Enrichment of Carbon in Mo Steel

by using Cast Iron and Graphite

Submitted in partial fulfillment of the requirements

of the degree of

Bachelor of Technology in Metallurgical Engineering

By

Ketan.M.Pande
MIS No: - 141211011

Pratik.M.Rekhate
MIS No: -111111045

Under The Guidance of

Dr. N.B.Dhokey

Prof. V.T.Thavale

Department of Metallurgy and Material Science

COLLEGE OF ENGINEERING PUNE

2014-2015

1
 CERTIFICATE

This is to certify that the thesis „Enrichment of carbon in Mo steel by using cast iron and
graphite‟ submitted by Ketan.M.Pande MIS No: - 141211011 and Pratik.M.Rekhate MIS
No: - 111111045 in the partial fulfillment of the requirements for the award of degree of
Bachelor of Technology in Metallurgical Engineering of College of Engineering Pune,
affiliated to the Savitribai Phule Pune University, is a record of their own work.

Signature Signature Signature

Prof. V.T.Thavle Dr. N.B.Dhokey Dr. S.T.Vagge

Guide Co-Guide Head of Department
Department of Metallurgy Department of Metallurgy, Department of Metallurgy,
and Material Science and Material Science and Material Science,
College of Engineering, College of Engineering, College of Engineering,
Pune. Pune. Pune.

Date:

Place: Pune

2
 Approval Sheet

This thesis

ENRICHMENT OF CARBON IN Mo STEEL BY USING CAST IRON

AND GRAPHITE
By

Ketan.M.Pande

MIS No: - 141211011

Pratik.M.Rekhate

MIS No: - 111111045

is approved for the degree of

Bachelor of Technology in Metallurgical Engineering

of

Department of Metallurgy and Material Science

College of Engineering Pune

(An autonomous institute of Govt. of Maharashtra)

Examiners Name Signature

1. External Examiner ________________________

2. Internal Examiner ________________________

3. Supervisor (s) ________________________

________________________

Date:

Place: Pune

3
 Declaration

We declare that this written submission represents our ideas in our own words and where
others' ideas or words have been included, we have adequately cited and referenced the
original sources. We also declare that we have adhered to all principles of academic honesty
and integrity and have not misrepresented or fabricated or falsified any idea/data/fact/source
in my submission. We understand that any violation of the above will be cause for
disciplinary action by the Institute and can also evoke penal action from the sources which
have thus not been properly cited or from whom proper permission has not been taken when
needed.

Signature Signature

Pratik.M.Rekate Ketan.M.Pande

111111045 141211011

Date:

Place: Pune

4
 ABSTRACT

Powder metallurgy is an emerging trend in manufacturing processes. Ferrous powders are

gaining wide application. Carbon is important alloying element chiefly governs the properties
of ferrous powder. Carbon is induced into ferrous powder through various sources and a
property varies with change of carbon source. Thus, it is the topic of study and proper
selection of source is essential. 0.3% C + 0.85% Mo steel powder was mixed with two
carbon sources. In one case graphite was used and in another case cast iron was used. Cast
iron showed more pearlite % after sintering than graphite powder. However there was
problem of increase in porosity associated with cast iron scrap powder.

5
6
 Table of contents

Chapter Title Page

no. no.
List of Figures I
List of Tables 7II
List of Abbreviations IV
1. Introduction
1.1 General introduction 1

1.2 Brief history 2

1.3 Challenges 2

1.4 Approach to present work 2

2. Literature review
2.1 Introduction 3

2.2 Graphite as carbon source 4

2.2.1 Effect of graphite as carbon source 5

2.3 Cast iron as a carbon source 8

2.3.1 Effect of cast iron 9

2.4 Factors Affecting The Process 11

2.4.1 Molybdenum as alloying element 11

2.4.2 Protective atmosphere during sintering 12

2.4.3 sintering temperature 12

2.4.4 Heat treatment 13

3. Summary of literature review 14

4. Experimental work
4.1 Objective 15

4.2 Flow chart 16

4.3 Raw material and equipment‟s 17

4.4 Procedure 17

5. Results and discussion

5.1 Results 20

5.1.1 Green density 21

7
 5.1.2 Sintered density 22
5.1.3 Hardness 23
5.1.4 Microstructure 24
5.1.5 Phase analysis 28
5.2 Comparison of results 30

6. Conclusion 34
7. Future Work 35

Appendices
Appendix I Estimation of Proportion of Powder during Mixing 36

Literature Cited 38
Acknowledgement 39

8
 List of Figures

Sr. no. Name Page no.

1. Fig. 2.1 Effect of carbon content and on mechanical 3
properties of steel
2. Fig. 2.2 Variation of microstructure of specimen from iron 6
powder containing (25% ash) graphite at various
temperature

3. Fig. 2.3 Fe-1.5% graphite-10% Kh30, sintered at 750 x200 7

at 1150°C.

4. Fig. 2.4 Variation of microstructure of specimen from iron 9

powder containing cast iron at various temperature

5. Fig. 2.5 Dependence of the shrinkage of materials 10

containing cast iron, and graphite on sintering temperature.

6. Fig. 2.6 Influence of molybdenum on iron 11

7. Fig. 4.1 Flowchart of experimental work 16

8. Fig. 4.2 Schematic sketch of atmosphere controlled tubular 18

sintering furnace
9. Fig. 5.1 Variation in green density with changing carbon 21
source and percentage carbon

10. Fig. 5.2 Variation in sintered density with changing carbon 22

source and percentage carbon
11. Fig. 5.3 Variation in hardness with changing carbon source 23
and percentage carbon

12. Fig. 5.4 Microstructure of Sample A containing pearlite 24

with proeutectoid ferrite. (a) at 100x (b) at 500x

13. Fig. 5.4 Microstructure of Sample B containing uniformly 25

distributed pearlite with fine proeutectoid ferrite (a) at
100x (b) at 500x

14. Fig. 5.5 Microstructure of Sample C containing pearlite 26

with very less Proeutectoid ferrite and porosity (a) at 100x
(b) at 500x
15. Fig. 5.5 Microstructure of Sample D containing Pearlite 27
with small islands of Proeutectoid ferrite with presence of

9
 high porosity (a) at 100x (b) at 500x

Sr. no. Name Page no.

16. Fig. 5.6 Phase analysis of sample A 28

17. Fig. 5.7 Phase analysis of sample B 28

18. Fig. 5.8 Phase analysis of sample C 29

19. Fig. 5.9 Phase analysis of Sample D 29

22. Fig. 5.10 Comparison between sintered density of graphite 30

and cast iron mixed sintered specimen

23. Fig. 5.11 Comparison between hardness of graphite and cast 31

iron mixed sintered specimen

24. Fig. 5.12 Comparison between amount of pearlite form in 32

graphite and cast iron mixed sintered specimen

25. Fig. 5.13 Comparison between percentage of porosity in 33

graphite and cast iron mixed sintered specimen

10
 List of Tables

Sr. no. Name Page no.

1. Table 5.1 Nomenclatures given to samples of different 20
composition
2. Table 5.2 Green density of samples 21
3. Table 5.3 Sintered density of samples 22
4. Table 5.4 Hardness of samples 23
5. Table 5.5 Phase analysis of Sample A 28
6. Table 5.6 Phase analysis of Sample B 28
7. Table 5.7 Phase analysis of Sample C 29
8. Table 5.8 Phase analysis of Sample D 29

11
 List of Abbreviation

Sr. no. Abbreviation Meaning

1. ρ Density of specimen, gm/cc
2. Weight in air, grams
3. Weight in fluid, grams
4. Density of fluid, gm/cc
5. Sample A 0.3% C + 0.85% Mo steel powder with graphite powder
addition, (total 0.5% C)
6. Sample B 0.3% C + 0.85% Mo steel powder with cast iron powder
addition, (total 0.5% C)
7. Sample C 0.3% C + 0.85% Mo Steel powder with graphite powder
addition, (total 0.7% C)
8. Sample D 0.3% C + 0.85% Mo steel powder with cast iron powder
addition, (total 0.7% C)
9. ( ) Percentage carbon in cast iron or graphite
10. ( ) Weight of cast iron or graphite powder in grams.
11. ( ) Percentage carbon in base metal powder
12. ( ) Weight of base metal powder powder in grams
13. ( ) Weight of carbon required in mixture in grams

12
 CHAPTER 1

Introduction

1.1 General introduction

Powder metallurgy has long been recognized as an effective technology for producing a
variety of parts to net or near-net shape. In the rapid developing industry, powder components
steels continue to gain wide use as prospective functional and structural materials for
examples Ferrite based powders are used for the production various automobile components
like bushings, self-lubricating bushings are produced and they require low porosity. Ferrite
based powder are also used as pole pieces of motor car alternator generators.
As with wrought steels, carbon is the most important alloy element also in sintered steels, and
most of the effects of carbon on the properties of wrought steels can also be transferred to
sintered steels. Thus, during production of Fe-based powder metallurgy components, its
carbon content is varied depending upon the type of component and its application and if
carbon percentage to be increase various carbon sources are used. Carbon has been
traditionally introduced into steels as fine admixed graphite powder, commonly those grades
being preferred that are highly soluble in the matrix. The dissolution kinetics of carbon in
sintered steels has been a matter of discussion; significant dissolution of graphite in Fe-C
compacts requires temperatures greater than 900°C even if very active graphite grades –
purified natural graphite or special grades of artificial graphite are used. Nevertheless,
introducing graphite through this route is a well-established technology.There is however
drawbacks linked to graphite admixing like low density of graphite than iron causing
segregation during sintering.
For the introduction of metallic alloy elements, ferrous powder metallurgy offers several
routes like diffusion bonding and prealloying, introducing carbon in ferrous material by using
cast iron powder or through carbide/masteralloy powder. Introducing carbon in ferrous
material by using cast iron powder containing cementite, diffusion during sintering can be
expected to be the faster process.

13
1.2 Brief history

By 1940s, iron based PM began its advance to commercial viability. PM emerged as a major
breakthrough in metal working technology by providing structural parts having superior
performance coupled with cost effectiveness of material conservation and longer operational
life. Since then there has been a steady increase in production of PM parts. In the more recent
years, more new and improved alloy compositions and production technologies are being
developed. In the last few decades, numbers of studies have been done kinetics of carbon
addition in ferrous material. A lot of research work related to use of graphite and cast iron to
enrich ferrous metal with carbon had been done by Soviet Union.

1.3 Challenges

Amount of uniform distribution and diffusivity of carbon during sintering of premix of ferrous
metal and carbon source powder controls properties of component and thus obtaining uniform
distribution by using best carbon source is a challenge i.e. a carbon source with good
diffusivity. Graphite has been widely used as a carbon source, but there are various problem
associated with it as mentioned in section 1.1 and also use of graphite powder increases the
overall production cost because of high cost of good quality graphite powder. So, use of
alternative carbon source is essential. Cast iron scrap powder can be looked down as a good
carbon source.

1.4 Approach to the present work:-

The present work is related to evaluate the properties of 0.3%C+ 0.85% Mo steel powder by
enriching it with carbon from via cast iron and graphite. The main aim of this project is to
study advantages of using cast iron scrap powder over graphite powder. Since, in many
industries cast iron scarp powder is obtained as waste material, so if it is used as carbon
source it will help in waste management.

14
 CHAPTER 2

Literature Review

2.1 Introduction

In general, as the carbon content increases the hardness of the powder component of steel also
increases, while the elongation decreases. On the other hand, the pearlite lamellar morphology
leads to undesirable cold working mechanical properties in highly stressed components, while
globular cementite morphology conduces to higher toughness, good cold workability and
machinability. In addition, it has been shown that carbon produces a small change in the
softening behavior at deformation temperatures above the non-recrystallization temperature.
The carbon content increases the self-diffusion coefficient of iron. The activation energy for
the self-diffusion of iron decreases with increasing carbon content. Therefore, it is expected
that the higher-carbon steels would have higher recovery rate.A. Calik[1] et al. showed effect
of carbon content and on mechanical properties on steel as follows

Fig 2.1. Effect of carbon content and on mechanical properties of steel[1]

Although pure iron is a weak material, steels have yield stress ranging from 200 to 2000 MPa.
The most distinctive aspect of strengthening of iron is the role of the interstitial solutes carbon
and nitrogen.The microhardness is not only a mechanical characteristic routinely measured,

15
but, in recent years, it has been developed because it has been established that it is sensitive to
structural parameters as well as to mechanical behavior (yield stress, modulus of elasticity,
some secondary relaxation transitions, etc.) micro-hardness changes linearly with the carbon
content and there is a considerable increase in hardness with increasing carbon content. These
elements also play a vital part in interacting with dislocations and in combining preferentially
with some of the metallic alloying elements used in steels.

A powder metallurgical product made from steel have very wide application, during
production of steel components by powder metallurgy, carbons is increase according to the
requirement or application and is very commonly done in industries. Carbon enrichment in
steel powders is generally done by using rich carbon sources like graphite and cast iron
powder. The effect of carbon addition using different sources has different effects on the
properties of steel and also on the dimensions of the component. Use of cast iron and graphite
powder on the properties of the component is described in detail in following sections.

2.2 Graphite powder as carbon source:-

R. Z. Vlasyuk[2] et al., showed impregnation of the iron with the carbon of the graphite in
steels occurs through the following mechanism. At temperatures above the α-γ phase
transformation point the carbon of the graphite forms a solid solution with the γ-iron. Here it
is assumed that direct chemical reaction at the points of contact between the iron powder and
graphite particles results in the formation of cementite. The graphite dissolution process may
be divided into two stages:

1. Passage of carbon atoms through contacts formed during pressing.

2. Passage through contacts formed in the course of sintering as a result of iron self-diffusion.

Among the factors playing an important part in the formation of the microstructure of these
materials, the following are mentioned most often: oxidation of the iron powder, presence of
impurities in the graphite, compact porosity, particle size of the iron powder, and uneven
impregnation of the austenite with carbon.
16
Thus, control over the structure formation process involves regulating the size of the
iron/carbon contact surface. The structure formation process is strongly affected by cooling
rate, whose regulation can be employed as a means of inhibiting graphitization or lowering the
amount of cementite in the structure. The appearance of coarse cementite inclusions among
ferritic grains is regarded as a specific abnormality of the structure of carbon steels produced
by the powder metallurgy techniques.Microstructure formation in iron-graphite materials is
influenced by the type of graphite used

2.2.1 Effect of graphite as a source:

R. Z. Vlasyuk[2] et al. showed that a fine reduced iron powder of 98.0% minimum purity and
2.2- to 2.5-g/cm2 apparent density pressed into specimens of 10-11% porosity, which were
then heated in a high-temperature.During heating to 900°C no significant changes (except
growth of crystalline iron grains) were detected in iron-graphite compacts with graphite (25%
ash). At 950°C, droplets of a liquid began to appear on the surface of a graphite particle
chosen for examination. Heating to1000°C increased the amount of the liquid to such an
extent that it increased the area occupied by the graphite particle, raising the temperature to
1100°C produced no further change in the shape and size of the graphite particle investigated.
The specimen was held at 1100°C for 30 min and then cooled at an average rate of 30⁰C/min.
After cooling, the part of the specimen observed during heating was first examined in a
scanning electron microscope and then etched in order to enable its microstructure tobe
studied. Examination in the scanning microscope revealed that at the site where graphite
particles had been embedded there was a pit with partially melted edges, on the bottom of
which could be seen the remains of undissolved graphite (Fig. 2).

17
Fig.2.2 Variation of microstructure of specimen from iron powder containing (25% ash)
graphite, x300: a) 1000°C; b) 1050°C;c) after cooling; d) remains of undissolved graphite
(scanning electron microscope, x500) [2].

The appearance of a liquid phase during the sintering of iron-graphite materials is in accord
with the constitution diagram of the iron-carbon system, from which it follows that at a carbon
concentration in iron of up to 4.3% a liquid phase forms at a temperature of 1130°C. It is at
temperatures of this order that the appearance of a liquid phase is observed in specimens with
low-ash grades of graphite. It would appear that during diffusion, iron zones adjacent to
graphite can pick up 4.3% of carbon and then, after the required temperature has been
reached, pass into the liquid state. The increase in the area originally occupied by a graphite
particle is evidence for the formation, around this particle, of a eutectic which fills pores in its
vicinity. In specimens with high-ash graphite‟s a liquid phase appears at a lower temperature
because the oxides present in the ash depress the eutectic point. The amount of free carbon
(i.e., undissolved graphite) in specimens with high ash graphite was several times greater than
that in specimens with low ash graphite. The poor solubility of high ash graphite was due to
partial melting of the iron surrounding the graphite particles. After passing into the liquid
state, the iron migrated under the action of capillary forces into pores, thereby decreasing the
iron/graphitecontact area and hindering carbon diffusion into the iron.

[3]
Xiaoxun Zhang et al. conducted an experimental investigation to study the effects of
graphite content and temperature on the microstructure and mechanical properties of iron-
based powder metallurgy parts which showed that with the sintering temperature increasing,
18
the microstructures of the sintered interface become uniform. The higher the sintering
temperature, the greater the coefficient of the atomic diffusion within the particles, and the
faster the sintering carried out and with the graphite content increasing, the hardness of the
iron-based powder sintered parts grows obviously.

A. M. Petrova[4] et al. studied Specimens of iron-chromium steel (Kh30) mixed with graphite
(20 mm in diameter and 10-mm height), with a porosity of 18-22%, were obtained by
hydraulic pressing in closed dies when subjected to sintering shrank at all temperatures. The
amount of shrinkage varied from 0.1 to 0.8% at temperatures from 750-1250°C the
microstructure consist of Graphite distributed in the iron matrix in the form of isolated
inclusions, or chains along iron particles and Kh30 inclusions.Graphite envelopes the Kh30
chromium-rich inclusions and prevents their oxidation during sintering, which eliminates
specimen growth, stabilizes shrinkage, and provides increased strength.

Fig.2.3 Fe-1.5% graphite-10% Kh30, sintered at 750 x200 at 1150°C. [4]

Herbert Danninger[5] et al. showed that there are however two drawbacks linked to graphite
admixing: on one hand, the fine graphite flakes, with a density much lower than that of the
base powder – 2.26 g.cm3 compared to 7.86 g.cm3 for iron – tend to segregate during mixing
and handling; the “dusting” effect caused by admixed graphite is well visible when pouring
Fe-C powder mixes from a container, indicated by the black cloud arising. This problem is the
more pronounced with higher carbon content.

19
2.3 Cast iron powder as a carbon source:-

Another method of introducing carbon into iron powder is to add cast iron powder, which
helps stabilize the structure of steel sintered at 1100-1150°C. According to R. Z. Vlasyuk[2] et
al., the mode of dissolution of a particle of white cast iron (The carbon content of the cast iron
was 3.3%) in iron (98.0% minimum purity and 2.2- to 2.5-g/cm 2 apparent density) proved to
be slightly different. Marked changes in the microstructure of the cast iron were observed at
temperaturesof 850-870°C, when a ledeburitic structure became replaced by granular pearlite
with coarser cementite inclusions (Fig 4 b). At a temperature of 1000°C separate cementite
inclusions were found only at boundaries of large austenitic grains (Fig 4c). No liquid phase
formation was observed during the whole heating operation, right up to 1150°C, due to the
low carburizing potential of the cast iron particles, and the particle shape remained essentially
unchanged. In order to determine the boundaries of zones impregnated with carbon at the
highest test temperature, a heated specimen was cooled at an average rate of 80 °C/min and
then subjected to metallographic examination. The location of a cast iron particle presented no
special difficulties thanks to the presence of round-shaped pores which had formed around its
periphery (Fig.4 e). Within this contour the microstructure consisted of ferrite and granular
pearlite. Outside the contour, as in the iron-graphite materials, the pearlite was unevenly
distributed. It should be pointed out that at the highest test temperature a tendency was
observed for the pearlitic zones to arrange themselves along the boundaries of the austenitic
grains.

20
Fig. 2.4. Variation of microstructure of specimen from iron powder containing cast iron,
×300: a) 20°C; b) 850°C; c) 1000°C;d) 1100°C; e) after cooling, ×500 (the dotted lines show
the boundaries of an austenitic grain).[2]

2.3.1 Effect of cast iron:-

Use of cast iron as carbon source is a topic of research and is relatively untouched.

A. M. Petrova[4] et al. studied Specimens of iron-chromium steel(Kh30) mixed with cast iron
(20 mm in diameter and 10-mm height), with a porosity of 18-22%, were obtained by
hydraulic pressing in closed dies when subjected to sintering. The volume of specimens from
the charge with cast iron increased at temperatures up to 1200°C shrinkage was observed at a
higher temperature.

Fig. 2.5 Dependence of the shrinkage of materials containing (1) Cast iron, and (2) Graphite
on sintering temperature.[4]

In the material containing cast iron, large inclusions of Kh30 were retained in the matrix after
sintering at 1150-1250°C. Some of these partially dissolved, with the formation of narrow
bands of chromium-alloyed pearlite possessing a micro-hardness of 3.2 GPa. Others retained
sharply defined boundaries, and exhibited an oxide film of FeCr204 containing 26-28 wt. %
O, 15-16% Fe, and 54-55% Cr. The oxide film is a barrier to the diffusion of chromium and
carbon from the inclusion into the matrix. This oxide film did not form in the specimens
containing graphite, which is explained by a high carbon concentration at the surface of the
Kh30 particles.Redistribution of carbon was activated at higher sintering temperatures.

21
Thus, maximum growth of the cast-iron containing specimens was observed at low sintering
temperatures, at which no appreciable solution of cast iron into Kh30 inclusions occurred.
Less growth occurred at higher temperatures, where the diffusion of carbon and chromium in
the matrix is more rapid. Diffusional processes in the material, therefore, are not responsible
for specimen growth, but rather the thermally activated relaxation of elastic stresses
introduced when charges containing a large amount of hard and rigid cast iron are
pressed.Thus, the instability of volume change in iron-chromium material containing cast iron
is explained by the formation of FeCr204 around inclusions of Kh30, and depends upon the
amount of oxidizing agent in the sintering atmosphere.

2.4 Factors affecting process:

2.4.1 Molybdenum as an alloying element

Properties of molybdenum and its effects in ferrous metal should be studied so that it will
help in establishing parameters of sintering. Molybdenum is widely used as an alloying
element in steels. Höganäs[6] showed that Molybdenum increases hardenability, tensile
strength, and compressibility of steels. Popular alloys of Mo-steel are astaloy and
destaloy.The hardness of the masteralloy powders is significantly increased by introduction of
carbon, but this increase of hardness – which of course means a drop of compactibility.
Alloying with carbide-forming elements such as Mo tends to increase the hardness further –
up to almost 480 HV. Muhammad Nabeel[7] studied effect of molybdenum on hardness of
iron is as follows

22
 Fig. 2.6 Influence of molybdenum on iron [7]

Addition of Cu, C and Mo results in increased dimensions during sintering, increased level
of Mo and C gives reduced impact energy of PM steels.

M. Kiniger et al. [8] concluded that temperature for the formation of α-Mo2C is between 700
and 900 ◦C depending on the oxygen content. Thereby a higher content of oxygen resulted in
a higher temperature of formation because the oxygen partly occupied the interstitial sites.
Thus formation of molybdenum carbide increases hardness of sintered compact.

2.4.2 Protective atmosphere during sintering:

Protective atmosphere has to be used in the sintering furnace to fulfill several important
requirements. The main purpose of the sintering atmosphere is to prevent oxidation and to
reduce possibly present oxides. There are several options available for sintering atmosphere
including H2, cracked ammonia and nitrogen. Among the above mentioned atmospheres, H2
and cracked ammonia are reducing atmospheres and have decarburizing effect, nitrogen is a
neutral atmosphere. Most commonly endothermic gas, which is produced through combustion
of hydrocarbons, is used as protective atmosphere.

Herbert Danninger et al. [5] carried out sintering with protecting gas atmosphere. During this
for studying the carbon dissolution in premix of masteralloy(Mo-steel alloy) and iron,
interrupted dilatometric runs were done in flowing N2-10% H2 using a pushrod to get
optimum result. Specimens prepared were far from optimized i.e. considerable further
potential can be expected here, in particular when combining high green density with intense
sintering.
23
2.4.3 Sintering temperature

Temperature plays an important role during sintering and overall properties and structure of
sintered compact depends on sintering temperature. During sintering increasing temperature
reduces sintering time.

[2]
R. Z. Vlasyuk et al. concluded that during sintering to 900°C no significant changes
(except growth of crystalline iron grains) were detected in iron-graphite compacts. At 950°C
liquid phase is formed and liquid phase increases upto 1100°C after that further change are not
seen and also in case of carbon added via white cast iron powder to an iron powder causes
stabilization of the structure of steel by sintering at 1100-1150°C.

[4]
A. M. Petrova et al studied specimens of iron-chromium steel. The materials after
sintering contained like concentrations of chromium, carbon, and oxygen. As already
discussed, the volume of specimens from the charge with cast iron increased at temperatures
up to 1200 shrinkage was observed at a higher temperature.

2.4.4 Heat treatment cycles

[9]
Herbert Danninger et al. showed steels with carbon contents between 0.2 and 0.5 mass%
can be effectively hardened by oil or gas quenching, and regular martensitic microstructures
are attained also after gas quenching. The quench hardness depends on carbon level, total
porosity, and high temperature sintering. Tempering is recommended either in the range
<200°C, for high hardness, or at 500-650°C for optimum strength toughness. Evidently for
both carbon levels the highest hardness is attained after quenching from 900°C, although of
course the hardness differs considerably. Even at 0.2%C quenching from 850°C results in
reasonable hardness, indicating that the material has been fully austenitic.

24
 Chapter 3
Summary of Literature Review

During literature review various theories and articles were studied and summary of all the
articles is comprised in following points:

 The dissolution of graphite in iron may take place with the formation of a liquid phase; the
temperature at which this phase appears is determined by the amount of ash impurities in the
graphite.
 As the ash content increases in graphite, liquid phase during sintering increases because oxide
content in ash reduces eutectic point.
 However, graphite causes problems like segregation.
 With specimens containing cast iron, after sintering at a temperature of 1060°C (pure solid-
phase sintering) a linear relationship between strength and density is seen. Using cast iron
powder as s carbon source has a promising approach towards achieving high strength
 During sintering of Fe-Cr alloy mixed with cast iron. Oxide film is formed over the surface of
Fe particle, preventing diffusion of carbon and chromium in Fe. Thus, carbon concentration
occurs over the oxide scale.
 In case of super alloys, Individual addition of Mo to Fe-Ni system also has a negative effect
on uniformity of Ni. However, the results showed that the Ni distribution was improved by
Mo when added to Fe-Ni-C. The phenomenon is attributed to decrease in chemical potential
of carbon due to Mo addition
 Sintered steels prepared from Cr-Mo prealloy powder, Astaloy and containing 0.2…0.5%C
can be effectively hardened both by oil and gas quenching.

25
 Chapter 4

Experimental work

4.1 Objectives

Based on literature review following objectives were decided to be taken into consideration
during experimental work

a) To study microstructural changes in 0.3% C+0.85% Mo steel using cast iron scrap powder
and graphite powder.

b) To study difference between properties obtain in 0.3% C+ 0.85%Mo steel by using graphite
and cast iron scrap powder and advantages of cast iron scrap powder over graphite powder.

c) To study effect of carbon % on properties of 0.3% C + 0.85% Mo steel.

4.2 Flow chart

26
 0.3%C+0.85% Mo

Steel Powder

Graphite powder Graphite powder Cast iron Powder Cast iron powder
for 0.5%C for 0.7%C for 0.5%C of 0.7%C
Enrichment Enrichment Enrichment Enrichment

1 2 3 4

Ball Milling, Ball to Ball Milling, Ball to

powder Ratio 10:1 powder Ratio 10:1

Conventional Conventional
compacting 600MPa compacting 600MPa

Sintering at 1120⁰c Sintering at 1120⁰c

with 100% N2 with 100% N2
(By volume) (By Volume)

Step cooling: Step cooling:

1) Furnace cool upto 1) Furnace cool upto
900⁰C 900⁰C
2) After 900⁰C air cool 2) After 900⁰C air cool

1 2 3 4
Material Characterization

Hardness Microstructure Density Phase Analysis

Note: 1,2,3,4 are four different routes.

Fig. 4.1 Flowchart of experimental work

27
4.3 Raw material

a) Cast iron scraps powder:

Chemical composition: C-1.41%, Si-0.793%, Mn-0.32%, S-0.04%, O2-3.206%,

N2-0.0227%, H2-0.580, rest Fe.

b) Graphite:

Chemical composition: C-98%, ash- 2%.

c) 0.3% C, 0.85% Mo steel powder:

Chemical composition: C- 0.3%, Mo-0.85%, rest Fe

4.2 Procedure

a) Mixing

First chemical analysis of both carbon sources was done to identify the chemical
composition. Depending upon the carbon % in both carbon sources equation mention in
appendix I was used to determine the weight proportion of carbon source powder and base
metal powder which will be used during mixing. Accordingly four different compositions of
20 grams each were produced which are as follows:

I) 0.3% C + 0.85% Mo steel powder with graphite powder addition, (total 0.5% C).

II) 0.3% C + 0.85% Mo steel powder with cast iron powder addition, (total 0.5% C).

III) 0.3% C + 0.85% Mo Steel powder with graphite powder addition, (total 0.7% C).

IV) 0.3% C + 0.85% Mo steel powder with cast iron powder addition, (total 0.7% C).

The powders were Ball milled for 2 hours. Stainless steel balls (SS 304) were used for ball
milling with BPR (Ball to powder ratio) 10:1.

28
b) Cold compaction

After mixing, three samples from each composition were cold compacted at room temperature
to. Pressure applied during cold compaction was 600 Mpa. Weight of mixed powder taken
during compaction was 6.10 grams for producing a cylindrical sample of Dia.10 x Height 10.
Cold compaction was done on Hydraulic press of Kejetherm Co. with maximum pressure of
50 tonne.

c) Sintering

After cold compaction, sintering was done at 1120°C with an inert atmosphere of N2of 100%
by volume. Typical cycle of sintering is as follows:

I) Heating at the rate of 5°C/min. upto 1120°C.

II) At 1120°C, specimens were hold for 30 minutes.

II) Step cooling was done, upto 900°C samples were cooled in furnace. Once 900°C was
achieved samples were taken out of the furnace and were subjected to air cooling.

Sintering was carried out in MoSi2 tubular furnace of Therelek Co. with maximum
temperature of 1600°C.

Specimen

Gas outlet

Gas inlet

Ceramic Boat

Heating Zone

Fig. 4.2 Schematic sketch of atmosphere controlled tubular sintering furnace

29
d) Material characterization

Finally, the samples were tested for hardness, microstructure, density, porosity, phase
analysis. The procedures involved in various testing methods are as follows:

I. Hardness test:
Hardness test was conducted on Rockwell hardness tester. F scale was used for
hardness test. In F scale measurement, a 1/16” ball indenter was used with major load
of 60 kg. For Rockwell hardness test samples were cut from middle and new surfaces
form, were made smooth and flat to take hardness.
II. Density measurement:
Both green and sintered density was measured with the help of Archimedes Principle.
Weights of sample was taken in air and then in water then the values were put in
following formulae to measure density:

( )

III. Microstructure analysis:

i. For microstructural analysis sample were cut from middle and surfaces were made flat
on grinding belt.
ii. After flattening of surfaces the samples were polished on emery papers of number 180,
400, 600, 800, 1000, 1500 followed by lapping on velvet cloth soaked in water. No
abrasive like alumina were used during lapping because it causes alumina pickup in
pores of powder metallurgy specimen. Lapping was done until mirror surface polish is
achieved.Continuous flow of water maintained during lapping.
iii. Once sample was done with lapping, etching was done by using Nital (2% nitric acid,
98% ethyl alcohol). Microstructure was revealed under optical microscope.

IV.Phase analysis:
For phase analysis Dixel image analysis software was used which differentiate phases
from each other on the basis of colour of phase and porosity was also measured. It gives
output in percentage.

30
 Chapter 5
Results and Discussion

5.1 Results

Results Obtained after material characterization are presented in tabular as well as statistical
form. From every composition three samples were made to get accurate results. Following
nomenclatures are given to specimen to help easy display of results:

Table5.1 Nomenclatures given to samples of different composition

Sr. Nomenclature Base material Carbon source Total carbon

no. after mixing
(%)
1. Sample A 0.3%C+0.85%Mo Graphite 0.5%
steel powder powder
2. Sample B 0.3%C+0.85%Mo Cast iron 0.5%
steel powder powder
3. Sample C 0.3%C+0.85%Mo Graphite 0.7%
steel powder powder
4. Sample D 0.3%C+0.85%Mo Cast iron 0.7%
steel powder powder

31
5.1.1 Green density:

Table 5.2 Green density of samples

Sr. no. Sample A Sample B Sample C Sample D

(gm/cc) (gm.cc) (gm/cc) (gm/cc)
1 6.89 6.54 6.91 6.2
2 6.86 6.57 6.98 6.24
3 6.85 6.58 6.94 6.23
Avg.
green 6.86 6.56 6.94 6.22
density

7.2
7
Green density gm/cc

6.8
6.6 sample no.1
6.4 sample no2
6.2 sample no.3
6
5.8
Sample Sample Sample Sample
A B C D

Fig. 5.1 Variation in green density with changing carbon source and percentage carbon

32
5.1.2 Sintered density:

Table 5.3 Sintered density of samples

Sr. no. Sample A Sample B Sample C Sample D

(gm/cc) (gm/cc) (gm/cc) (gm/cc)
1 7.35 6.91 7.36 6.52
2 7.30 6.99 7.36 6.57
3 7.34 6.98 7.37 6.53
Avg.
sintered 7.33 6.96 7.36 6.54
density

7.6
7.4
Sintered density, gm/cc

7.2
7
sample no.1
6.8
sample no2
6.6
sample no.3
6.4
6.2
6
Sample Sample Sample Sample
A B C D

Fig. 5.2 Variation in sintered density with changing carbon source and percentage carbon

33
5.1.3 Hardness:

Table 5.4 Hardness of samples

Sr. no. Sample A Sample B Sample C Sample D

(HRF) (HRF) (HRF) (HRF)
1 93,88,89 77,77,74 95,97,98 80,81,81
2 91,94,92 75,74,75 99,95,96 79,80,81
3 93,92,92 77,78,78 97,97,96 76,78,76
Avg. 91.33 76.06 96.6 79.06
Hardness

120

100

80
Hardness, HRF

sample no.1
60
sample no.2
40 sample no.3

20

0
Sample Sample Sample Sample
A B C D

Fig. 5.3 Variation in hardness with changing carbon source and percentage carbon

34
5.1.4 Microstructure:

a) Sample A

Ferrite (white region)

Pearlite (lamellar region)

(a)

Ferrite (white region)

Pearlite (lamellar region)

(b)

Fig. 5.4 Microstructure of Sample A containing pearlite with proeutectioid ferrite. (a) at 100x
(b) at 500x

35
b) Sample B

Ferrite (white region)

Pearlite (lamellar region)

(a)

Ferrite (white region)

Pearlite (lamellar region)

(b)

Fig. 5.4 Microstructure of Sample B containing uniformly distributed pearlite with fine
proeutectoid ferrite (a) at 100x (b) at 500x

36
c) Sample C

Ferrite (white region)

Pearlite (lamellar region)

(a)

Ferrite (white region)

Pearlite (lamellar region)

(b)

Fig. 5.5 Microstructure of Sample C containing pearlite with very less Proeutectoid ferrite and
porosity (a) at 100x (b) at 500x

37
d) Sample D

Ferrite (white region)

Pearlite (lamellar region)

(a)

Ferrite (white region)

Pearlite (lamellar region)

(b)

Fig. 5.5 Microstructure of Sample D containing Pearlite with small islands of Proeutectoid
ferrite with presence of high porosity (a) at 100x (b) at 500x

38
5.1.5 Phase analysis:

a) Sample A

Table 5.5 Phase analysis of

Pearlite Sample A
Phase Percentage
(%)
Ferrite Porosity 5.34%

Pearlite 53.16%
Porosity Ferrite 41.50%

Fig. 5.6 Phase analysis of sample A

b) Sample B
Table 5.6 Phase analysis of
Pearlite Sample B

Phase Percentage
(%)
Ferrite
Porosity 7.59%

Pearlite 61.70%
Porosity Ferrite 31.81%

Fig. 5.7 Phase analysis of sample B

39
c) Sample C:
Table 5.7 Phase analysis of
Sample C

Pearlite Phase Percentage (%)

Porosity 2.71%
Ferrite
Pearlite 79.48%

Ferrite 17.81%
Porosity

Fig. 5.8 Phase analysis of sample C

d) Sample D:

Table 5.8 Phase analysis of

Pearlite Sample D

Phase Percentage
(%)
Ferrite
Porosity 10.21%

Porosity Pearlite 81.20%

Ferrite 8.59%

Fig. 5.9 Phase analysis of Sample D

40
5.2 Comparison of results:

a) As percentage carbon increases, the sintered density of 0.3%C + 0.85% Mo steel

powder mixed with graphite powder increases. While that mixed with cast iron powder
decreases.

7.6

7.4

7.2

7
Sintered density,

6.8
gm/cc

with graphite
6.6 with cast iron

6.4

6.2

6
0.5% C 0.7% C
Carbon, wt. %

Fig. 5.10 Comparison between sintered density of graphite and cast iron mixed
sintered specimen

41
b) As percentage carbon increases, the sintered density of 0.3% C + 0.85% Mo steel
powder mixed with graphite powder and that mixed with cast iron powder shows very
little increment.

120

100

Hardness, HRF 80

60
with graphite
with cast iron
40

20

0
0.5% C 0.7% C
Carbon, wt. %

Fig. 5.11 Comparison between hardness of graphite and cast iron mixed sintered
specimen

42
c) 0.3%C + 0.85% Mo steel powder mixed with cast iron powder shows more amount of
pearlite formation at all carbon % level than that of powder mixed with graphite
powder.

90

80

70

60
Pearlite, wt. %

50

40 with graphite
with cast iron
30

20

10

0
0.5% C 0.7% C
Carbon, wt. %

Fig. 5.12 Comparison between amount of pearlite form in graphite and cast iron
mixed sintered specimen

43
d) Porosity % increase with increasing amount of cast iron powder in 0.3%C + 0.85%
Mo steel powder. While it decreases with increasing amount of graphite powder in it.

12

10

8
Porosity, wt. %

6
with graphite
with cast iron
4

0
0.5% C 0.7% C
Carbon, wt. %

Fig. 5.13 Comparison between percentage of porosity in graphite and cast iron
mixed sintered specimen

44
 Chapter 6

Conclusion

In the present work, carbon percentage in 0.3% C+0.85% Mo steel was increase to 0.5% C and
0.7% C by using two carbon source a) graphite powder b) Cast iron scrap powder, to study
effect of cast iron as carbon source. This was achieved by using by mixing in ball mill. After
mixing, cold compaction was done then sintering in controlled atmosphere was carried out.
After analysis, following conclusion were made.

a) Cast iron scarp powder is more effective than graphite powder as a carbon source as
more amount of percentage pearlite has formed which proves that carbon has diffused
more uniformly and rapidly. However, due to presence of high amount of oxygen about
3.206% causes increase in porosity causing reduction in hardness and density. During
sintering this oxygen reacts with carbon to form CO gas causing formation of porosity.

b) With increase in cast iron proportion, both sintered as well as green density reduces
because of increasing oxygen content in mix. While graphite enrich alloy shows increase
in density because with increasing graphite, more liquid phase sintering occurs. Thus
pores get filled easily.

c) Hardness of alloy in graphite as carbon source shows more hardness at carbon

percentage level because it has less amount of porosity. However, if porosity of alloy
enriched with cast iron is reduced than there are chances of increase in hardness.

45
 Chapter 7
Future scope

As a part of continuous development, cast iron scrap powder can looked as an effective
alternative carbon source to compete with the graphite; the following line of action is suggested
for future work.

a. Using cast iron powder with negligible oxygen content.

b. Cast iron scrap powder can be treated before using to remove oxygen. To remove oxygen
cast irons crap powder can be subjected to hydrogen gas with nitrogen as carrier gas at
1100°C. So that oxygen present in powder can be removed.

46
 Appendix I

Estimation of Proportion of Powder during Mixing

Equation used for estimation proportion of powder during mixing:

[ ( ) × ( )] + ( ) ( ) = ( )

1) A 20 gram powder mixture was made using 0.3%C + 0.85% Mo powder with 0.3% carbon
and cast iron powder with 1.41% carbon. Therefore the proportion of powders required to
obtained 0.7%C in final mixture was calculated by using above equation

Solution:

I) By using equation proposed equation

[ ( ) × ( )] + ( ) ( ) = ( )

II) Let,
( = yThen, (
) ) = 20-y
Also 0.7% of 20 gm. is 0.14 gm
III) Substituting values in equation

[ × ]+ ( ) =0.14

0.0141y + 0.06 – 0.003y = 0.14

0.0111y = 0.08, y = 7.21 Grams

Therefore, weight of cast iron scrap powder is7.21 Grams and that of 0.3% + 0.85% Mo steel
powder is 12.79Grams.

2) Similarly weight proportion for getting 0.5% C in final mixture of cast iron scrap powder
and base metal powder of 20 grams was calculated and the weight proportion was obtained as
follows:
Cast iron scarp powder: 3.60 grams, 0.3% + 0.85% Mo steel powder: 16.39 Grams

3) Same equation was used to find out weight proportion of graphite powder and base metal
powder for 20 grams and the weight proportion was obtained as follows:
For 0.7% C in final mixture:
a) Graphite powder: 0.082 grams b) 0.3% + 0.85% Mo steel powder: 19.91 grams

47
For 0.5% C in final mixture:
a) Graphite powder: 0.0402 grams b) 0.3% + 0.85% Mo steel powder: 19.95 grams

48
 Literature cited
1) Adnan Calik et al (2009), Effect of Carbon Content on the Mechanical Properties of
Medium Carbon Steels, Department of Mechanical Education, Technical Education
Faculty, Suleyman Demire University,Isparta, Turkey. Z. Naturforsch. 65a, pp. 468 – 472
2) R.Z. Vlasyuk 1977, Characteristics of Graphite and Cast iron particle dissolution in Iron
during Sintering, Institute of Materials Science, Academy of Sciences of the Ukrainian.
Poroshkovaya Metallurgiya, No. 10(178), pp. 15-21,
3) Xiaoxun Zhang et al. (2012, Effects of Graphite Content and Temperature on
Microstructure and Mechanical Properties of Iron-Based Powder Metallurgy Parts,
Shanghai 201620, China. Journal of Materials Science Research; Vol. 1, No. 4; 2012
4) A.M.Petrova et al. (1998), effect of carbon on volume changes during the sintering of an
iron-chromium material, Ukrainian Academy of Sciences. Powder Metallurgy and Metal
Ceramics, Vol. 37, Nos. 5-6, 1998
5) Herbert Danninger et al. (2011), Iron-carbon masteralloy – a promising approach for
introducing carbon into high density sintered steels, Vienna University of Technology,
Austria
6) Höganäs PM-school, sintered iron-based materials, Höganäs iron powder information PM
95-2 (1995).
7) Muhammad Nabeel,(2011), Diffusion of Elemental Additives during Sintering, Royal
Institute of Technology SE-100 44 StockholmSweden.
8) M. Kiniger et al. (2008), Carbide formation upon heat treatment of molybdenum layers
deposited on carbon substrates: comparison of experimental data with a cellular
automaton model,Surf. Interface Anal. 2008;40: 786–789
9) Herbert Danninger,(2001), Heat Treatment of Cr-Mo Sintered Steels Based on Astaloy
Crm, Technische Universität Wien, Vienna, Austria.

49
 ACKNOWLEDGEMENT

It is our privilege to express our sincerest regards to our project guide, Prof. V.T.Thavle and Co-
guide Dr. N.B.Dhokey for their valuable inputs, able guidance encouragement, whole-hearted
cooperation and constructive criticism throughout the duration of our project.

We deeply express our sincere thanks to our Head of Department Prof. Dr. S.T.Vagge for
encouraging and allowing us to present the project on the topic “Enrichment of carbon in
0.3%C-0.85%Mo Steel by using cast iron and graphite” at our department premises for
project.

We take this opportunity to thank all our lecturers who have directly or indirectly helped our
project. Last but not the least we express our thanks to our friends for their cooperation and
support.

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