperature, usually room
temperatureT3 to form supersaturated solid solution of phase. As shown in Fig 3 and 4
respectively.
 Fig. 4 - Schematic temperature versus time plot showing both solution &
precipitation heat treatments for age hardening [67]

3. Ageing: ageing the solution heat-treated and quenched alloy sample is necessary so as
to form a finely dispersed precipitate. These fine precipitates in alloy impede dislocation
movement during deformation by forcing the dislocations to either cut through the
precipitates or go around them. By restricting the dislocation motion during deformation,
the alloy is strengthened. The ageing curve is shown as in Fig. 5
2.9 Ageing Curve: The microstrutural evolution and age hardening is given in the form
of ageing curves. Ageing curves usually represent the effect of ageing time on strength
and hardness of a precipitation strengthened that has been solution treated and quenched.
The reduction in strength that occurs after long periods of time is known as overaging as
shown in Fig: 5.

Fig. 5 - Schematic ageing curve for an Al-Cu alloy composite[33]

2.9.1 Effect of aging time and temperature: Decomposition products are created by the
ageing of a supersaturated solid solution of a precipitation hardenable alloy, the highest
energy is for the supersaturated solid solution, and the lowest energy level is for the
equilibrium precipitate. The alloy can go spontaneously from a higher energy level to a
lower one if there is sufficient energy of activation for the transformation and if the
kinetic conditions are favourable. The supersaturated solid solution state is highly
unstable and the alloy tends to seek a lower energy state by the spontaneous
decomposition of the supersaturated solid solution into the metastable phases or the
equilibrium phase.

Fig.6 (a) Decomposition Products created by ageing the supersaturated solution[33],

(b) Precipitation sequence in Al-Cu alloy
GP1 Zone: these precipitate zones are formed at lower ageing temperatures and are
formed by copper atoms segregating at SSS- . These segregated regions have a shape of
disk of few atoms thick and 8-10nm in diameter. GP1 Zones are said to be coherent with
the matrix lattice as shown in Fig: 7 since Cu atoms just replace Al atoms in the lattice.

GP2 Zones: these precipitation zones have a tetragonal structure and are coherent with
much larger in size than GP1 Zone formed in due course with time.

Fig.7(a) Coherency of the precipitates, (b) Geometry of Guinier Preston Zones[33]

θ’-phase: this phase nucleates heterogeneously on dislocations and are incoherent with
the matrix as shown in Fig: 7, have a tetragonal structure with a thickness of 10-150nm.
θ-phase: this is the equilibrium phase incoherent and composition CuAl2.this has the
BCT structure and form from the θ’ or directly from the matrix.
2.9.2 Hardening of GP zones
 Fig. 8(a) Hardening of different zones [71], (b) Al-Cu phase diagram along
with metastable phase boundaries for GP zones, θ’ and θ”, together
with the equilibrium solvus line for the θ phase.[33,68]

Figure 8(b) shows the Al-rich corner of the equilibrium Al–Cu phase diagram, and
includes the metastable solvus boundaries for GP zones, θ “and θ’. Over many studies
[4–29], it has been proposed that the decomposition sequence in this system contains one
or more of the following processes:

Supersaturated solid solution: GP Zones → θ” → θ’ → θ

The complete precipitation sequence can only occur when the alloy is aged at
temperatures below the GP zone solvus Fig. 8(b). Various steps in this process may be
suppressed by aging at temperatures close to or above the intermediate solvus
temperatures. The first stage of hardening at 180°C is contributed to GP1 zones. After
reaching a critical diameter of between 5 and 10nm, an incubation period commences,
during which the zone size and the hardness remain constant [32]. Further aging results in
a second rise in hardness, attributed to θ” precipitation. The formation of θ” is also
followed by a shorter incubation period and the subsequent formation of the metastable
θ’ phase. Prolonged aging results in the formation of the equilibrium θ phase. Example of
hardening mechanism is illustrated in Fig8(c) given below:
Fig. 8(c) - Example of hardening behavior in Al-Cu alloy [69]
2.9.3 Effect of quenching medium

The objectives of quenching are to suppress the precipitation during quenching and to
retain solute atoms and quenched-in vacancies in solution . The best combination of
strength and ductility is achieved from a rapid quenching. Cooling rates should be
selected to obtain the desired microstructures and to reduce the duration time over certain
critical temperature range during quenching, in the regions where diffusion of smaller
atoms can lead to precipitation at potential defects [60].
The quenchants used for quenching aluminum alloys include water, brine solution and
polymer solution [61-62]. Water used to be the dominant quenchant for aluminum alloys,
but water quenching most often causes the distortion, cracking, and residual stress
problems [63,64].
Traditionally there are two ways to tackle these problems; one method is to increase the
water temperature so that the temperature gradient between water and the part being
quenched can be reduced [63]. It is reported that the water temperature affects properties
of cast aluminum alloy A356 subjected to T6 heat treatment once the water temperature
exceeds 60-70°C, with UTS and YS being significantly more sensitive than ductility [60].
However, the distortion problem can’t be effectively solved by this method. The other
method is to use the polymer solution. Quenching in polymer solution is used more
widely nowadays since varying the polymer concentration can effectively reduce the
distortion problem and more uniform quench can be readily obtained [64, 65]. Although a
high quench rate is essential to achieve the high strength, in many cases, such a quench
rate can’t be used due to problems of high internal stress and distortion. This is especially
true for cast components with the complex shapes and thin sections. To ensure that the
minimum required strength is obtained throughout a cast component, the effects of
quench rate on the strength of casting alloys need to be understood.

For age-hardenable aluminum alloys, the goal of quenching is to suppress the

precipitation of a secondary phase during quenching process without distortion and
excessive residual stress. Quenching media commonly used for aluminum alloys include
brine solution, water, and polymer solutions [60]. Cold water had been the dominant
quenchant for heat-treating aluminum alloys. However, in many cases, cold-water quench
produces unacceptable distortion or high residual stress due to high thermal gradients
generated upon cooling .
These parameters must be controlled to optimize the quenching process in terms of alloy
microstructure, properties, and performance. Some investigations have been carried out
by the researchers to study the effect of water temperature and the concentration of
polymer solution on the mechanical properties of wrought aluminum alloys. Emadi et al
[65] reported that increasing the water temperature or using air quench reduced the
cooling rate and increased the chance of precipitation of a secondary phase during
quenching.
Oil baths are not generally used in the wrought Al-alloys yet a variety of applications
available in heat treatment of steels [66]. However, such data is scarce for cast aluminum
alloys in the literature and quantitative measurement of the effects from each individual
process parameter is not available.
 Chapter 3
EXPERIMENTAL DETAILS

3.1 Materials

Nominal composition of the alloy used in this study is 4.5wt%Al (bal.) reinforced with
zircon sand particles with an average size of 65 µm, produced by stir casting route.

Quenching Media

Water, Transformer Oil, Salt brine solution (7%)

Experimental Techniques

Fig. 9 - Experimental Techniques followed

3.2 X-Ray Diffraction and Microscopy

X-ray diffraction patterns of zircon particles and composite were recorded.

Microstructural characterization studies were primarily accomplished using an optical
microscope and scanning electron microscope (SEM) equipped with an energy dispersive
X-ray spectrometer (EDS). The monolithic alloy and composite samples were
metallographically polished and etched with Keller’s reagent.

3.3 Ageing studies

The hardness measurements were done by Vickers microhardness tester. Five sets of
readings taken for each sample for better accuracy.

The following steps in age hardening treatment of the alloy composite after choosing a
proper composition of alloy: --
1. Solutionising: heating the alloy to a temperature at about 540°C to obtain a single-
phase solid solution α.
2. Quenching: the solutionised alloy is cooled rapidly to retain the high temperature
single-phase supersaturated solid solution at room temperature.
3. Ageing: age hardening by holding the quenched alloy at elevated temperature 180°C.

The hardness measurements were done by Vickers microhardness tester. Five sets of
readings taken for each sample for better accuracy.
The thermal cycling of the composite is done by repeatedly solutionising the composite
and taking the hardness measurements each time for a number of eight cycles.
 Chapter 4
RESULTS AND DISCUSSION

4.1 Characterization of Zircon Particles

Scanning electron micrographs of zircon particles of various average particle size 65 µm

are shown in Fig. 10. It shows that coarser particles are more spherical in shape compared
to the finer ones.

Fig. 10 - Scanning electron micrographs of the composite showing uniform

distribution of zircon sand particles
Fig. 11 - Scanning electron micrographs showing good particle matrix bonding

4.2 Microstructural examination of Composite

Scanning electron micrographs at low magnification show uniformly distributed zircon

particles throughout the matrix (Fig.10). Scanning electron micrograph of as-cast
composite at high magnification shows the presence of uniformly distributed secondary
phase in the alloy matrix (Fig.11). There is no evidence of voids at the particle matrix
interface, indicating a strong continuous bond between zircon particle and the alloy
matrix.

X-ray diffraction pattern of as cast composite shows the presence of Al, CuAl2 and zircon
sand (Fig. 12). This confirms the presence of zircon particles and CuAl2 phase in the cast
composite. There is no crystallographic change in the tetragonal zircon during the
synthesis process, confirming the stability of zircon particles.
Fig.12 Typical X-Ray diffraction pattern for as cast composite

Optical micrograph of the as-cast alloy is shown in Fig. 13. The matrix of the composite
has the cellular structure, where the size of the cell depends on the zircon particle size
and amount in the composite

µm
100µ

Fig. 13 - Optical microstructures of as cast composite

A polished metallography sample reveals circular grain type morphology of dendrites. In

the present investigation, monolithic alloy shows dendritic structure. . In general there
appears to be a reasonably uniform distribution of zircon sand particles. (Fig. 13)
4.3 Ageing Studies of the composite

The Hardness measurements were done by Vicker’s microhardness tester at a load 25g
and for a dwell time of 20 seconds. A set of five readings is taken for better accuracy

Table 5-Ageing data of the composite in Water

Ageing
Mean
Time Microhardness Hv
Hv
(hrs)
0 65.7 67.1 66.0 66.4 66.6 66.36
2 66.0 67.5 66.7 65.7 65.8 66.34
4 66.6 71.0 70.8 69.2 68.6 69.24
6 68.17 70.03 66.6 67.3 68.6 68.14
8 68.6 70.0 71.0 66.0 72.6 69.64
10 70.8 66.0 70.44 69.09 69.4 69.14

Table 6-Ageing data of the composite in Oil

Ageing Microhardness Hv Mean

Time Hv
(hrs)
0 65.5 64.6 63.8 65.0 66.3 65.04
2 70.5 68.4 68.56 68.17 67.7 68.66
4 72.5 68.3 69.22 69.76 68.56 69.66
6 67.39 67.65 66.23 67.0 66.37 66.92
8 68.17 68.83 68.56 68.69 69.36 68072
10 69.23 69.76 68.04 66.5 67.5 68.20

Table 7-Ageing data of the composite in Salt brine solution

Ageing
Mean
Time Microhardness Hv
Hv
(hrs)
0 69.09 67.91 67.7 68.56 66.62 67.97
 2 69.09 69.49 69.66 70.72 70.44 69.88
4 71.0 72.1 73.27 72.98 71.28 72.12
6 70.58 72.2 72.12 72.12 72.98 71.98
8 71.5 70.31 69.9 67.26 69.96 69.78
10 67.26 67.52 67.65 65.75 67.26 67.08

Ageing curves

Fig. 14: Age hardening behavior of the composite in different quenching media

Table 8-Ageing Conditions

Solutionizing Temperature 540°C

Solutionizing Time (hour) 2 hours
 Ageing Temperature 180°C
Ageing Time (hour) 2 4 6 8 10

Figure 14 shows the variation in microhardness as a function of ageing time for zircon
sand particulate reinforced composite in different quenching media water, oil and salt
bath. Water quenched samples takes longer time to attain the peak hardness values
subjected to the ageing treatment. More dislocations are generated at the particle matrix
interface due to their CTE mismatch as compared to the interparticle region. This causes
copper atoms from the matrix to diffuse through the interfacial region. The concentration
of Cu atoms in the matrix gradually decreases that’s why the precipitation is delayed due
to this copper leaned area and it shows peak hardness at larger ageing times. Here water
quenched samples show peak hardness around 8 hrs in contradictory to oil quenched
samples at around 4 hrs. Oil is classed as an intermediate quench. It has a slower cooling
rate than brine or water. Distortion and danger of cracking is lower as compared to water
or brine. Oil quenched sample show peak hardness at early stages of ageing, it is near 6
hrs as shown in Fig 14. This can be attributed to the presence of less dislocations after oil
quenching, so that the copper atoms from the interparticle region does not diffuse
significantly and their concentration is enough to cause early precipitation.
In salt brine quenched samples a large number dislocations are generated around the
particle matrix interface, as it does not form the vapour blanket stage as in case of water.
The time to peak hardness occurs in between water and salt brine quenched samples since
the dislocation annihilation takes place after some time and the diffusion of copper atoms
from the interparticle region to the particle matrix interface is not so much as in case of
water quenched but more than oil quenched samples.
It will be clearer with the schematic illustration as shown in Fig 15
 Fig.15 - Schematic diagram to show dislocations around the interparticle matrix
interface

From Fig.15 initially the Cu solute atoms are dissolved uniformly in the matrix. The
concentration of Cu atoms in matrix is more as compared to the particulate matrix bond
region as a result, the diffusion/segregation of Cu atoms through this interfacial region
and the enhanced dislocation density increases the hardness value as compared to the
inter particle matrix region. Dislocations are more near interface as compared to
interparticle region as shown but it is still more as compared to the monolithic alloy.
That’s why the composites usually show peak-aged condition much early as compared to
monolithic alloy.

Under all the heat treatment conditions, the micro-hardness increases with the aging time
to a peak value and then decreases with a prolonged aging time. This can be explained by
the evolution of CuAl2 precipitates with the aging time and the interaction between the
precipitates and dislocations.

Salt solution has the advantage of providing more uniform quench over water by
extending the vapor blanket stage to a lower temperature that’s why more hardness
obtained, but there is a danger of distortion and cracks in the sample so it is not
commonly used for thin sections.

4.4 Thermal Cycling

Thermal cycling of the composite is done by solutionising repeatedly and taking the
hardness meaurement each time.

Table 9-Thermal cycling data of the composite in Water

No. of
Therm Mean
Microhardness Hv
al Hv
Cycles
1 65.7 67.1 66.0 66.4 66.6 66.36
2 71.5 71.56 72.4 72.9 73.4 72.35
3 75.66 73.8 72.6 70.8 75.97 73.76
4 69.7 72.4 69.76 72.1 71.0 70.99
5 69.36 69.9 70.03 66.7 66.0 68.39
6 67.6 66.88 66.7 69.05 67 67.44
7 66.37 66.5 65.5 65.38 65.75 65.9
8 65.5 64.23 64.2 65.3 64.8 64.8

Table 10-Thermal cycling data of the composite in Oil

 No. of
Therm Mean
Microhardness Hv
al Hv
Cycles
1 65.5 64.6 63.8 65.0 66.3 65.0
2 69.36 64.4 65.75 66.37 64.53 66.08
3 65.8 62.1 61.7 66.0 65.26 64.17
4 64.6 63.63 65.03 64.05 65.0 64.46
5 64.2 63.69 65.13 62.64 64.29 63.99
6 64.5 63.5 62.87 63.8 65.75 64.08
7 64.2 61.17 61.85 64.77 65.6 63.51
8 62.4 60.51 61.85 62.53 61.51 61.76

Table 11-Thermal cycling data of the composite in Salt brine solution

No. of
Therm Mean
Microhardness Hv
al Hv
Cycles
1 69.09 67.91 67.7 68.56 71.42 68.93
2 69.3 72.1 71.0 68.04 67.52 69.59
3 66.6 66.7 66.78 66.88 66.0 66.79
4 66.0 65.87 66.0 63.58 64.17 65.12
5 62.3 66.88 62.64 62.76 63.11 63.53
6 61.4 62.8 62.41 62.5 65.75 62.35
7 64.89 63.46 61.2 62.41 62.99 62.99
8 62.64 62.87 62.99 63.81 62.99 63.06
Thermal cycling Curves
 Fig.16 - Thermal cycling of the composite in different quenching media

The thermal cycling curve of this alloy composite has two distinct stages: the first stage is
a rapid hardness increase in initial stages of thermal cycling observed until the maximum
hardness occurs. (Figure 16). After this rapid reaction, the hardness curve exhibits a
gradual drop with increasing number of thermal cycles.

When the specimen is heat-treated and quenched a large number of dislocation are
generated due to the difference in CTE between the particulates and matrix. During initial
thermal cycles the dislocation density gets enhanced drastically causing the rapid
hardening. After a fixed number of thermally cycling the composite eventually a state is
reached where the dislocations cancel each other due to the reduced interparticle spacing
among themselves and forming a loop structure. In other words they annihilate and show
the drop in hardness responsible for the plateau kind of stage in the graph.
After continuously thermally cycling the composite the hardness values drop as less
dislocations are now generated. And after one or more thermal cycles the interface starts
to crack under the thermally induced stress, it is more in salt brine.

If there is a strong interaction between the dislocation and the segregated solute atoms,
dislocations become locked and hardening would precede the heterogeneous
precipitation.

Water quenched samples produces more dislocations than oil quenched samples, while
salt brine quenched samples attain the maximum hardness due to large number of
dislocations as it does not form any kind of vapor blanket as in case of water.
Oil is less severe quenching medium; it produces less stresses hence hardness is
minimum.
 Chapter 5
SUMMARY AND CONCLUSIONS

• Zircon particles can be uniformly dispersed in Al-4.5wt% Cu alloy by the casting

route.
• Under all the heat treatment conditions, the micro-hardness increased with the
aging time to a peak value and then decreased with a prolonged aging time.
• Water quenched samples showed the peak hardness at later stages of ageing time,
this can be attributed to the diffusion of copper atoms from the matrix to the
interface region of the composite thus reducing the copper concentration in the
interparticle region required for precipitation.
• Oil quenched samples showed the peak hardness in early stages of ageing
hardness while salt brine quenched samples showed time to attain peak hardness
in between water and oil quenched samples.
• Thermal cycling of the composite reveals that the microhardness of the composite
increases with repeated solution heat treatment, attains a maximum and gradually
drops with increasing number of heat treatment cycles. All the samples in
different quenching media show a similar kind of behavior.
• Initial stage hardening is due to the increased number of dislocation during first
few thermal cycles, and hardness drops at a later stage where the dislocations
interact among themselves and annihilate each other with increasing the number
of thermal cycles. Continuously thermally cycling causes the particle matrix
interface to crack under the thermally induced stress. Cracking and distortion is
more in case of salt brine solution.
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