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STUDY ON THE EFFECT OF HIGH ENERGY BALL

MILLING (A NANO MATERIAL PROCESS) ON THE
MICROSTRUCTURE AND MECHANICAL PROPERTIES
OF A (Al-Si-Fe-Cu) ALLOY

A THESIS SUBMITTED IN PARTIAL FULFILLMENT

OF THE REQUIREMENTS FOR THE DEGREE OF

Bachelor of Technology
In
Metallurgical and Materials Engineering

By
KAUSHAL KISHORE SINGH
SUDIPTO BHATTACHARJEE

Department of Metallurgical and Materials Engineering

National Institute of Technology
Rourkela
2007
 STUDY ON THE EFFECT OF HIGH ENERGY BALL
MILLING (A NANO MATERIAL PROCESS) ON THE
MICROSTRUCTURE AND MECHANICAL PROPERTIES
OF A (Al-Si-Fe-Cu) ALLOY

A THESIS SUBMITTED IN PARTIAL FULFILLMENT

OF THE REQUIREMENTS FOR THE DEGREE OF

Bachelor of Technology
In
Metallurgical and Materials Engineering

By
KAUSHAL KISHORE SINGH
SUDIPTO BHATTACHARJEE
Under the Guidance of
Prof. Dr.A.K.PANDA

Department of Metallurgical and Materials Engineering

National Institute of Technology
Rourkela
2007
 National Institute of Technology
Rourkela

CERTIFICATE

This is to certify that the thesis entitled, “Study on the effect of high energy ball
milling (a nano material process) on the microstructure and mechanical properties of
a(Al-Si-Fe-Cu) alloy” submitted by Sri Kaushal Kishore Singh and Sri Sudipto
Bhattacharjee in partial fulfillment of the requirements for the award of Bachelor of
Technology Degree in Metallurgical and Materials Engineering at the National
Institute of Technology, Rourkela (Deemed University) is an authentic work carried
out by them under my supervision and guidance.

To the best of my knowledge, the matter embodied in the thesis has not been
submitted to any other University / Institute for the award of any Degree or Diploma.

Date: Prof. Dr.A.K.Panda

Dept. of Metallurgical and Materials Engineering
National Institute of Technology
Rourkela – 769008

i
 ACKNOWLEDGEMENT
During the entire project work, we have received endless help and guidance from
Prof.Dr.A.K.Panda right from deciding the topic till the final presentations. We wish
to express our deep gratitude to all those who extended their helping hands towards
me in various ways during our one year project work.We really appreciate the support
we have received during our project from our guide who were available not only
within institute hours but beyond that and sometimes even late night. We are thankful
to Prof.Dr.A.K.Panda who gave us all the facilities and resources at his disposal that
were needed for our project work.We would like to express our sincere thanks to the
department of Metallurgical and Materials Engineering for allowing us to access the
computers in the lab for hours together.
The project could not have been completed without the constant support and technical
inputs that we received from Sri.Uday Kumar Sahoo who helped us to get past some
tricky situations which we encountered during my work.

April, 2007
Kausahal Kishore Singh
Sudipto Bhattacharjee
Dept. of Metallurgical and Materials Engineering
National Institute of Technology
Rourkela - 769008

ii.
 CONTENTS

Sl. No. Topic Page

1 Certificate i
2 Acknowledgement ii
3 Contents iii
4 Abstract iv
5 List of Figures v
6 List of Tables vi
7 Chapter 1: Introduction. 1
Properties. 3
Method of synthesis. 4
8 Chapter 2: Applications. 7
Thermodynamics of solution formation. 8
Typical Composition. 10
Process variables. 11
Types of alloying equipment. 12
Mechanism of Mechanical alloying. 16
Previous work done. 17

9 Chapter 3: Experimental. 18
X-Ray Diffraction. 18
Particle size calculation 20

10 Chapter 4 : Results and Discussion 22

Microstructure 25

11 Chapter 5 : Conclusion 27
Refrences 28
 National Institute of Technology
Rourkela

ABSTRACT

Mechanical alloying is a solid-state powder processing technique involving repeated

welding, fracturing, and rewelding of powder particles in a high-energy ball
mill.Mechanical Alloying has now been shown to be capable of synthesizing a variety
of equilibrium and non-equilibrium alloy phases starting from blended elemental or
prealloyed powders.Materials have been found to attain unusual properties in their
nano level sizes which are not found in their conventional form.Al-Si alloys
containing other transition metals are used in the as cast condition for automotive and
aerospace for the engine components.
Srivastava etal have studied Al-18%Si-5%Fe-1.5%Cu by rapid solidification
technique and have compared the microstructure with that in the cast condition .In the
present work an attempt was made to develop this alloy through mechanical alloying
route.

iv.
 LIST OF FIGURES

Figure no. Name Page

2.1 Free energy of mechanical mixture. 8
2.2 Schematic illustration of the evolution of an atomic solution by 9
the progressive reduction

2.3 SPEX shaker mill. 12

2.4 Attritor mill. 13
2.5 Planetary ball mill. 14
2.6 Types of forces acting on the particles during milling. 14
2.7 Particle size Vs Milling time. 15
2.8 Ball-powder-ball collision of powder mixture during Mechanical 16
alloying
3.1 Typical X-ray diffractogram of mechanically alloyed (Al- 18
18%Si-5%Fe-1.5%Cu) powder.

3.2 Shows the overlapped first peak of Aluminium. 19

3.3 Particle size as a function of milling time. 21
4.1 Microphotograph of simply mixed sample(1000X) 25
4.2 Microphotograph of mechanically alloyed sample(3500X) 26

v.
 LIST OF TABLES

Table no. Name Page

2.1 Compositions (wt %) of some typical alloys 10
3.1 Tabulation of decrease in particle size with increase in 20
milling time.
4.1 Schedule for compaction followed by sintering. 22
4.2 Comparison of compressive strengths between pellets 23
(simple mixing).
4.3 Comparison of compressive strengths between pellets 24
(simple mixing) and (mechanically alloyed)

vi.
INTRODUCTION
 INTRODUCTION
Nanomaterials are experiencing a rapid development in recent years due to their
existing and/or potential applications in a wide variety of technological areas such as
electronics, catalysis, ceramics, magnetic data storage, structural components etc. To
meet the technological demands in these areas, the size of the materials should be
reduced to the nanometer scale. For example, the miniaturization of functional
electronic devices demands the placement or assembly of nanometer scale components
into well-defined structures. As the size reduces into the nanometer range, the materials
exhibit peculiar and interesting mechanical and physical properties, e.g. increased
mechanical strength, enhanced diffusivity, higher specific heat and electrical resistivity
compared to conventional coarse grained counterparts. Nanomaterials (nanocrystalline
materials) are materials possessing grain sizes on the order of a billionth of a meter.
They manifest extremely fascinating and useful properties, which can be exploited for a
variety of structural and non-structural applications. Nanomaterials can be classified
into nanocrystalline materials and nanoparticles. The former are polycrystalline bulk
materials with grain sizes in the nanometer range (less than 100 nm), while the latter
refers to ultra fine dispersive particles with diameters below 100 nm. Nanoparticles are
generally considered as the building blocks of bulk nanocrystalline materials. Research
in nanomaterials is a multidisciplinary effort that involves interaction between
researchers in the field of physics, chemistry, mechanics and materials science, or even
biology and medicine. It has been stimulated by the interest for basic scientific
investigations and their technological applications. Nanomaterials and most of the
applications derived from them are still in an early stage of technical development.
There are several issues that remain to be addressed before nanomaterials will become
potentially useful for industrial sectors. These issues include synthesis of high purity
materials with large yield economically and environmentally, characterization of new
structures and properties of nanophase materials, fabrication of dense products from
nanoparticles with full density and less contamination, and retention of the ultrafine
grain size in service in order to preserve the mechanical properties associated with the
nanometer scale. Novel fabrication technology of nanoparticles is versatile and includes
a wide range of vapor, liquid and solid state processing routes.

1
Available techniques for the synthesis of nanoparticles via vapor routes range from
physical vapor deposition and chemical vapor deposition to aerosol spraying.The liquid
route involves sol–gel and wet chemical methods. The solid-state route preparation
takes place via mechanical milling and mechanochemical synthesis. Each method has
its own advantages and shortcomings. Among these, mechanical milling and spray
conversion processing are commonly used to produce large quantities of nanopowders.
Nanoparticles synthesized from several routes may have different internal structures
that would affect the properties of materials consolidated from them. Processing
nanoparticles into fully dense, bulk products or coatings which retain the nanometer
scale grain size is rather difficult to achieve inpractice. Due to their high specific
surface areas, nanoparticles exhibit a high reactivity and strong tendency towards
agglomeration. Moreover, rapid grain growth is likely to occur during processing at
high temperatures. As unique properties of nanocrystaline materials derived from their
fine grain size, it is of crucial importance to retain the microstructure at a nanometer
scale during consolidation to form bulk materials.It is also noticed that pores are
generated in bulk nanocrystalline materials consolidated from nanoparticles prepared
by inert-gas condensation. Such nanopores can lead to a decrease in Young’s modulus
of consolidated nanocrystalline materials. Electrodeposited samples are believed to be
free from porosity, but they contain certain impurities and texture that may degrade
their mechanical performances. Therefore, controlling these properties during synthesis
and subsequent consolidation procedures are the largest challenges facing researchers.
The unique properties of nanocrystalline materials are derived from their large number
of grain boundaries compared to coarse-grained polycrystalline counterpartes. In
nanocrystalline solids, a large fraction of atoms (up to 49%) are boundary atoms. Thus
the interface structure plays an important role in determining the physical and
mechanical properties of nanocrystalline materials. Huang reported that nanocrystalline
copper has a much higher resistivity and a larger temperature dependence of the
resistivity than bulk copper. They attributed this effect to the grain boundary enhanced
scattering of electrons. Despite recent advances in the development of nanocrystalline
materials, much work remains to be done to achieve a basic understanding of their
deformation and fracture behaviour.

2
1.1 Properties of nanomaterials

Nanostructured materials are a broad class of materials, with microstructures modulated

in zero to three dimensions on length scales less than 100 nm. These materials are
atoms arranged in nanosized clusters, which become the constituent grains or building
blocks of the material. Conventional materials have grains sizes ranging from microns
to several millimetres and contain several billion atoms each. Nanometre sized grains
contain only about 900 atoms each. As the grain size decreases, there is a significant
increase in the volume fraction of grain boundaries or interfaces. This characteristic
strongly influences the chemical and physical properties of the material.

Nanophase metals exhibit significant increases in yield strength and elastic modulus. It
has also been shown that other considerable interest in the generation of carbon
nanostructures, which are related to the famous Buckyball. In addition, the use of
nano-sized materials as fillers for composite materials is generating interest.
Specifically in the case of polymer nanocomposites. All materials are composed of
grains, which in turn comprise many atoms. These grains are usually invisible to the
naked eye, depending on their size. Conventional materials have grains varying in size
anywhere from 100’s of microns (µm) to millimetres (mm). A nanometre (nm) is even
smaller a dimension than a µm, and is a billionth (10-9) of a meter. A nanocrystalline
material has grains on the order of 1-100 nm. The average size of an atom is on the
order of 1 to 2 angstroms (Å) in radius. 1 nanometre comprises 10 Å, and hence in one
nm, there may be 3-5 atoms, depending on the atomic radii. Nanocrystalline materials
are exceptionally strong, hard, and ductile at high temperatures, wear-resistant, erosion-
resistant, corrosion-resistant, and chemically very active. Nanocrystalline materials, or
nanomaterials, are also much more formable than their conventional, commercially
available counterparts.

3
1.2 Method of synthesis

There are five widely known methods of production of nanomaterials they are given as
follows:

Sol-gel synthesis.

Inert gas condensation.

Mechanical alloying or high-energy ball milling.

Plasma synthesis.

Electrodeposition.

1.2.1 Sol-Gel Synthesis:

Sol-gel Synthesis is the synthesis of primarily metal oxides (binary, ternary…) by

hydrolysis and condensation reactions of suitable precursors that has also been applied
to non-oxide material.

12.2 Inert Gas Condensation:

A modification that consists of a scraper and a collection funnel allows the production
of relatively large quantities of nanoparticles, which are agglomerated but do not form
hard agglomerates and which can be compacted in the apparatus itself without exposing
them to air. The group of Birringer and Gleiter pioneered this method. Increased
pressure or increased molecular weight of the inert gas leads to an increase in the mean
particle size. This so-called Inert Gas Condensation method is already used on a
commercial scale for a wide range of materials.

4
1.2.3 Mechanical Alloying or High Energy Milling:

Mechanical alloying was originally invented as a method to manufacture oxide

dispersion strengthened nickel alloys It is a high energy ball milling process, where
alloying is the result of the repeated fracture and cold welding of the component
particles. Highly metastable materials such as amorphous alloys and nanostructured
materials can be prepared by the process. Scaling up to industrial quantities seems
straight forward. In addition to attrition and agglomeration, high energy milling can
induce chemical reactions, which can be used to influence the milling process and the
properties of the product. This fact was utilized to prepare magnetic oxide-metal
nanocomposites via mechanically induced displacement reactions between a metal
oxide and a more reactive metal. High energy ball milling can also induce chemical
changes in non-metallurgical binary systems, including silicates, minerals, ferrites,
ceramics, and organic compounds. The research area of mechanochemistry was
developed to study and utilize these processes. As many mechanical alloying processes
involve chemical changes, the distinction between mechanical alloying and
mechanochemistry is often arbitrary.

1.2.4 Plasma Synthesis:

Plasma Synthesis has been used in the preparation of advanced materials such as new
ceramics, nanometric metallic powders, biomaterials and superconductors. The typical
size of the nanoparticles produced ranges from 20 to 100 nm, depending on the quench
conditions employed. Such small-scale materials display unusual properties (chemical,
physical, electrical, optical, mechanical, magnetic, etc.) as compared to their bulk
states. The production of nanopowders is one the most notable applications of induction
plasma. The induction plasma torch possesses a high flexibility and tolerance to the
processing chemistry because there are no metallic electrodes to react with the
reactants, and therefore oxidising or reducing atmospheres can be used.

5
1.2.5 Electrodeposition:

Electrodeposition is an electrode reactions involving oxidation/reduction of a solid

metal and its dissolved ion. e.g., if a copper metal rod is immersed in a copper sulphate
solution, the copper cations can be cathodically reduced to copper metal, or the copper
metal can be anodically oxidized to copper ions. Compare with a redox reaction where
both the oxidized and the reduced species are in solution.The terms "Electrodeposition"
and "Electrodissolution" are often used to describe these reactions.

1.2.6 Epitaxy:

This technology is quite similar to what happens in CVD processes, however, if the
substrate is an ordered semiconductor crystal (i.e. silicon, gallium arsenide), it is
possible with this process to continue building on the substrate with the same
crystallographic orientation with the substrate acting as a seed for the deposition. If an
amorphous/polycrystalline substrate surface is used, the film will also be amorphous or
polycrystalline.

6
LITRATURE SURVEY
 LITRATURE SURVEY

2.1APPLICATION OF NANO MATERIALS

Since nanomaterials possess unique, beneficial chemical, physical, and mechanical

properties, they can be used for a wide variety of applications. These applications
include, but are not limited to, the following:

High strength application.

Electric and magnetic material.

High-sensitivity sensors.

Hydrogen storage.

Biotechnology.

Semi conducting properties of dielectric.

Kinetic Energy (KE) penetrators with enhanced lethality.

High energy density batteries.

Longer-lasting satellites.

Longer-lasting medical implants.

Large electrochromic display devices.

7
 2.2THERMODYNAMICS OF SOLUTION FORMATION

The alloy is in a mechanically homogenized nonequilibrium state, and that prolonged

annealing at low temperatures should lead to, for example, the clustering of chromium
atoms. Solution formation normal thermodynamic theory for solutions begins with the
mixing of component atoms. In mechanical alloying, however, the solution is prepared
by first mixing together lumps of the components, each of which might contain many
millions of identical atoms. We examine here the way in which a solution evolves from
these large lumps into an intimate mixture of different kinds of atoms without the
participation of diffusion or of melting and this leads to interesting outcomes which
have implications on how we interpret the mechanical alloying process. Consider the
pure components A and B with molar free energies µo A and µo B respectively. If the
components are initially in the form of powders then the average free energy of such a
mixture of powders is simply:
G {mixture} = (1 − x) µoA + xµo ; where x is the mole fraction of B
.

Fig. 2.1: (a) The free energy of a mechanical mixture, where the mean free energy is
simply the weighted mean of the components. (b) The free energy of an ideal atomic
solution is always lower than that of a mechanical mixture due to configurational
entropy.
8
It is assumed that the powder particles are so large that the A and B atoms do not
“feel” each other’s presence via interatomic forces between unlike atoms. It is also
assumed that the number of ways in which the mixture of powder particles can be
arranged is not sufficiently different from unity to give a significant contribution to
configurational entropy of mixing. It has a free energy that is simply a weighted mean
of the components. In contrast to a mechanical mixture, a solution is conventionally
taken to describe a mixture of atoms or molecules.

Fig. 2.2: Schematic illustration of the evolution of an atomic solution by the progressive
reduction in the size of different particles, a process akin to mechanical alloying.

9
There will in general be an enthalpy change associated with the change in near
neighbour bonds. Because the total number of ways in which the “particles” can
arrange is now very large, there will always be a significant contribution from the
entropy of mixing, even when the enthalpy of mixing is zero. The free energy of the
solution is therefore different from that of the mechanical mixture. The difference in the
free energy between these two states of the components is the free energy of mixing,
the. The problem is illustrated in Fig.2.2 which shows the division of particles into ever
smaller particles until an atomic solution is achieved.

2.3TYPICAL CHEMICAL COMPOSITION

The intense deformation associated with mechanical alloying can force atoms into
positions where they may not prefer to be at equilibrium. The atomic structure of solid
solutions in commercially important metals formed by mechanical alloying process can
be studied using field ion microscopy and atom probe.

Table.2.1: Compositions (wt %) of some typical alloys.

10
2.4 PROCESS VARIABLES

Mechanical alloying is a complex process and hence involves optimization of a number

of variables to achieve the desired product phase and/or microstructure. Some of the
important parameters that have an effect on the final constitution of the powder are:

Type of mill

Milling container

Milling speed

Milling time

Type, size, and size distribution of the grinding medium

Ball-to-powder weight ratio

Extent of filling the vial

Milling atmosphere

Process control agent

Temperature of milling.

All these process variables are not completely independent. For example, the optimum
milling time depends on the type of mill, size of the grinding medium, temperature of
milling, ball-to-powder ratio, etc

11
 2.5 TYPE OF MILLING EQUIPMENTS USED FOR MECHANICAL
ALLOYING

Different types of high-energy milling equipment are used to produce mechanically

alloyed powders. They differ in their capacity, efficiency of milling and additional
arrangements for cooling, heating, etc.

SPEX shaker mills

Attritor mills

Commercial mills

Planetary ball mills (To be used in our experimentation)

2.5.1SPEX shaker mills

Shaker mills such as SPEX mills, which mill about 10±20 g of the powder at a time, are
most commonly used for laboratory investigations and for alloy screening purposes.

Fig-2.3: SPEX shaker mill

12
2.5.2Attritor mills
A conventional ball mill consists of a rotating horizontal drum half-filled with small
steel balls. As the drum rotates the balls drop on the metal powder that is being ground.

Fig 2.4: Attritor mill

2.5.3Planetary ball mills:

Another popular mill for conducting MA experiments is the planetary ball mill
(referred to as Pulverisette) in which a few hundred grams of the powder can be milled
at a time. The planetary ball mill owes its name to the planet-like movement of its vials.
These are arranged on a rotating support disk and a special drive mechanism causes
them to rotate around their own axes. The centrifugal force produced by the vials 12
rotating around their own axes and that produced by the rotating support disk both act
on the vial contents, consisting of material to be ground and the grinding balls. Since
the vials and the supporting disk rotate in opposite directions, the centrifugal forces
alternately act in like and opposite directions. This causes the grinding balls to run
down the inside wall of the vial the friction effect, followed by the material being
ground and grinding balls lifting of and traveling freely through the inner chamber of
the vial and colliding against the opposing inside wall the impact effect (Fig.2.6).
13
 Fig.2.5: Planatery ball mill

Fig-2.6: Showing types of forces acting

Even though the disk and the vial rotation speeds could not be independently controlled
in the earlier versions, it is possible to do so in the modern versions. Grinding vials and
balls are available in eight different materials agate, silicon nitride, sintered corundum,
zirconia, chrome steel, Cr+Ni steel, tungsten carbide, and plastic polyamide. Even

14
though the linear velocity of the balls in this type of mill is higher than that in the SPEX
mills, the frequency of impacts is much more in the SPEX mills.

Fig-2.7: Plot of Particle size Vs Milling time

15
2.7 MECHANISM OF MECHANICAL ALLOYING

In the planetary ball mill its vials are arranged on a rotating support disk.

A special drive mechanism causes them to rotate around their own axes.

The force of the impact plastically deforms the powder particles.

The particles get work hardened and fracture.

The new surfaces created enable the particles to weld together.

Particle contains substantially all of the starting ingredients, in the proportion

they were mixed together

Fig-2.8: Ball-powder-ball collision of powder mixture during mechanical alloying.

16
2.8 PREVIOUS WORK DONE

1. Development of magnetic and superconducting properties.eg: Oxide

superconductor:Bi2Sr2CaCu20x by plasma synthesis processing of fine
particles, especially of high-tech ceramic materials. Peter C. Kong and Y. C.
Lau, Pure &App/. Chem., Vol. 62, No. 9, pp. 1809-1816,1990,

2. Aluminium alloy with nominal composition of Al–18%Si–5%Fe–1.5%Cu

(wt.%) has been spray deposited and its microstructural features have been
studied V.C.Srivastava , S.N.Ojha, P.Ghosal. Materials Letters vol 56 (2002)
,page797– 801.

3. Lithium ion intercalation is done to enhance its anodic properties. Ball-

milling in liquid media. Raphafel Janot, Daniel Guerard , Materials Science 50
(2005) 1–92

4. Nanocrystalline materials and coatings. S.C. Tjong, Haydn Chen.

Materials Science and Engineering R 45 (2004) 1–88.

5. Concerning the magnetic properties, some fine-particle systems exhibit good

hard magnetic properties and used as soft magnets R. Hamzaoui, O. Elkedim,
N. Fenineche, E. Gaffet, J. Craven Materials Science and Engineering A360
(2003) 299-/305.

17
EXPERIMENTAL
 EXPERIMENTAL

The composition which has been studied:

Al-18%Si-5%Fe-1.5%Cu
Stoichiometric amounts of the powders are weighed and mixed. Milling carried out
in a planetary ball mill. In Planetary ball mill the milling was schedule as milling time
10 min and pause 15min, this was done because in milling high amount of energy is
evolved and it can cause hazards. The milling was carried out in the medium, in order
to maintain the powder mixture at at room temperature.Type of container used was
ZrO2 .Total milling time employed was 25Hrs with suitable milling speed of 300rpm.

3.1X-RAY DIFFRACTION
Samples were taken out for XRD analysis after for every 5 Hrs of milling which was
carried out in Phillips expert system. Fig-3.1 shows the typical diffractograms. The
comparison of the diffractograms reveals progressing line broadening as a function of
time of milling, Fig- shows the overlapped first peak of Aluminium.

Fig-3.1: Typical X-ray diffractogram of mechanically alloyed (Al-18%Si-5%Fe-

1.5%Cu) powder.
18
Fig-3.2 Shows the overlapped first peak of Aluminium

Fig-3.2 shows the comparison between the different diffractograms for the first peak
of aluminium for the samples obtained by simple mixing and milled for 5,10,15,20,25
hrs and it reveals progressing line broadening as a function of time of milling.

19
3.2PARTICLE SIZE CALCULATION

The crystallite size and lattice strain in the powder particles can be determined by the
X-ray peak broadening techniques. X-ray diffraction peaks are broadened due to:
1. Instrumental effects,
2. Small particle size,
3. Lattice strain in the material.
However, if one is interested only in following the trend of change of crystallite size
with milling conditions, this simple technique may be acceptable. While the X-ray
peak broadening due to small crystallite size is inversely proportional to cos θ. The
decrease in particle size with increase can be seen in Table3.1

Table-3.1

SlNo. Milling Time (Hrs) Particle Size(Angstrom)

1 5 283.83
2 10 266.96
3 15 256.81
4 20 237.95
5 25 238.22

Most commonly the crystallite size is determined by measuring the Bragg peak width
at half the maximum intensity and putting its value in scherrer’s formula which is
mentioned below:

20
 Scherrer formula:
d=0.9 λ/ (B cosθ)

Where:
d is the crystallite size,
λ is the wavelength of the X-radiation used,
B is the peak width at half the maximum intensity, and θ is the Bragg angle.
The particle size as a function of milling time is shown in Table-3.1 and
the curve is plotted and shown in Fig-3.3

Particle size Vs Milling time

400
P article size(A ngstrom )

350
300
250
200
150
100
50
0
0 5 10 15 20 25 30
Milling Time(hrs)
Fig-3.3: Particle size as a function of milling time.

21
RESULTS AND DISCUSSION
 RESULTS AND DISCUSSION

XRD analysis shows a compound formation between Al,Fe,Si the exact compound is
to be conformed .V.C. Srivastava, P. Ghosal, S.N. Ojha .has found compound
between these element as Al4Si2Fe and Al5SiFe using energy dispersive Xray
analysis.The plot between particle size Vs milling time Fig- 3.3 reveals that particle
has become finer with the increase in milling time.The milling has been carried out
for 25 hrs and results are presented.Out of the mechanically alloyed powder mixture ,
green pellets of 10 & 15 mm dia.and 12mm height,by applying pressure of 6.5 tons
using hydraulic machine.Then they were sintered at 450oC for ½ hr.
Additionally another set of experiment was planned which is as given below. Powder
mixture of same composition was made using mixing machine resulting in ordinary
mixing.This powder mixture was used for making green pellets followed by sintering
adopting the schedule as mentioned in Table No.4.1

Table-4.1

SlNo. Sintering Pressure(T)

temperature(oC) ( X2 )
(X1)

1 400 5

2 500 5
3 400 8

4 500 8

5 450 6.5

22
After green pellets were sintered one batch was tested in INSTRON 1195 for
compressive strength where as the other batch was used for revealing the
microstructure by optical microscopy. The compression strengths of the
samples are tabulated along with the schedule of experiment and shown in
Table-4.2

Table- 4.2
SlNo. Sintering Compaction Compressive
temperature(oC) Pressure(Tons) strength(MPa)
( X1) (X2)

1 400 5 125.4

2 500 5 146

3 450 6.5 183.3

4 400 8 171.9

5 500 8 198.4

A regression equation was formulated by using the method of statistical

design of experiments.
Compressive strength (MPa):160.425+11.77X1 +24.725X2 +1.475X1X2
Where, X1 is the symbol assigned for sintering temperature and X2 for
compaction pressure.
The coefficients of X1and X2 have large positive values indicating that both
temperature and pressure have large increasing influence ,though pressure has
got larger influence than temperature .The experiment carried out with 450oC
and 6.5 Ton compaction pressure resulted in a compressive strength of
183.3MPa which is quite close to the value of bo is 160.425 MPa .Thus this
equation is valid within the range of variables used.Table-4.3 shows a
comparison between the compressive strength of the samples prepared by
mixing machine and mechanical alloying.
23
 Table-4.3

SlNo. Type of Sintering Compaction Compressive

mixing/milling Temperature Pressure(T) Strength
(oC) (MPa)

Simple mixing 450 6.5 183.3

1.

Mechanical
2. Alloying 450 6.5 212.5

Mechanical
3.
Alloying 450 8 254.4

The compressive strength of the pellets made out of mechanically alloyed

powder (time of milling of 25hrs and the compaction pressure applied was
6.5T & sitering temperature 450oC temperature and time of sintering ½ an
hour) was found to be 212.5MPa. This value is higher than 183.3MPa
obtained for the powder made out of ordinary mixing this value is attributed to
the better bondage between the particles in mechanically alloyed sample
because of high reactivity resulted out of creation of large surface .
Another mechanically alloyed sample but with 8tons of compaction pressure
for same temperature 450oC mechanically alloyed but 8T of compaction
temperature shows a compressive strength of 254.4MPa this is attributed to
the more effective compaction and more effective bonding between particles.

24
 MICROSTRUCTURE

The SEM photographs of samples

a. Mixed by simple mixing.
b. Mechanically Alloyed (25 Hrs).
were taken after subjecting them to a compaction pressure of 6.5 Ton and a sintering
temperature of 450oC for ½ hr. are shown in Fig-4.1 and Fig4.2

Fig-4.1: (1000X)

25
 Fig-4.2: (3500X)

The microphotographs reveal the following features .In the ordinary mixed sample
(6.5 T and 450oC) there are large number of pores (Fig.4.1), where as in the
mechanically alloyed sample such pores are less in number (Fig.4.2).The size of the
particles in a mechanically alloyed sample are comparable at 3500X(Fig.4.2) with
those of ordinary mixed sample at 1000X(Fig.4.1).In addition grainboundaries can be
seen in some areas in mechanically alloyed sample (Fig.4.2) indicating that alloy
formation has occured where as in ordinary mixed samples this is absent.There are
some white phases presumably intermetallic compounds formed by Al-Fe-Si. in
mechanically alloyed sample. This is revealed by XRD data analysis. The exact
stoichometric formula of this intermetallic compound between Al-Fe-Si is yet to be
confirmed.

26
CONCLUSION
REFRENCES
 CONCLUSION

1. XRD shows a compound formation between Al, Fe, and Si.The exact
composition is to be conformed.
2. The particles have become finer as a function of milling time as revealed by
broadening of the XRD peaks.
3. Compaction pressure and sintering temperature has increasing influence,
though pressure has got larger influence than temperature as revealed by the
regression equation.

27
 REFRENCES

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formation in spray-deposited Al–18%Si–5%Fe–1.5%Cu alloy” Materials
Letters, volume56 (2002): page 797– 801.

3. Suryanarayana .C,”Mechanical Alloying and Milling” Progress in Materials

Science, volume 46 (2001):page1-184.

4. Zhang .D.L, Ying .D.Y,” Solid state reactions in nanometer scaled diffusion
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5. Wang. C.X, Yang G.W,” Thermodynamics of metastable phases

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7. Madaah Hosseini H.R, Bahrami.A” Preparation of nanocrystalline Fe–Si–Ni

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