High Car Boony

The University of New South Wales
Faculty of Science
School of Materials Science and Engineering
Strain Ageing Of Low Carbon Steel

Wire Rods
A Thesis in
Materials Science and Engineering
By
Sujatha Mehta
Submitted in Partial Fulfilment

of the requirements for the Degree of
DOCTOR OF PHILOSOPHY
FEBRUARY 2003
CERTIFICATE OF ORIGINALITY
I hereby declare that this submission is my own work and to the best of my
knowledge it contains no materials previously published or written by another
person, nor any material which to a substantial extent has been accepted for the
award of any degree or diploma at UNSW or any other educational institution,
except where due acknowledgement is made in the thesis. Any contribution made
to the research by others, with whom I have worked at UNSW or elsewhere, is
acknowledged in the thesis.
I also declare that the intellectual content of this thesis is the product of my own
work, except to the extent that assistance from others in the project's design and
conception or in style, presentation and linguistic expression is acknowledged.
Signed-----
11
To my parents, husband Arun and lovely daughters, Shreya and Srishti
iii
ACKNOWLEDGEMENTS
I wish to express my deepest sense of gratitude and appreciation to my supervisor Dr.
Peter Krauklis, for his continuous support and encouragement throughout my research. I
also wish to express my gratitude to Associate Professor Brian Gleeson for his
unrelenting support and guidance. I would also like to sincerely thank Mr. Barry Jessop,
formerly Manager, BHP Newcastle, for his guidance during this research.
I wish to acknowledge the support of the Australian Research Council and BHP
Newcastle and BHP Laboratories, Melbourne for their funding and support towards
supply of test material and use of hot torsion testing facilities.
I would also like to place on record my sincere gratitude to the following people:
Dr. Alan Brownrigg, formerly Manager, BHP Laboratories, Melbourne, currently at
Deakin University; Mr Brendon Perrett for his unrelenting support during hot torsion
testing, the hot torsion testing team at Deakin University; John Sharp, Inna Bolkovsky,
John Budden of the School of Materials Science and Engineering; Associate Professor
Paul Munroe and Viera Piegorova from the UNSW Electron Microscopic Unit, for their
guidance during transmission electron microscopy work.
I would also like to thank Dr. Arslan Kaya, former postdoctoral fellow at the School of
Materials Science and Engineering for his unrelenting support throughout transmission
electron microscopy.
IV
Finally, I would like to thank my family- my parents, Arun and my lovely daughters
Shreya and Srishti for their constant support and inspiration during my research.
V
ABSTRACT
A major problem encountered during metal forming operations, in particular wire
drawing is strain ageing. This phenomenon manifests itself as an increase in strength
and a decrease in ductility due mainly to the diffusion of free nitrogen and/or carbon to
dislocations. These interstitials form atmospheres around dislocations, effectively
impeding further movement. At lower temperatures, nitrogen typically plays a greater
role in strain ageing than does carbon. A common method of reducing the free
nitrogen content in steel is to add alloying elements, which form stable nitrides. This
project was therefore aimed at studying the strain ageing phenomenon in low carbon
steels as a function of temperature, time and other process variables during wire
drawing. For this purpose, hot torsion laboratory teats were adopted to simulate
conditions during industrial wire drawing operations. The main focus of this study has
been to determine the effects of strain ageing on the mechanical properties and
therefore the drawability of low carbon steels. For completeness, the behaviour of EAF
(electric arc furnace) grades have been compared with the BOS (Basic Oxygen) grades.
Four grades of steels were studied, three of which were BOS grades and one, an EAF
grade. The compositional differences were mainly based on the nitrogen content and
the boron content. These steels were subjected to hot torsion tests at temperatures of
130°C and 200°C with holding times of 30 and 600 seconds after an initial prestrain.
The effect of these test parameters on the general stress-strain curve, work hardening
vi
rate, ageing index, strain to failure and maximum stress were deteremined as a function
of material composition.
Hot torsion tests revealed occurrence of strain ageing m these materials under
conditions typical of industrial wire drawing. However, the absence of precipitate
formation under test conditions led to a conclusion that the ageing phenomenon in these
steels was due to atmosphere formation around dislocations.
Hot torsion tests at a combination of 130°C and 200°C at delay times of 30 and 600
seconds have indicated that although the BOS high B+N grade shows a lower degree of
work hardening, the ageing index does not show an appreciable and consistent
improvement over the other grades. This result has further been confirmed by 'free
nitrogen' analyses in which only a small amount of boron has been found in the
combined form.
It is concluded that boron additions of 0.0012wt% and 0.0038wt% to steels of 0.006-
0.008 wt% N have not been effective in fixing all of the free nitrogen under the cooling
conditions of water quenching from 1100°C to 900°C and subsequent cooling to room
temperature at a cooling rate of 2°C/s.
vii
TABLE OF CONTENTS
PAGE
CERTIFICATE OF ORIGINALITY ii
ACKNOWLEDGEMENTS IV
ABSTRACT VI
TABLE OF CONTENTS Vlll
LIST OF FIGURES XI
LIST OF TABLES XXll
CHAPTER 1 INTRODUCTION
CHAPTER 2 PHYSICAL METALLURGY OF LOW CARBON

GRADE STEELS USED FOR WIRE/ROD PRODUCTS 6
2.1 STEELS COMMONLY USED FOR WIRE/ ROD PRODUCTS
AT BHP, NEWCASTLE 7
2.2 WIRE DRAWING - A GENERAL DESCRIPTION 7
2.3 PHYSICAL METALLURGY OF LOW CARBON GRADES USED FOR
WIRE/ROD PRODUCTS 9
2.3.1 Fe- Fe3C phase diagram 10
2.3.2 Transformations during continuous cooling 14
2.3.3 Effect of alloying elements 16
2.3.4 Classification of alloying elements in steel 16
CHAPTER 3 PRECIPITATION KINETICS 23

3.1 PRECIPITATION KINETICS 23
3.1.1 Diffusion 23
3.1.2 Nucleation of a solid in a liquid 31
3.1.3 Nucleation in solids 36
3.1.4 Experimental methods of monitoring precipitation kinetics 42
CHAPTER 4 STRAIN AGEING OF LOW CARBON STEELS 53

4.1 GENERAL FEATURES 54
4.2 THEORIES OF STRAIN AGEING 59
4.2.1 Atmosphere formation 62
4.2.2 Precipitation on dislocations 65
4.2.3 Effect of dislocation sources 71
4.2.4 Factors affecting strain ageing 72
4.2.5 Static Strain Ageing 73
viii
PAGE
4.2.6 Dynamic Strain Ageing 119
4.2. 7 Strain dependence of Static and Dynamic ageing 125
CHAPTER 5 RESEARCH OBJECTIVES 127
CHAPTER 6 EXPERIMENTAL METHODS 131

6.1 STEEL COMPOSITION AND PROCESSING 132
6.2 ROOM TEMPERATURE MECHANICAL PROPERTIES 132
6.3 MICROSTRUCTURAL CHARACTERISATION 132
6.3 .1 Optical microscope 132
6.3.2 Transmission electron microscope characterisation {TEM) 133
6.4 ELECTRICAL RESISTIVITY 134
6.5 HOT TENSION TESTS 134
6.6 HOT TORSION TESTS 135
CHAPTER 7 RESULTS 139

7.1 OPTICAL MICROSCOPIC EXAMINATION 140
7.2 DETERMINATION OF "FREE NITROGEN" CONTENT IN THE STEEL
GRADES 143
7.4 TRANSMISSION ELECTRON MICROSCOPIC EXAMINATION 144
7.4 HOT TENSILE TESTS 145
7.6 HOT TORSION TESTS 146
7 .6.1 Consistency of hot torsion tests 148
7 .6.2 Hot torsion test results 148
7.6.3 Results of transmission electron microscopic examination 176
CHAPTER 8 DISCUSSION 180

8.1 OPTICAL MICROSCOPY EXAMINATION 181
8.3 HOT TORSION PROPERTIES 182
8.3.1 Influence of temperature on the stress -strain behaviour of the
four steel compositions 182
8.3.2 Influence of delay time after prestrain on the stress - strain
behaviour of the four steel compositions 208
8.3.3 Influence of material composition 227
8.4 TRANSMISSION ELECTRON MICROSCOPIC EXAMINATION 255
CHAPTER 9 CONCLUSIONS 256

9.1 USE OF HOT TORSION TESTING AS A SIMULATION OF
THE WIRE ORA WING PROCESS 257
9.2 INFLUENCE OF VARIOUS PARAMETERS ON THE STRAIN
AGEING BEHAVIOUR 257
9.2.1 Influence of temperature 257
9.2.2 Influence of delay time between prestrain and strain to failure 259
ix
PAGE
9.2.3 Influence of material composition 260
REFERENCES 265
APPENDIX A 275
APPENDIXB 279
APPENDIXC 296
X
List of Figures
LIST OF FIGURES
Figure 1.1 Load elongation curve for a low carbon steel strained to
point A, unloaded and then restrained immediately-curve
(a) or after ageing-curve(b).
Figure 2.1 Fe-Fe3C equilibrium phase diagram
Figure 2.2 (a) Body centred cubic structure
Figure 2.2 (b) Face centred cubic structure
Figure 2.3 Relationship between the Fe-Fe 3C and the CCT curves
0and the structural transformations resulting from various
cooling curves in steels containing a) 0.8%C b) 0.45%C
and c) 1.0%C
Figure 2.4 Effect ofsubstitutional alloying elements on the hardness of
ferrite
Figure 2.5 Effect of chromium on the ferrite region
Figure 2.6 Effect of molybdenum on austenite region
Figure 2.7 Solubility of nitrogen in different phases ofsteel
Figure 3.1 Free energy and chemical potential changes during

diffusion - (a) and (b) down hill diffusion and (c) and (d)
uphill diffusion
Figure 3.2 Interstitial positions in FCC and BCC structures
Figure 3.3 Interstitial atom in (a) equilibrium position (b) at the
position of maximum lattice distortion (c) Variation of.free
energy of the lattice as a function of the position of the
interstitial
Figure 3.4 Variation offree energy with embryo radius
Figure 3.5 Variation of r* and rmax with the amount of undercooling
Figure 3.6 Variation of L1G and N with undercooling for homogenous
and heterogenous nucleation
Figure 3.7 %Bversus %N
Figure 3.8 Change in resistance during precipitation
Figure 3.9 The peak strain as a function of the holding time at
temperature before deformation. The first plateau
indicates precipitation start time and the second, the finish
time
Figure 3.10 A precipitation time -temperature diagram for as obtained
from data in figure 2.16
Figure 3.11 Flow curves in terms of equivalent stress versus equivalent
surface strain for a low carbon steel determined at 600 'C
at nine strain rates
Figure 3.12 Flow curves in terms of equivalent stress versus equivalent
surface strain for a low carbon steel determined at 600 'C
at nine strain rates
XI
List of Figures
Figure 4.1 Load elongation curve for a low carbon steel strained to
point A, unloaded and then restrained immediately-curve
(a) and after ageing-curve(b).
Figure 4.2 The effect of ageing on the properties of mild steel temper
rolled 1.4%
Figure 4.3 Schematic diagram showing potential energy of a solute
atom as a function of the distance R from the centre of a
dislocation
Figure 4.4 Four different stages ofstatic strain ageing
Figure 4.5 Ferrite field showing equilibrium between Fe-N2 gas, Fe-
Fe,,N and Fe- Fe 1~2
Figure 4.6 Solubility of carbon and nitrogen as a function of
temperature
Figure 4.7 Internal friction curves of a dual solid solution of carbon
and nitrogen in ferrite vs temperature. Curves a and b are
the internal nitrogen and carbon peaks.
Figure 4.8 Solubility of nitrogen in equilibrium with dislocations and
precipitated nitride as a function of temperature
Figure 4.9 Diffusion coefficients of nitrogen and carbon
Figure 4.10 Strain ageing of iron -nitrogen and iron carbon alloys
strained 10% and aged for 2 hours at different
temperatures
Figure 4.11 Strain ageing of 0. 029%nitrogen-iron alloy followed by
change in the yield stress(upper curves) and solute content
offerrite as measured by internal friction
Figure 4.12 Increase in the yield stress after prestraining 3% and 8% vs
ageing time at 60 °C (Josefsson and Backstrom(5BJ ).
o-----o 0.02 C, 0.003 N; ---.0.03C0.008N; L1--
L10. 03C0. 008N
Figure 4.13 Increase in the yield stress after prestraining 3% and 8%
vs ageing time at 60 °C o-----o 0.02 C, 0.003 N; ---.0.03C
0.008N; Lt-- L10.03C 0.008N
Figure 4.14 Effect of nitrogen content on the flow stress of low carbon
steel aged at 100 °C for 20 seconds after 6% strain
Figure 4.15 Effect of nitrogen content on decrease in total elongation
due to ageing
Figure 4.16 Effects of (a) nitrogen level in solution and (b) carbon level
in solution on the change in yield stress, on prestraining
and ageing for 1hour at 100C using the following
prestrains Stephenson 10%; Enrietto 12%; Seking,
Fujishima , Butler 7.5% . Dissolved carbon and nitrogen
were determined by internal friction
Figure 4.17 Effect of level of manganese in solid solution on the rate of
strain ageing of commercial rimmed steels prestrained
10% in tension
XII
List of Figures
Figure 4.18 Stress strain curves at 2rfC and 205°C for (b) rimmed steel
which showed pronounced strain ageing and (c) aluminium
killed steel which showed no strain ageing
Figure 4.19 Influence of A/IN ratio on the solute nitrogen after
continuous annealing at 825C
Figure 4.20 Fe-B Phase diagram
Figure 4.21 Diffusion coefficient of boron (firm line) as compared to
carbon (dotted line)
Figure 4.22 Equilibrium phase diagram calculated for Fe-B-N system
Figure 4.23 Typical spherulite morphology of BN in steel
Figure 4.24 Precipitates in a furnace cooled steel from 80rfC after
heating at 130rfC for one hour and hot rolling. A/N grows
radially on BN
Figure 4.25 Schematic illustration ofprecipitation behaviour during the
manufacturing process
Figure 4.26 Type ofprecipitate formed under stee/making conditions
Figure 4.27 Influence of BIN ratio on the elongation
Figure 4.28 Stress strain curves for (a) low carbon steel 0.005%
nitrogen and (b) addition of0.06% vanadium
Figure 4.29 Precipitation temperatures of titanium compounds
Figure 4.30 Mechanical properties of rods containing titanium
additions
Figure 4.31 Effect of titanium on the ageing index of the wire
Figure 4.32 Effect of excess titanium on the tensile strength of low
carbon steel
Figure 4.33 A normal stress -strain curve (2rfC) and corresponding
curves illustrating dynamic strain ageing as a function of
temperature
Figure 4.34 Force-velocity diagram for a mobile dislocation
Figure 6.1 Typical dimensions of a hot torsion sample.
Figure 6.2 Test schedule used for hot torsion tests
Figure 7.1 Optical microstructure ofBOS low nitrogen steel
Figure 7.2 Optical microstructure ofBOS high nitrogen steel
Figure 7.3 Optical microstructure ofEAF low boron steel
Figure 7.4 Optical microstructure of BOS high boron steel
Figure 7.5 (a) TEM micrograph of a BOS grade high nitrogen steel
Figure 7.5 (b) TEM micrograph of a BOS high boron steel
Figure 7.6 Consistency in hot tension tests
Figure 7.7 A typical true stress-strain curve derived from the hot
torsion data
Figure 7.8 Consistency of hot torsion results on EAF steel containing
low boron and high nitrogen, when tested at 200C and a
delay time of 30 seconds after prestrain.
Figure 7. 9 (a) Error band calculated for the stress values
Figure 7.9 (b) Error band calculated for the strain values.
Xlll
List of Figures
Figure 7.10 Stress-strain curves of BOS low N steel as a function of test

temperature tested after a delay time of 30 seconds after
prestrain.
Figure 7.11 Stress-strain curves of BOS high N tested as a function of
prestrain.
Figure 7.12 Stress-strain curves of EAF low B steel as a function of
prestrain.
Figure 7.13 Stress-strain curves of BOS high N+B steel as a function of
prestrain.
Figure 7.14 Stress-strain curves of BOS low N steel as function of
prestrain.
temperature tested after a delay of 600 seconds after
prestrain
Figure 7.16 Stress-strain curves of BOS high N steel as a function of
prestrain
Figure 7.17 Stress-strain .curves of BOS high N+B steel as a.function of
temperature tested after a delay of 600 seconds after
prestrain.
Figure 7.18 Stress-strain curves of BOS low N steel as a function of
delay time after prestrain tested at l 30°C.
delay time tested at J30°C
delay time tested at l 30°C.
delay time after prestrain tested at J3a°C
Figure 7.22 Stress-strain curves of BOS low N steel as a function of
delay time after prestrain tested at 200°C
Figure 7.26 Stress-strain curves of the four material compositions
tested at 130 °c and 30 seconds delay time after prestrain
tested at l 30°C and a delay time of 600 seconds after
prestrain
XIV
List of Figures

tested at 200°C and a delay time of 30 seconds after
prestrain.
Figure 7.29 Stress-strain curves offour material compositions tested at
200°C and a delay time of 600 seconds after prestrain.
Figure 7.30 Transmission electron micrograph showing a very high
density of dislocations and a matrix devoid ofprecipitates
in BOS low nitrogen grade ofsteel tested at 20rf C after a
delay of 600 seconds.
in BOS high nitrogen grade of steel tested at 20rf C after a
in EAF low boron grade ofsteel tested at J3rfC after a
in BOS high nitrogen+ boron grade of steel tested at J3()°C
after a delay of 600 seconds.
Figure 7.34 Transmissio11; electron micrograph showing a very high
in BOS high nitrogen+ boron grade ofsteel tested at 200°C
after a delay of 30 seconds.
in BOS low nitrogen grade ofsteel tested at 20a°C after a
Figure 8.1 Comparison of work hardening exponents in the prestrain
region as a function of temperature tested at 30 seconds
delay after prestrain
Figure 8.2 Comparison of work hardening exponents obtained in the
prestrain region as a function of temperature after 600
seconds delay after prestrain
Figure 8.3 Stress strain behaviour as a function of temperature BOS
Low N tested at 30 seconds delay after prestrain
Figure 8.4 Stress-strain. behaviour as a function of temperature of
BOS High N steel tested at 30 seconds delay after prestrain
Figure 8.5 Stress-strain behaviour as a function of temperature of
EAF low B steel tested at 30 seconds delay after prestrain
BOS high N+ B steel tested at 30 seconds delay after
prestrain
xv
List of Figures

BOS Low N steel tested at 600 seconds delay after
prestrain
BOS high N steel tested at 600 seconds delay after
prestrain
EAF Low B steel tested at 600 seconds delay after prestrain
BOS high N+ B steel tested at 600 seconds delay after
prestrain
Figure 8.11 Comparison of maximum stress values obtained in the
prestrain region as a function of temperature
Figure 8.12 Comparison of maximum stress values in the strain to
failure region as a function of temperature after a delay of
30 seconds after prestrain
Figure 8.13 Comparison of maximum stress values as a function of
temperature after a delay of 600 seconds after prestrain
Figure 8.14 Comparison of total strains to failure as a function of
temperature tested at 30 seconds delay after prestrain
Figure 8.15 Comparison of total strains to failure as a function of
temperature tested at 600 seconds delay after prestrain
Figure 8.16 Comparison of ageing indices as a function of temperature
at 600 seconds delay after prestrain
region as a function ofdelay time after prestrain at 13V°C
region as a function of delay time after prestrain at 20V°C
Figure 8.19 Stress-strain behaviour of BOS low N as a function of delay
time after prestrain tested at J3V°C
Figure 8.20 Stress-strain behaviour of BOS high N as a function of
delay time after prestrain tested at 13V°C
Figure 8.21 Stress-strain behaviour of EAF low B steel as a function of
delay time tested at 13V°C
Figure 8.22 Stress-strain behaviour of BOS High N+ B steel as a
junction of delay time after prestrain tested at 13V°C
Figure 8.23 Stress-strain behaviour of BOS Low N as a function of
Figure 8.24 Stress-strain· behaviour of BOS High N as a function of
Figure 8.25 Stress-strain behaviour of EAF low B steel as a function of
Figure 8.26 Stress-strain behaviour of BOS high N+B steel as a
function of delay time after prestrain tested at 20V°C
XVI
List of Figures

failure region as a function of delay time after prestrain
tested at 13D°C
failure region as a function of delay time after prestrain
tested at 20D°C
Figure 8.29 Comparison of values of total strain to failure as a function
of delay time after prestrain tested at 13D°C
Figure 8.30 Comparison of values of total strain to failure as a function
of delay time after prestrain tested at 20D°C
Figure 8.31 Comparison of ageing indices as a function of delay time
after prestrain tested at 13D°C
Figure 8.32 Comparison of ageing indices as a function of delay time
after prestrain tested at 20D°C
Figure 8.33 Stress-strain behaviour of the four different steel
compositions tested at 13D°C and 30 seconds delay after
prestrain
Figure 8.34 Stress-strain behaviour of the four steel compositions tested
at 13D°C and 600 seconds delay after prestrain
Figure 8.36 Stress strain behaviour of the four steel compositions tested
at 20D°C and 30 seconds delay after prestrain
Figure 8.37 Stress strain behaviour of the four steel compositions tested
at 20D°C and 600 seconds after prestrain
Figure 8.38 Variation of work hardening exponents (prestrain region)
and interstitial content for the four different steel
compositions tested at 13D°C and 30 seconds
Figure 8.39 Variation of work hardening exponents (prestrain) and
interstitial content for the different steel compositions
tested at 13D°C and 600 seconds
interstitial content of four different steel compositions
tested at 20D°C and 30 seconds
interstitial content of the four steel compositions tested at
200°C 600 seconds
Figure 8.42 Maximum stress at constant strain (1. 08) for the four steels
at 13D°C and 30 seconds
Figure 8.46 Variation of interstitial content and ageing index for the
four steel compositions tested at 13D°C and 30 seconds
xvu
List of Figures
four steel compositions tested at I 30°C and 600 seconds
four steel compositions tested at 20V°C and 30 seconds
Figure 8.49 Variation in the interstitial content and ageing index for the
four steel compositions tested at 20V°C and 600 seconds.
Figure A-I Hot tensile curves of EAF Low B steel tested at I 3V°C after
a delay of 600 seconds.
Figure A-2 Hot tensile curves of EAF Low B steel tested at I 3V°C after
a delay of 30 minutes.
Figure A-3 Hot tensile curves of BOS high N steel tested at J3(fC after
a delay of 600 seconds.
Figure B-1 Stress-strain curve of BOS Low N tested at 130°C for a
Figure B-2 Stress-strain curve of BOS Low N steel tested at I 30°C
after a delay time of 600 seconds after prestrain
Figure B-3 Stress-strain curve for a BOS Low N steel tested at 200°C
and 30 seconds after prestrain.
Figure B-4 Stress-strain curve for a BOS Low N steel tested at 200°C
and 30 seconds after prestrain
Figure B-5 Stress-strain curve of a BOS Low N steel tested at 200°C
after a delay time of 600 seconds after prestrain..
Figure B-6 Stress-strain curve of a BOS High N steel tested at I 30°C
after a time delay of 30 seconds after prestrain
Figure B-7 Stress-strain curve of a BOS high N steel tested at J30°C
after a time delay of 600 seconds after prestrain.
Figure B-8 Stress-strain curve of a BOS high N steel tested at 200°C
Figure B-9 Stress-strain curve of a BOS high N steel tested at 200°C
after 600 seconds delay after prestrain.
Figure B-10 Stress-strain curve of an EAF low B steel tested at 130°C
after a time delay of 30 seconds after prestrain.
Figure B-11 Stress-strain curve of an EAF low B steel tested at J30°C
after a time delay of 600 seconds after prestrain
Figure B-12 Stress-strain curve of an EAF low B steel tested at 200°C
Figure B-13 Stress-strain curve of an EAF low N+B steel tested at
200°C after a time delay of 600 seconds after prestrain.
Figure B-14 Stress-strain curve of a BOS high N+B steel tested at
I 30°C after a delay time of 30 seconds after prestrain
130°C after a delay of 600 seconds after prestrain.
200°C after a delay of 30 seconds after prestrain.
200°C after a delay of 600 seconds after prestrain
xvm
List of Figures
Figure C-1 Work hardening exponent in the prestrain region of the

stress strain curve of BOS low N tested at 130°C and 30
seconds delay time after prestrain.
stress strain curve of BOS high N steel tested at J30°C
after 30 seconds delay after prestrain.
Figure C-3 Work hardening exponent in the prestrain region of strain
curve of EAF low B tested at 130°C and 30 seconds delay
time after prestrain
stress strain curve of BOS high N+ B tested at 130°C and
30 seconds delay time after prestrain.
Figure C-5 Work hardening exponent in the prestrain reton of the
stress strain curve of BOS low N tested at 130 C and 600
seconds delay time after prestrain.
stress strain curve of BOS high N tested at 130OC and a
time delay of 600 seconds after prestrain
stress strain curve of EAF low B tested at 130°C after a
stress strain curve of BOS high N+B tested at J30°C and a
stress strain curve of BOS low N tested at 200°C after a 30
Figure C-10 Work hardening exponent in the prestrain reton of the
stress strain curve of BOS high N tested at 200 C after 30
stress strain curve of EAF low B tested at 200 C after 30
stress strain curve of BOS high N+B tested at 200 C after
30 seconds delay after prestrain
stress strain curve of BOS low B tested at 200°C after 600
stress strain curve of BOS high N tested at 200°C after 600
stress strain curve of EAF low B tested at 200°C after 600
xix
List of Figures

stress strain curve of BOS high N+B tested at 200°C after
Figure C-17 Work hardening exponent in a portion of 'strain to failure'
region of the stress-strain curve of BOS low N tested at
130°C and 30 seconds delay after prestrain
region of the stress-strain curve of BOS high N tested at
J30°C and 30 seconds delay after prestrain
region of the stress-strain curve of EAF low B tested at
region of the stress-strain curve of BOS high N+B tested at
J30°C and 30 seconds delay after prestrain.
region of the stress-strain curve of BOS low N tested at
0 .
130 C and 600 seconds delay after prestrain
region of the stress-strain curve of BOS high N tested at
130°C and 600 seconds delay after prestrain
region of the stress-strain curve of EAF low B tested at
region of the stress-strain curve of BOS high N+B tested at
Figure C-25 Work hardening exponent in 'strain to failure region of the
stress-strain curve of BOS low N tested at 200 C and 30
Figure C-26 Work hardening exponent in the 'strain to failure 're§_ion of
the stress-strain curve of BOS high N tested at 200 C and
30 seconds delay after prestrain.
Figure C-27 Work hardening exponent in the 'strain to failure 're§.ion of
the stress-strain curve of EAF low B tested at 200 C and
30 seconds delay after prestrain.
Figure C-28 Work hardening exponent in the 'strain to failure 'region of
the stress-strain curve of BOS high N+B tested at 200°C
and 30 seconds delay after prestrain
Figure C-29 Work hardening exponent in the 'strain to failure 're§.ion of
the stress-strain curve of BOS low N tested at 200 C and
Figure C-30 Work hardening exponent in the 'strain to failure 're§_ion of
the stress-strain curve of BOS high N tested at 200 C and
XX
List of Figures

the stress-strain curve of EAF low B tested at 200 C and
the stress-strain curve of BOS high N+ B tested at 200°C
and 600 seconds delay after prestrain
-xxi
List of Tables
LIST OF TABLES
Table 2.1 Commonly used grades of low and high carbon steels in
BHP, Newcastle.
Table 4.1 Measurements of strain ageing kinetics in slowly cooled or
quench-aged Fe-C and Fe-N alloys(J.D Baird35J)
Table 4.2 Measurements of strain ageing kinetics in quenched Fe-C and
Fe-N alloys (J.D Baird35J)
Table 4.3 Distribution of boron atoms as observed by Watanabe et a/<74·
75)
Table 4.4 Typical steel compositions studied by Morgan and Shyne (79J_
Table 4.5 Mechanical properties of the steels listed in Table 4.4
(Morgan and Shyni79J).
Table 7.1 Image analysis
Table 7.2 Nitrogen analysis of steel grades after hot extraction with
hydrogen.
Table 7.3 Room temperature mechanical properties of steels used in
current study.
Table 8.1 Values of work hardening exponents of the four different steel
compositions under various test parameters.
Table 8.2 Values of maximum stress obtained in the four different
compositions in the prestrain and strain to failure regions
under various test parameters
Table 8.3 Values of total strain to failure of different steel compositions
under various test parameters.
Table 8.4 Values of strain ageing indices in samples tested at 130 and
200°C after a time delay of 30 seconds after prestrain.
Table 8.5 Values of strain ageing indices in samples tested at 130 and
20V°C after a time delay of 600 seconds after prestrain.
Table 8.6 Work hardening exponents of the four grades of steels as a
function of delay time.
Table 8. 7 Variation in work hardening exponents with the interstitial
content for the four steel compositions.
Table 8.8 Comparison of calculated values(using Gladman 's equation)
of flow stress and measured values of flow stress at a true
strain of0.8.
Table 8.9 Values of maximum stress obtained for the four different steel
Table 8.10 Variation of total strain to failure as a function of
steel composition.
Table 8.11 Variation in the ageing index, interstitial content (C+N) and
the boron content, in the four steel compositions.
xxii
Chapter 1 Introduction
CHAPTER]
INTRODUCTION
1
INTRODUCTION
Steels are by far the most popular materials for various applications ranging from
simple structural load-bearing ones to the more sophisticated aerospace applications.
Steels are ductile and are capable of being formed by most forming processes,
including forging, rolling and drawing. Certain grades of steels are capable of being
drawn into very thin wires. The drawability of a metal or alloy is dependent on the
process variables and the mechanical properties(l>. The mechanical properties of a steel
(or any other engineering material) are controlled to a major extent by its chemical
composition and thermal processing. Ideally for optimum drawability the steel should
possess a combination of good strength and ductility. However, it has been noted that
factors which result in an increase of strength, normally decrease ductility and hence
drawability<2>.
The drawability of plain carbon steel wire can be particularly affected by two
phenomena, which may occur either before or during the drawing operation - strain
ageing and quench ageing. Strain ageing manifests itself by an increase in yield stress
on ageing after or during plastic straining< 3>_ Figure 1.1 illustrates the effects of strain
agemg. Suppose a steel specimen is strained to a point A and then unloaded. If it is
then reloaded immediately and strained further,, the stress-strain relationship would
follow curve (a). If, however, after unloading from point A, the specimen was aged at
room temperature for several hours and then tested, a higher yield point would reappear
and the stress-strain relationship would follow curve (b ). These features and other
characteristics of strain ageing are described more fully in Chapter 4.
2
Ageing after straining is called static strain ageing and ageing during straining is called
dynamic strain ageing. The process of strain ageing is important commercially as it has
both beneficial and detrimental effects.
A Y = chan1• in yield stress due to strain a1ln1

AU == chance in U.T.S. due to strain a1in1
.6E • chan,a In elon1ation due to strain a1in1
a
' I •I
INITIAL LOWER
YIELD
EXTENSION
(LUOERS STRAIN
PRE-STRAIN
STRAIN
Figure 1.1 Stress-strain curves for a low carbon steel strained to point A, unloaded
and then restrained immediately-curve (a) or after ageing-curve (b) (JD Baird<37 >).
Among the beneficial effects is strengthening. For instance, static strain ageing is a
viable strengthening mechanism in some alloy systems<4 >_ Dynamic strain ageing can
be incorporated into thermomechanical treatment to improve room-temperature tensile
properties. The detrimental effects include an undesirable decrease in the ductility and
hence formability and drawability; lowered toughness; and formation of stretcher strain
markings during forming.

3
Quench ageing may be defined as any change in the properties of the material resulting
from the precipitation of a second phase at low or moderate temperatures< 5>. The
phenomenon normally increases the hardness, yield and tensile strength; and decreases
ductility. It is effective in preventing strain ageing in many cases but at the same time
it also results in hardening of the matrix, which may adversely affect the ductility and
therefore, drawability.
Worldwide, production of rod and bar steel products is moving from the conventional
method of BOS (basic oxygen steelmaking process) to the newer and efficient EAF
(electric arc furnace) method. The advantages of EAF include flexibility of raw
material, which include use of coal and scrap, no necessity for the raw material to be
prepared in a special form e.g. agglomerates or sinters and the EAF process is
economical for small scale production. However, the EAF steel grades contain higher
nitrogen contents than the BOS grades. Due to the higher temperature produced in the
arc furnace , nitrogen in the atmosphere tends to dissolve to a greater extent in the steel
as compared to that in the BOS process. Nitrogen has been known to play a very
detrimental role during further cold rolling of stee1<2· 7, 8' 9 ). This is due to the solubility
of nitrogen in ferrite and its high diffusion coefficient at room temperature, and also a
high binding energy to dislocations<J, 4, 13, 14, 28, 29, Jo, 31, 36, 37, 44, 49, 51-55, 57-59, 103). These
effects are reviewed in Chapter 4, section 4.1.4.1 of this thesis. Since the EAF process
is being adopted more widely for rod and bar steels, it is worthwhile to study and
understand the effects of nitrogen on the strain ageing of such steels, particularly those
used in wire production. This project is therefore aimed at studying the strain ageing
phenomenon in low carbon steels as a function of temperature, time and other process
variables during wire drawing. The main focus of this study will be to determine the
4
effects of strain ageing on the mechanical properties and therefore the drawability of
low carbon steels, to be more specific. For completeness, the behaviour of EAF grades
will be compared with the BOS grades. The project has been sponsored by BHP Rod
and Bar Division, Newcastle and the Australian Research Council.
This project is an evaluation of the strain ageing phenomenon in low carbon steels
containing some residual nitrogen. Therefore the following sections in the document
will concentrate particularly on the physical and mechanical metallurgical principles
and factors affecting the strain ageing process in low carbon steels. Chapters 2, 3 and
4 contain a comprehensive literature survey of strain ageing and factors that affect
strain ageing. The objectives of this research project are stated in Chapter 5. The
experimental details are described in Chapter 6. Initially, the laboratory work
commenced with hot tension experiments. However, subsequently it became evident
that industrial drawing conditions are better simulated by hot torsion testing and this
technique was adopted as the main focus of the experimental work. Chapters 7 and 8
report the main results and discuss these findings in comparison to reported literature,
respectively. The main conclusions drawn from this research work are discussed in
Chapter 9. Appendix A contains some of the hot tension plots obtained for the four
grades of steels. For ease of reference, the stress-strain curves obtained from hot
torsion experiments for various combinations of times and temperatures, have all been
placed in Appendix B. Appendix C contains the work hardening plots derived from the
hot torsion data for the four materials under various combinations of temperatures and
times.
5
Chapter 2 Physical metallurgy of low carbon steels
CHAPTER2
PHYSICAL METALLURGY OF LOW CARBON
STEELS USED FOR WIRE/ROD PRODUCTS
6
The focus of this Chapter is the physical metallurgy of low carbon steel grades
commonly used for wire/rod products. However, a section on the actual grades of steels
being produced in BHP, Newcastle and an introduction to the wire drawing process
have been included at the beginning of this Chapter.
2.1 STEELS COMMONLY USED FOR WIRE/ ROD PRODUCTS AT BHP, NEWCASTLE
The commonly used grades of low and high carbon steels at BHP, Newcastle are listed
in Table 2.1. The main applications are structural and as welding rods, hence properties
like drawability/formability, strength, toughness, corrosion resistance and weldability
are important.
2.2 WIRE DRAWING - A GENERAL DESCRIPTION
The reduction in the diameter of a solid bar/rod by a successive drawing operations is
called wire drawing<!). Drawing is normally carried out at ambient temperature but as a
result of large amounts of friction generated, the temperature rises during the drawing
process somewhere in the range of 40-70°C. In extreme conditions it may exceed
100°c< 1>. Reductions per pass may range from 5 to 50%. The drawing speeds normally
range from 15 cm/sec to 150 cm/sec and in most modem machines the speeds may
reach 2500 cm/sec<!). Wire drawing is an important commercial process and, a variety
of products are produced by this process. It is compatible with various materials like
aluminium and its alloys, copper and its alloys and a number of steel grades, both plain
carbon and alloy steels.
7
Table 2.1 Common grades of steels used for wire/rod products. Compositions listed are in terms of weight percent.
Grade C p Mn Si s Ni Cr Mo Cu N
WS1033 0.3/0.35 0.04 0.8/1 0.35 0.05
WS1043 0.4/0.45 0.04 0.6/0.85 0.35 0.04
WK1005 0.05 0.04 0.5 0.1/0.35 0.04
5
WK1006 0.08 0.04 0.3/0.6 0.1/0.2 0.04 0.2 0.2 0.1 0.4 0.012
WK1013 0.12/0.16 0.04 0.4/0.7 0.1/0.2 0.04 0.2 0.2 0.1 0.4 0.012
WK10B30 0.28/0.34 0.03 0.6/0.9 0.4/0.6 0.03 B0.0014/0.003 ;Ti0.02min;A10.02/0 0.3
.05
WK1033 0.28/0.33 0.04 0.6/0.8 0.15/0.35 0.05
WK1036 0.35/0.40 0.04 0.65/0.85 0.15/0.35 0.04
WK1043 0.39/0.47 0.04 0.6/0.8 0.15/0.35 0.04
WK1047 0.44/0.52 0.04 0.6/0.8 0.15/0.35 0.04
WK1050 0.48/0.51 0.025 0.6/0.75 0.15/0.35 0.02
5
WK1054 0.49/0.57 0.04 0.6/0.8 0.15/0.35 0.04
W2K1054 0.51/0.54 0.025 0.6/0.8 0.15/0.35 0.02
5
WK1057 0.54/0.62 0.04 0.55/0.8 0.15/0.35 0.04
WK1062 0.59/0.67 0.04 0.6/0.8 0.15/0.35 0.04
W2K1062 0.59/0.62 0.025 0.5/0.7 0.15/0.35 0.04
WK1066 0.63/0.69 0.04 0.8/1.05 0.15/0.35 0.04
WK1068 0.64/0.72 0.03 0.6/0.8 0.15/0.35 0.03 0.0 l 5/0.025Al
WK1070 0.70/0.75 0.025 0.4/0.6 0.15/0.35 0.02
5
WK1072 0.69/0.77 0.04 0.6/0.8 0.15/0.35 0.04
WK1077 0.77/0.81 0.04 0.6/0.8 0.15/0.35 0.04
W2K1077 0.76/0.80 0.025 0.65/0.75 0.25/0.40 0.03
W3K1077 0.74/0.81 0.025 0.6/0.8 0.25/0.35 0.04
8
The die materials used for drawing must be such that they possess good wear
resistance, be able to resist high temperatures generated by friction arising during the
drawing process, and exhibit no reaction with the metal being drawn at any
temperature. The normal die materials are tungsten carbide or steel dies with tungsten
carbide inserts. The bearing surface is that portion which guides the wire /rod as it exits
from the die and the approach angle is that portion of the die where the actual reduction
takes place.
The starting material for a given steel wire drawing process is a wire rod. Prior to
drawing, the rod is cleaned by pickling in a sulphochrome bath (sulphuric acid -
chromic acid) in order to remove the mill scale present on the surface which otherwise
could result in surface defects and excessive die wear. The rod is then coated with a
thin layer of lime or plated with a layer of copper or tin. The lime serves as an absorber
or carrier of lubricant during dry drawing and it also serves to neutralise any acid
remaining from the pickling process. In dry drawing, the lubricant is either grease or
soap powder. In wet drawing, the whole die set-up is immersed in a lubricating fluid.
For coarse wires, reductions are usually given using a single bull block in which a
single reduction may range from 25 - 50%. For fine wires, a large number of bull
blocks are used in one continuous operation and the wire is passed through a number of
dies until it is reduced to the final size. Reductions in this latter case are 5 to 25% per
pass. For steels containing greater than 0.25% carbon, a special patenting treatment is
given (t)_ This consists of heating the wire above a certain critical temperature and
subsequent controlled cooling or transforming in a lead bath held at a temperature
around 500° C in order to produce a fine pearlite microstructure. This results in the best
9
Chapter 2 Physical metallurgy of/ow carbon steels
combination of strength and ductility for successful drawing. Defects that commonly
occur during wire drawing are (a) those already present in the rod like seams, embedded
scales and piping defects; and (b) those arising out of the deformation process, like
chevron cracks or a centre burst generally referred to as cupping. These internal defects
develop as a result of " secondary tensile stresses" which occur in situations where the
mean thickness of the die (h) and the length of the deformation zone, (L) is very high
(i.e 8 = h/L >> 1) (I)_ Temperature gradients resulting in chilled zones of metal caused
when the die meets the workpiece can cause regions of low or practically no
deformation leading to the development of shear bands. Localisation of flow into such
bands may result in shear fracture. Avitzur, as cited by Dieter< 1> modelled this wire
drawing process and found that the model can be successfully used to predict the
combination of semi-die angles and reduction which would prevent the occurrence of
defects.
2.3 PHYSICAL METALLURGY OF LOW CARBON GRADES USED FOR WIRE/ROD
PRODUCTS
The low carbon steels used for wire/rod products in Table 2.1 contain carbon contents
varying from 0.05% to 0.2% (all compositions will be given in weight percent unless
stated otherwise). The major alloying elements are manganese (0.25 - 0.90%) and
silicon (0.07 - 0.25 %). The elements chromium, nickel, molybdenum are in the range
of 0.05%, while sulphur and phosphorus are maintained between 0.025 to 0.040%.
Nitrogen levels vary from a minimum of 0.008 to 0.012 %.
10
The compositions of steels produced by the BOS and EAF processes show a very
distinct difference in the total nitrogen contents. The EAF grade contains higher
nitrogen content than the BOS grade.
2.3.1 Fe - Fe3C phase diagram
Figure 2.1 shows the Fe- Fe3C metastable phase diagram. The carbon content of Fe3C
is 6.67%, is not shown in the above diagram because it has been truncated at 5 %
carbon. The diagram indicates the presence of different phases as a function of the
temperature and carbon content. The various phases in the diagram are defined below.
a) (a - Fe)- ferrite phase which is a solid solution of carbon in iron. This is a soft
phase and has a body centered cubic (BCC) crystal structure (Figure 2.2a) and
occurs at temperatures lower than about 910°C; however the exact temperature
depends on the carbon content of the steel.
b) (8 - Fe)- ferrite phase, which has the same body centred cubic structure as the low
temperature a - Fe, but occurs at temperatures higher than 1410°C.
c) (y- Fe) - austenite phase which is a solid solution of carbon in iron and occurs at
temperature ranges higher than 727°C and below 1410°C depending on the carbon
content of steel. This phase is face centred cubic (FCC) in crystal structure (Figure
2.2b).
d) Fe3 C - cementite, an interstitial compound formed between iron and carbon. This
phase has an orthorhombic crystal structure.
11
Atomic%
0 2·5 5 7·5 10 12·5 15 17·5 20
1800
1700
1600
A Liquid
p- 1300
!
i 1200
l r
! 1100 1147·
1000
T+ Fe3C
727 K-
600 - a+Fe 3 c
500
0 0-5 1·0 1·5 2·0 2-5 3-0 3·5 4·0 4·5 5·0
Weight % Carbon
Figure 2.1 Fe-Fe3C equilibrium phase diagram (Krauss').
e) Pearlite (a - Fe + Fe3C) - this is a micro-constituent consisting of ferrite and
pearlite, and forms by the decomposition of austenite of composition "S" in Figure
2.1 at temperatures below 727°C. The phase commonly occurs as lamellae, with
ferrite and cementite as alternate layers.
12
(a) (b)
Figure 2.2 (a) Body centred cubic structure (b) Face centred cubic structure
(Honeycombe 10>
The main constituents of a low carbon steel microstructure are typically (in descending
order of volume percentage)
1. ferrite (a - Fe)
2. pearlite (a - Fe+ Fe3C); and
3. finely dispersed constituents such as various nitrides / carbides / sulphides or
carbonitrides ( e.g AlN, VN, TiN, V4 C, MnS, TiCN etc.)
The equilibrium amount of pearlite in a Fe-C steel containing 0.2% carbon would be
about 25 volume% (Figure 2.1 ). There is often also a dispersion of very fine
nitrides/carbides in the ferritic matrix or grain boundaries of the low carbon stee1<3>· A
brief paragraph on the possible transformations on continuous cooling of steels 1s
included in the next section.
13
2.3.2 Transformations during continuous cooling :
Many of the heat treatments performed on steel involve continuous cooling conditions,
and the transformations that occur are represented by transformation diagrams(?).
These diagrams can be experimentally determined through the use of dilatometry in
which changes in length are measured as a function of temperature and time. Figure
2.3 shows the relationship between a transformation diagram and the Fe- Fe3C phase
diagram for steels of three different carbon contents.
As illustrated in Figure 2.3, the transformation diagrams indicate the different types of
phases obtained when a steel of a certain composition is cooled. If the cooling rate
employed is such that it cuts the pearlite-ferrite curves, then these are the phases
expected in the steel. However, if a cooling rate that would result in avoiding
intersection with the pearlite-ferrite curves were used, the metastable and brittle
martensite phase would form. The minimum cooling rate that is tangential to the
leading nose of the curves is called the critical cooling rate. Any rates above this would
result in the formation of martensite.
Transformations are very much influenced by the steel composition i.e type and amount
of alloying elements present in steel. The exact effects are discussed very briefly in the
following sections.
14
nnp•ratur•
.
C
900 900
100 800
700 700
600 600
n,
500 500
m P•B
400 400
300 300
200 200
100 100
0
(a)
0 0.2 0.4 0,6 0.1 ,.o 1,2¥, C
0
0.1 I 10 102 103 104 105 s
Tim•
T•mprrature
9c c
900
800
700
Ilf'•P
600
mP+B
500
400 400
300 300
200 200
100 100
(b)
0
0 0,2 Q,4 a., a.e 1,0 1,2 .,.c 0
0.1 I 10 10 10) 10 10 s
Tim•
T•mp.,.at-
c •C
900
800
700
600
SOO
400
300 300
200
100 100
0 0
(cl 0 0.2 a., o., a,,, ~o 1,2 °/o C 0.1 I 10 10 I 10 4 10 s
Tim•
Figure 2.3 Relationship between the Fe-Fe 3C and the structural transformations
resulting from various cooling curves in steels containing a) 0.8%C b) 0.45%C and
c) 1.0¾C (K.E Thelning< 11))
15
2.3.3 Effect of alloying elements:
Plain carbon steels are quite limited in their range of applications due to their narrow
span of useful properties. Alloying elements are added to steels for purposes mainly
aimed at overcoming the limitations of plain carbon steels. Some of the important
advantages achieved are an increase in hardenability and improved mechanical
properties at room temperature and increased corrosion and oxidation resistance.
Each alloying element has a characteristic effect on the properties of the particular steel
being alloyed. Generally the effects may be divided into the effects on the Fe-Fe3C
diagram and the kinetic effects that occur during heat treatment. The effects during
heat treatment are well represented by the effect on the continuous cooling curves. By
affecting the phase stability and kinetics of transformation behaviour, the alloying
elements may raise or lower the transformation temperature, shift the eutectoid
composition, and alter the position of the continuous cooling curves to the left or right.
2.3.4 Classification of alloying elements in steel:
There are two distinct effects:
1. Alteration of the relative stability of ferrite and austenite by the element- hence
classification as austenite stabilising elements or ferrite stabilising elements.
2. Alteration of the relative stability of graphite and cementite/carbide phase -
hence classification as graphite stabilising or carbide forming elements.
16
However, it must be noted that these are equilibrium effects and there are other effects
based on kinetic factors.
The specific effects of each of the common alloying elements added to low carbon
steels have been reviewed by Clark and Varney< 8>, Porter and Easterling<9> and
Honeycombe< 10>and the following text provides a brief summary.
• Manganese
The diffusion of carbon in austenite is retarded by manganese< 8>. Manganese provides
solid solution strengthening to ferrite. Manganese has an unlimited solid solubility in
austenite and has a 3% solid solubility in ferrite< 8>. Manganese shifts the CCT curve to
the right, lowering the critical cooling rate and increasing the tendency to form
martensite (increasing hardenability). Manganese decreases the extent of strengthening
with a reduction in the grain size. i.e. it decreases the value of 'k' in the Hall-Petch
relationship. Manganese also affects the modulus of elasticity and the shear modulus.
• Silicon
Silicon strengthens ferrite(s, 12> (Figure 2.4). It is a ferrite phase stabiliser and shifts the
eutectoid carbon compositions to lower carbon contents. Silicon delays the formation
of pearlite, shifting the CCT curve to the right. This decreases the critical cooling rate
and increases the tendency to form martensite. Silicon has a solid solubility of 2% in
austenite and 18.5% in ferrite cs, 12>. Silicon partitions to the ferrite phase and exhibits a
positive thermodynamic interaction parameter with carbon thus raising the activity of
carbon in austenite. This means that carbon will not only diffuse away from regions of
17
high carbon concentration but also from regions rich in siliconC9>_ Silicon is used as a
general deoxidiser .
.........
HV
240
p Si Mn
220
: ,,I /
200 I I/ __,.. ,,,,,,, Mo
V
1eo I I /
r
~ 1-'P-
.,,,,,,,,,.._ i -'
,.o /, I __,,Ni _.,,,,,. ~ i.,.-'"

.' / ,,,, ~~ ~ -- - ~
....---- w
J I,, , ,,- ......~ ~ ~ ---- ---

140 i- Cr
120
100
~ ~
j , ".A'.. ~ --
~ ::;..-- -- --- ~
eo
0 2 · 4 8 8 10 ·12 14 19 18 20 22 24 .,.
Concentration of a l l ~ element in J..- iron I fenite J
Figure 2.4 Effect of substitutional alloying elements on the hardness of ferrite

(Bain and Paxton< 13>)
• Chromium
Chromium is a strong ferrite stabiliser as shown in Figure 2.5 and therefore raises the
eutectoid transformation temperaturecs, 13 >_ It also shifts the eutectoid carbon
composition to the left, i.e, to lower carbon compositions. Chromium has a high solid
solubility in ferrite and a 12.8% solubility in austenitec 8>. Chromium also has a
tendency of delaying the formation of pearlite, thereby shifting the CCT curve to longer
times and increasing the tendency for martensite formation. Chromium has a tendency
to retard the austenitic decomposition by formation of chromium-rich carbides, since
these carbides are thermodynamically more stable than cementiteC 12>. These carbides
lead to greater undercooling and therefore finer interlamellar spacing in pearlite02 >.
These chromium-rich carbides also act to improve the wear resistance of steel.
Chromium decreases the growth rate of pearlite and partitions to the cementite phase of
18
pearlite02 >. Chromium also increases the corrosion and the oxidation resistance of
steel.
2800.....---r-----,r--...._--,r---r----.---------
- 2200t---'1f----bl~-'!-'-71r__-R-,::::!!lf,,-..::-=+-=:---+---+------t
lL
0
-;_ 2000 1---.,__-+---+-+---f.

E
~ 1800 If----+---+-+-,,,<-~-
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8

Carbon ( per cent)
Figure 2.5 Effect of chromium on the ferrite region (E.C Bain and Paxton< 13>).
• Nickel
Nickel is a very strong austenite stabiliser and thus increases the range of temperatures
over which austenite is stable. Nickel also shifts the eutectoid composition to lower
carbon content. Nickel has an unlimited solid solubility in the austenite phase and 10%
solid solubility in ferrite<S).. Nickel increases hardenability and shifts the CCT curve to
the right, thus lowering the critical cooling rate. But nickel tends to retain austenite
with high carbon< 8>.
Nickel contributes marginally to the solid-solution strengthening of ferrite. Nickel has
the effect considerably decreasing the ductile-to-brittle transition temperature< 8>. The
transition temperature is lowered considerably, thereby increasing the toughness of
steels. Nickel does not form carbides.
19
• Molybdenum
Molybdenum is known to raise the grain coarsening temperature of austenite<S)_ It
provides slight solid-solution strengthening to ferrite and shifts the CCT curve to the
right, thus lowering the critical cooling rate and increasing hardenability (i.e the
tendency to form martensite ). The effect of molybdenum on the austenite phase field
is shown in Figure 2.6. Molybdenum is a strong carbide former and contributes to
secondary hardening during tempering. Molybdenum has a higher solubility in ferrite
(37.5%) than in austenite (3%i 8' ' 3)_ It is added to steels to counteract the tendency
towards temper embrittlement. Molybdenum forms abrasion-resistant carbides which
in tum raise the hot hardness of the steel(s, 11 >.
• Niobium
Niobium forms a very stable carbide, nitride and carbonitride. As such, the presence of
niobium in steels slows the recrystallisation process during hot working, leading to a
refinement in the ferrite grain size. Niobium has very limited solid solubility in
austenite and is a major contributor to precipitation hardening.
• Vanadium
Vanadium has an unlimited solid solubility in ferrite and up to 4% in austenite< 8>. It has
a moderate solid-solution hardening tendency in ferrite. Vanadium shifts the CCT
curve to the right, and correspondingly lowers the critical cooling rate and thereby
increases the tendency to form martensite. Vanadium forms very stable carbides and
nitrides.
20
2aoo------.---,--~----------------,
26001--_..,_--+-...;.a,.~---+---+--+---+---+---t-----l
1400 1----+------li--;;;;:-=---s-.:::-:::-_-'"ff""lc..,_--+---t---+--t---1
12000 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8

0.2
Carbon ( per cent)
Figure 2.6 Effect of molybdenum on austenite region (E.C Bain and Paxton< 13>).
• Cobalt
Cobalt has an unlimited solubility in austenite and is soluble upto 75% in ferrite< 8> • It
hardens ferrite considerably by solid solution hardening. Cobalt in solution has a
tendency to decrease hardenability and therefore shifts the CCT curve to shorter times,
thus increasing the critical cooling rate.
• Nitrogen
Nitrogen forms an interstitial solid solution with ferrite< 3>_ Nitrogen addition to steel
results in an expanded y phase field(S, 10>. Interstitial, or free nitrogen is the most
common form in steel and gives rise to strain ageing problems at temperatures lower
than 100°C (as will be discussed in detail in further sections). The solubility of nitrogen
in ferrite, at various temperatures has been studied by Leslie <3, 14> (shown in Figure
2.7). It is seen that for a steel with a nitrogen content of 0.01 wt%, the solubility is only
21
exceeded during cooling below 1173K (900°C). The extrapolated solubility of
nitrogen at room temperature is in the range 10·4 to 10-5 wt%.
0,05
0,04
l
0,0.3
N
Wt.% 0,02
0,01 ,,," s
,,
I
,/
0
700 1100 1500 1900
DEGREES, ° K
Figure 2.7 Solubility of nitrogen in different phases of steel (L.S Darken cited by
Leslie< 14>).
22
Chapter 3 Precipitation kinetics
CHAPTER3
PRECIPITATION KINETICS
23
3.1 PRECIPITATION KINETICS:
As will be discussed in detail in section 4.1.1, strain ageing is due to the combined
effects of solute atom atmosphere formation around dislocations and also precipitation.
It is therefore very relevant to study the kinetics of precipitation. The process of
precipitation is typically diffusion controlled and takes place by nucleation and growth.
An understanding of the nature of these processes is very important in order to find an
effective way of controlling or offsetting strain ageing.
3.1.1 Diffusion:
Before understanding the kinetics of the diffusion process, a few basic thermodynamic
terms need to be defined.
Gibb's Free Energy: The relative stability of a system is determined by the Gibb's
free energy( 9), which is defined by the equation
G = H -TS-------------------------------------3.1
where H is the enthalpy, T is the absolute temperature and S is the entropy of the
system. Enthalpy is a measure of the heat content of the system and is given by
H = E + PV-----------------------------------3.2
where E is the sum of the internal energies of the system, P is the pressure and V the
volume.
A system is stated to be at equilibrium when it is at its most stable state, which in
thermodynamic relationships translates to the lowest possible value of Gibb's free
energy. This means that high stability is obtained with the best compromise between
24
low enthalpy and high entropy. Therefore any transformation, which results in a
decrease in the Gibb's free energy, is possible. The transformation, however need not
go directly to the minimum free equilibrium state, but can pass through several
intermediate metastable states where the free energy values lie at a local minimum.
Most of the phase transformations that occur in steel are diffusion controlled and hence
depend on temperature and time in a non-linear manner<9>. The driving force for the
diffusion process is the inherent tendency of a system to attain the lowest possible
energy state where it becomes stable. Diffusion is typically related to the concentration
gradients across a system. The common principle that governs this process is that an
element diffuses across a concentration gradient, such that long-range diffusion ceases
only when the concentration of the element becomes equal in the two regions. Figure
3.1 illustrates this process in two systems, where point A indicates 100% of element A,
µ 1A, µ 18 and µ2A, µ28 are the chemical potentials of A and B in two different solid
solutions 1 and 2.
Chemical potential is the partial molar free energy of the element. This term is
introduced to understand the effect of addition or removal of atoms on the total free
energy of a given phase such that
dG - µA dnA -------------------------------------------- 3.3
This relation holds true when the temperature, pressure and the number of atoms of the
second element are constant. This proportionality constant in the equation is the
chemical potential, and it depends on the composition of the phase. Therefore dnA must
be so small that the composition of the phase is not significantly altered. As indicated
25
in Figure 3 .1, diffusion of a given element always occurs down its gradient of chemical
potential.
~
8-rich A-rich
(o) (b) A ® (D B
~@I
8-rich A-rich
(c) (d)A ® (D 8
µl µi
µi µi
µr µi
µl µi
(e)
A ® (D 8
(f)
A ®CD 8
Figure 3.1 Free energy and chemical potential changes during diffusion - (a)i and
(b) down hill diffusion and (c) and (d) uphill diffusion (Porter and Easterling< >)
The two mechanisms by which atoms diffuse through a solid depend on the type of site
occupied by the element in question in the lattice of the matrix. The two mechanisms
are as outlined below.
(a) Substitutional diffusion- atoms diffuse through vacancy defects present m a
material.
(b) Interstitial diffusion - atoms force their way through the interstices between the
matrix atoms without permanently displacing any one of them< 15 )_
26
Whether a solute goes into solution interstitially or substitutionally, depends on the size
of the solute atom (IS)_ An empirical rule based on x-ray data indicates that in cubic
lattices, a solute will dissolve interstitially only if it atomic radius is less than 0.59 times
that of solvent. However, practically, it has been observed that solute with radii up to
0.85 times that of the solvent can dissolve interstitially< 15 >_ Since strain ageing is related
to the diffusion of interstitial atoms only, this section will discuss only interstitial
diffusion.
3.1.1.1 Interstitial Diffusion
Fig 3.2 shows the interstitial sites in body centred and face centred cubic structures.
Usually the interstitial concentration is so low that only a very small fraction of the
indicated sites are occupied. This would mean that the interstitials are surrounded by a
number of vacant sites, which can be occupied as often as the energy conditions would
favou/ 9). This mechanism has been explained using figure 3.3. For the interstitial
atom in position I to move to position 2, atoms in positions 3 and 4 would have to
move apart, i.e a distortion in the lattice has to occur. The ease with which this happens
is the basis for diffusion of interstitials through interstice positions. This process could
take place as a "random jump" process in either a steady state situation or a non-steady
state one.
27
(a) • Melal a1oms (b) e Metal atoms

•.) Oclahedral inlerslices o Tetrahedral interstices
Octahedral (a) and tetrahedral (b) int· stitial voids in fee struc-
turc.
·O·f,.o
··
.o ·:
(a) e Metal aroms (b) e Me1aI a1oms

o Octahedral inlerslices o Tetrahedral inlerslices
Octahedral (a) and tetrahedral (b) interstitial voids in bee

structure.
Figure 3.2 Interstitial positions in FCC and BCC structures (Porter and
Easterling<91).
28
(a) (b)
o.oo 0 0
000
~
0
l
G '1Gm (c)
j
a.
X _,.
Figure 3.3 Interstitial atom in (a) equilibrium position (b) at the position of
maximum lattice distortion (c) Variation of free energy of the lattice as a function of
the position of the interstitial (Shewmon< 15>).
• Random Diffusion:
This mechanism of diffusion can be explained by assuming a dilute interstitial solid
solution <9>_ The parent atoms (A) are arranged on a simple cubic lattice and the solute
atoms (B) are accommodated in the interstitial positions in the crystal structure.
Another assumption is that the solution is so dilute, that every interstitial atom is
surrounded by six vacant interstitial sites. If the concentration of B varies along say,
only one dimension in the material, i. e direction x, then B will continue to diffuse to
regions of low concentration tuntil the chemical potential of B is the same everywhere.
The local flux of B atoms diffusing in unit time, is given by Fick's first law of diffusion
Je = - De (oCe / ox)---,--- ---------------3.4
The partial derivative indicates the concentration gradient and implicitly assumes that
(oCe I ox) a µe/ox --------------------------------3.5
29
Ds is the diffusion coefficient of atom B which is independent of the concentration of B
and is given by
De = 1/6 (f' e/ a 2) - - - - - - - - - - ----3.6

Here, r s is the number of times an interstitial atom would jump per second and a is the
average separation between planes.
Diffusion is a process which is dependent on both temperature and time. Due to the
thermal energy of a solid, all atoms are in a continuous process of vibration. An
occasional extreme oscillation could result in a jump of the interstitial atom to another
position. In order to move an interstitial atom to a new position, the atoms of the matrix
have to be forced apart as shown in Fig 3.3(b). This causes an increase in the free
energy of the system by say, Ii Gm, which is in other words is the activation energy for
this process (Figure 3.3(c)). The energy of the atoms changes as they continuously
collide with one another. The fraction of atoms having an energy of Ii G or more than
the mean energy is given by the Boltzmann relation exp (-Ii G / RT). If the interstitial
atom vibrates with a mean frequency v in the x direction it makes v attempts in a given
time to jump to the next available site.
The fraction of the attempts that are successful is given by exp (-Ii Gm/ RT). If there
are z number of sites available, then the frequency of jumps is given by the following
equation.
f' 8 = zv exp (-Ii Gm/ RT)-------------------------- 3. 7
!l.Gm = !l.Hm -T!l.Sm ------------ -------3.8
where !l.Hm is the activation enthalpy and !l.Sm is the entropy term. The diffusion
coefficient at this temperature will be given by

30
Ds = Dso exp (-Q IRT)------------·-----3.9

where, from equation 2.5,
Dso = 1/6 a 2 zv exp(~ Sm/ R)------------ --3.10
and Q- ~ Hm-----------------------------------3.11
D or r has been found to increase exponentially with temperature at a rate determined
by the activation enthalpy Q. Equation 3.9 is found to agree with experimental
measurements of diffusion coefficients in interstitial systems. It has been found that the
activation energy in these systems is only dependent on the activation energy barrier to
the movement of interstitial atoms from one site to another< 9 • 15 ).
Once atoms of a given element diffuse to regions of low chemical potential, there is a
point in time when the concentration of the element is such that it could combine in
stoichiometric ratios with other similarly diffusing elements to form a compound,
which could nucleate and grow as a function of time and temperature. The next section
attempts to explain mechanisms of nucleation and growth in very general terms.
3.1.2 Nucleation of a solid in a liquid:
The principles of nucleation can be most easily treated by considering solid nucleation
in a liquid cooled below its equilibrium melting temperature<9l_ Nucleation is a process
through which the smallest stable particle of a new phase is formed< 16l. The driving
force for solidification (GL - Gs) would allow the liquid to solidify (where GL and Gs
are free energies of the liquid and solid phase respectively). The nucleation process is
not instantaneous and liquids can be undercooled and held at the undercooling
temperature for a long time without anything happening. This is particularly observed
when the solid is forced to nucleate homogeneously, i.e when solid nuclei form within
the volume of the liquid itself. The process of homogenous nucleation requires a very
31
high degree of undercooling. There are several theories proposed to explain the
nucleation process.
Gibbs explained this nucleation process thermodynamically <16>. Consider a liquid
system with a free energy G1, which is represented as
G1 = VL GvL-------------------------------3.12
If an embryo of a new solid phase forms, the free energy of the system changes to G2,
which is given by
where Vs is the volume of the solid sphere, VLthe volume of the liquid, AsL, the solid-
liquid interfacial area, Gv8 and Gi are the free energies per unit volume of solid and
liquid respectively. Due to the formation of a new surface, this embryo is associated
with some interfacial energy YsL- This in tum serves to increase the free energy of the
system. Any stable system sustains itself by attaining the lowest free energy state.
Therefore, an increase in free energy of the embryo would naturally tend towards
dissolution of the embryo in the parent phase. However, if an embryo of a specific
chemical and crystallographic orientation (eg. a spherical shape), forms, the increase in
the interfacial energy could be offset by a decrease in the chemical free energy, thus
increasing the stability of the embryo<9>_ Therefore, the net free energy now becomes
~ G = -4/3 7t r 3 ~ Gv+ 4n r 2 ysL ----------------------------3.14
Figure 3.4 illustrates this variation in the free energy change associated with nucleation
as a function of the embryo radius r*. As shown in the figure, the positive interfacial
energy term is proportional to the second power of the linear dimension of the embryo
(Gocr2); while the volume free energy change Gv is proportional to the third power of
32
the linear dimension of the embryo. Therefore, creation of solid particles will always
lead to an increase in the free energy of a system. At small embryo sizes, the addition
of each atom will make the total free energy change AG, more positive. It can be seen
that for a certain degree of undercooling, there is a certain radius r*, which is associated
with a maximum excess free energy<9, 16>. If r < r* (the critical embryo/cluster radius)
then the system can lower its free energy by dissolution of the solid, while in a situation
where r >r* (nuclei), the free energy of the system decreases if the solid grows. The
effect of interfacial energy can be overcome only when 8AG/ 8r = 0, this defines the
critical size nucleus r* or the number of atoms in the critical size nucleus n* and the
free energy of activation for the formation of this critical size nucleus, A G*.
r* = 2 YsL I A Gv --------------------------- 3.15
and A Gv= Lv AT/ Tm-------------------,----3.16
AG* =l61t YsL3/3 (A Gv )2 =(l61t r3sL T2m)/ (3Lv2 A T2) 3.17
where Tm = melting point , A T = degree of undercooling and Lv = latent heat of
fusion. As the amount of undercooling increases, the critical size of cluster required to
be stable decreases.
Since AGv is often found to be proportional to the ratio of y3 to undercooling AT, where
y is the surface energy of the new surface created. The following general equation holds,
L1G* = k y I (L1T) 2 ------------------------------- 3.18
where k is the constant of proportionality, which depends on the slope of the solvus
boundary. Thus, the nucleation rate, both in a solid and in a liquid, increases for a
given system as the surface energy decreases and AT increases.
33
.6G
+
0 r
Figure 3.4 Variation of free energy with embryo radius (Porter and Easterling<9>)
Gibbs related .1G* to the volume of the critical nucleus V* as follows <9, 16>
AG*= - (V*/2) AGv ----------------------------------------- 3.19
Thus any mechanism that would reduce V* and AGv would result in a reduction of.1G*
and hence, an increase in the nucleation rate at a given temperature. The value of
V*can be decreased by nucleation on a foreign surface or on a defect, such as a grain
boundary or dislocation< 15>_ This is referred to as heterogenous nucleation.
34
Figure 3.5 Variation of r* and rmax with the amount of undercooling (Porter and
Easterling(9>).
The variation of ~G* with the amount of undercooling, for both homogenous and
heterogenous situations is shown in Figure 3.6.
It has been observed that that a much smaller undercooling is needed for the onset of
nucleation kinetics in heterogenous than in the homogenous process
The steady state nucleation rate N is given by( 16>
N = Z /3*0 exp ( - LIG* I kT) exp ( r-lt) -----------------------3.20
where Z is the Zeldovich non-equilibrium factor, /3* is the rate at which atoms are
added to the critical nucleus or the frequency factor, 0 is the number of nucleation
sites per unit volume, LIG* is the critical free energy for nucleation , k is the
Boltzmann's constant and T is the absolute temperature. The Zeldovich factor converts
the metastable equilibrium number of nuclei to the smaller number actually present
because some are lost to the growth stage of transformation. Normally Z= 10· 1- 10·2• f3
* is proportional to the diffusivity of an element in the matrix phase or nucleus: matrix

35
boundary diffusivity. 0 is dependent on whether the nucleation is homogeneous or
heterogenous.; however, this parameter is unaffected by the alloy composition, reaction
temperature and time< 16>. T is the incubation time and is affected by temperature and
composition. Figure 3 .6 shows the variation of the steady state nucleation rate N with
the reaction temperature for a given alloy composition and the precipitate phase< 16>. It
is evident from the above equation that the rate of nucleation would increase if AG*
decreases. There is a large reduction in the amount of undercooling that is required for
an increased nucleation rate. This would mean that a number of nuclei could form
under conditions of heterogenous nucleation more easily than for a homogenous
condition, and more importantly, for a smaller degree of undercooling.
Although initially, the stage of solid nucleation has been studied on a system where
solid forms in the liquid, similar studies have been extended to formation of a new solid
in an already solidified system. The following paragraphs concentrate on the
nucleation of a solid in a solid system.
3.1.3 Nucleation in solids:
Solid-state nucleation is usually related to phase transformations which are thermally
activated atomic movements<9 , 15 >. There are several types of transformations possible.
However, this section will only be concerned with the mechanisms of precipitation.
Precipitation, in general, can be expressed as follows:
d ---+ a + P-----------------------------------1.21
36
where a1 is a metastable supersaturated solution, f3 is the stable or metastable
precipitate and a is a more stable solid solution with the same crystal structure as a1,
but with a composition closer to equilibrium<9>.
'\
\
tJ.G~ \
\
\
\
\ tJ.Ghet
. Criticol value
for detectable
nucleation
\
' I'-
---~---- --'---
(a) 0
I
I
I
--- -- I
I
- ------AT
I I
I I
1 I
I I
I I
N I
I
Nhet I Nhom
I
I I
I I
I I
I I
I I
I I
I
(b) 0
Figure 3.6 Variation of ~G and N with undercooling for homogenous and

heterogenous nucleation (Porter and Easterling<9))
As dealt with in section 3 .1.2, this precipitation phenomenon will be explained in terms
of first homogenous process principles and then in terms of heterogenous process
principles.
3.1.3.1 Homogenous nucleation in solids
Consider a solid /3, which is rich in B and forms in a supersaturated A-rich solution.
For nucleation of /3, B atoms within the matrix must first diffuse together and for a
37
compound to precipitate, its concentration at a particular temperature must exceed the
solubility product in the matrix phase. The solubility product K, is given by the product
of element concentrations in the phas, at a particular temperature.
K - [A]x [B]Y --------------------------------------- 3.22
where, A and B are the two elements in question that form a compound AxBy.
The larger the value of the difference from the solubility product at a particular
temperature, the higher is the driving force for the nucleation of the compound
precipitate. Figure 3.7 shows the relationship between % B and % N in austenite at
1000 °C. Points A and B are two B-N concentrations in two different steels. It is
evident that both the alloys have exceeded the solubility product of BN at this
temperature. It is expected however, the alloy at Point B will precipitate BN more
easily than that at A, due to a larger driving force available for it to do so.
%Bvs%N
0.000002
0.0000018
0.0000016
0.0000014
0.0000012
ID
~ 0.000001
~
0.0000008
0.0000006
0.0000004
0.0000002
0
0 0.002 0.004 0.006 0.008 0.01 0.012
wt%N
Figure 3. 7 % B versus ¾N (Maitrepierre cited by Franks and Kirkcaldy (73 >)
38
As with the liquid to solid transformation, an a Ip interface must be created during the
precipitation process and this leads to an activation energy barrier. In addition, the
transformed volume will not fit perfectly into the space originally occupied by the
matrix and this gives rise to a misfit strain energy ~Gs per unit volume of p The
strain energy acts as a barrier to nucleation. The free energy change associated with
the nucleation process will have the following three contributions:
• At temperatures where the p phase is stable, the creation of a volume V of
p will cause a volume free energy reduction of V~Gv.
• The creation of a new surface will give a free energy increase of A 1.
• In general, the transformed volume will not fit perfectly into the space
originally occupied by the matrix and this gives rise to a misfit strain
energy ~Gs per unit volume of p
Summing this up leads to the total free energy term as
LlG = - V LlGv + A y+ V LlGs _ _ _ _ _ _ _ ___,,23
Assuming that the nucleus is spherical with a radius of curvature r ,
LlG = - 47!1 (LlGv - LlG.J + 4m-2 r------------------------------3.24
On differentiating equation 3.24, we get
r* = 2y/ (LlGv - LlG.J-------------------------------- 3.25

and
LlG* = 161fyl 3 I (LlGv - LlG.J 2-----------------------3.26
This expression is similar to that for a nucleation of a solid from a liquid (solidification),
except that the chemical driving force, which is the misfit strain energy, LlGs, is reduced
by a positive strain energy term. The homogenous nucleation rate is expressed as

39
N = wCo exp (-LI G,,/kT) exp (-LIG*lkT)--------------------3.27

Where OJ is a factor that takes the frequency of vibration and the area of the critical
nucleus.
3.1.3.2 Critical energy for heterogenous nucleation:
As mentioned earlier, homogenous nucleation rarely occurs in practice and it is
heterogenous nucleation that is the most important factor. Both the situations of
coherent and incoherent nucleation at the dislocations have been extensively studied (9,
15 ' 16>. Coherency arises out of a perfect match at the interface plane of two crystals in
such a way that the two lattices are continuous across the interface. This can be
achieved if the interfacial plane has the same atomic configuration in both phases.
Incoherent interfaces have very different atomic configurations in the two phases. In
both these situations, it has been found that the volume strain energy may be reduced,
thus aiding nucleation. During incoherent nucleation on the dislocations, it was
observed that a destruction of a portion of the dislocation core and the subsequent
elimination of the dislocation's strain field leads to a change in the free energy which
accelerates nucleation( 16>. While in coherent nucleation, the nucleus forms on the
tensile/compressive side of the dislocation core, depending on whether the volume
change is negative or positive and at a distance away from dislocation core so as to
minimise the volume strain energy of the nucleus. This could result in the partial
nullification of the strain field around the dislocation and reduce ~G* further.
Although the dislocation does aid coherent nucleation to a much smaller extent than
incoherent nucleation, this effect is decreased to a large extent as a result of the high
nucleus: matrix interfacial energy associated with incoherent nucleation. However,
40
both incoherent and coherent nucleation on dislocations have common features such as
higher rates of nucleation at edge that at a screw dislocations< 16>. The nucleation rate
also increases with increasing values of ~Gv , and at dislocations with longer Burgers
vector and at planes parallel to the particular habit plane which allows a maximum
relief of strain energy.
Strain ageing is a phenomenon associated with the segregation of free nitrogen and
carbon to the dislocations and precipitating on them. It is therefore very relevant to
study the principles of heterogenous nucleation on dislocations. In order to determine
the nucleation rate, the free energy barrierL1G* <16> that must be overcome by nucleation
must be understood. As indicated in the above equations, it is obvious that the
nucleation rate decreases exponentially as the critical free energy decreases. This
critical free energy term L1G* can be determined from the free energy - size relationship
during nucleus formation. According to the classical nucleation theory<9, 16) , the free
energy change that accompanies the formation of a nucleus on a dislocation
(heterogenous nucleation) L1G°, is represented in equation 3.29.
L1G° = V ( L1Gchem + L1Gc) + S~y----------3.29
where L1Gchem is the chemical driving force for nucleation, L1Gc is the volume strain
energy that is created by the formation of a new volume (nucleus) , y is the interface
energy and ~ is a y modifier that is associated with the presence of dislocations. V and
S are the volume and surface area of the nucleus Assuming that the precipitate is
spherical, the critical free energy L1G*, for the formation of a particle of critical
diameter d can be written as
L1G* = J6,r~ 3 y 3 I 3( L1Gchem + LiGc/----------------------------3.30
41
This Chapter hitherto has described mechanisms of nucleation and growth of a
precipitate. The following section is focussed on the description of three important
experimental methods of monitoring the kinetics of the precipitation process.
3.1.4 Experimental methods of monitoring precipitation kinetics:
A number of techniques have been used to study the precipitation process. These
include microhardness, internal friction measurement( 122' 123 ), electrical resistivity(!?, 18)
and more recently constant strain rate hot compression testing(l 9)_
In the chemical and electrochemical extraction methods (20 , 21 ), precipitates of the order
of 10 °A in diameter or less are extremely difficult to extract. While in the method of
evaluation by electron microscopy, extraction replicas vary in quality from operator to
operator. Moreover small precipitates do not always remain on the replica upon
extraction. Another disadvantage is that the area observed is extremely small,
sometimes making data obtained not statistically meaningful. Evaluation methods
using bulk properties as a measure of the precipitation process, i.e hardness and
electrical resistivity are dependable (l 3)_ But the results obtained should be carefully
interpreted as various other phenomena could influence the measurements.
It is prudent therefore to use more than one of these methods in order to clearly
evaluate the situation. Three methods of analysis are highlighted in this literature
review.
42
3.1.4.1 Electrical resistivity
The electrical resistivity or, inversely, the conductivity of pure metals follows a
periodical variation with atomic number similar to other electronic properties, but with
individual differences< 17• 18>. The conductivity of the noble metals is the greatest while
the transition metals are considerably lower. Electrical resistance in single crystals
varies with crystallographic direction, a characteristic, which is not very distinct in
polycrystals unless a strong texture develops.
The elementary interpretation() 7> of resistance assumes that it results from the vibration
of atoms which scatter the electrons moving through the lattice. These vibrations
increase with temperature. The mean kinetic energy of the vibrating atoms is given by
mean kinetic energy=½ 4,I V MX1 ------------------------3.31
where, M is the mass of the atom ; v is the frequency of vibration and X is the mean
square of the displacements from the mean lattice position.
The resistance R is proportional to the probability of scattering<22 >, which is
proportional to X 1 and inversely proportional to the mean free path of an electron.
Therefore the kinetic energy per atom for each of the three directions at 90° is given by
2,r 1 v 1 MX1 = l/lkT--------------------------------------3.32
Quantum theory associates an energy h v with a fundamental frequency of vibration v.
The relationships for temperature variation naturally involve functions of h v lkT.
Therefore the above equation becomes
X1 = (h 1 I 4 ,Ik OM)* T/0-------------------------------3.33
43
and
PIT= Constant * X 2-------------------------------3.34
where /JJT is the main resistance component that varies with temperature and 0 = h v
lk, a characteristic temperature. This, therefore gives the relationship between
temperature and resistivity such that resistivity increases with increasing temperature.
It is obvious that there will be a change in the frequency of atom vibration when there is
a change in the composition, i. e., the size of the atoms may vary resulting in varied
scatter of the electrons and therefore a different value of resistivity. The application of
resistance measurements therefore proves to be an excellent tool used to study the
metallurgical changes. For example, an important metallurgical change that can be
studied by resistance measurements is the progress of precipitation of a second phase
by nucleation and growth. A typical example is shown in Figure 3.8. The resistance of
an alloy system of A-Bis shown in (a) where a is the primary solid solution and p the
phase that precipitates. For a temperature T0 , and a composition x % of B, only the a
phase is present. The resistance of this is indicated by curve (b1). At room
temperatures, the resistance would be as indicated in curve (b2). This would apply if
there was no precipitation or a phase change. Equilibrium at T2 (room temperature)
would however involve precipitation to give a p phase of composition c2 leaving a of
composition a2. In practice an alloy would be quenched from above To and aged at T,,
between T O and T 2. In this case the p phase would have a slightly different
composition, c 1 and the matrix composition would move towards a composition a,.
The resistance of the alloy of composition x would be ao at To and b1 at T, at the start of
ageing. The equilibrium resistance at T I is p 1 the mean of a, and c1 weighted according
to the proportion of the phases. The rate of change in the resistance will depend on the
44
nucleation and growth rate and will be affected by several variables. A general form of
the curve is shown in figure c; showing a slow initial rate and then a faster change
followed by a decreasing rate towards the end of ageing. On cooling to room
temperature the final resistance will decrease according to the temperature coefficient
between T1 and T2.
The activation energy for diffusion, Q, plays an important role in precipitation process.
The rate of precipitation can be represented by the rate of change in resistance in the
following way:
dpldt = K exp - (A+Q/RJ)-----------------------------------3.35
where A is a second energy which is not necessarily constant with varying temperature.
Taking ~p from the start of precipitation at time t =O,
log Ap = log t- (A+QIRT) + log K---------------------------3.36

log t = B+ (A+QIRT)------------------------------------3.37
where B = log Ap- logK = constant for a constant change in resistance ~P-
The resistance method may make use of the classical four- probe technique, which
utilises two outer probes for current and two centre probes for voltage. The two
voltage probes are maintained at a fixed distance apart for all samples. The sample
dimensions are also maintained constant throughout a set of experiments. The
resistivity p is given by
p - RA/ L------------------------------------------3. 38
where R is the resistance measured on the samples, A is the area of cross-section and L
is the constant distance between the two voltage probes. The resistivity values so
measured are temperature sensitive, and also dependent on orientation of the samples.
45
It is therefore necessary to keep these variables constant. The changes in resistivity
measured are very small and accuracy in measurements necessitates the use of a high
precision instrument that is capable of registering such a minute change.
The errors associated with the resistance method include inconsistent readings as a
result of variation in temperature and contact between probe and specimen. The
sensitivity of the instrument must be very high in order to measure the extremely small
changes in resistance values.
3.1.4.2 Constant Strain Rate Hot Compression Test:
Earlier experiments attempted to follow the progress of precipitation through its effect
on the high temperature yield strength<23 )_ This procedure is the isothermal equivalent
of using hardness measurements or yield strength at room temperature after periods of
ageing or tempering at elevated temperatures. A shortcoming of this technique,
however, is that throughout the temperature range of precipitation, there is often hardly
any change in the yield strength.
The inadequacy of the above technique led to the development of an alternative test
method. This was based on the measurement of strain to the peak stress <23 •28 >, Ep, This
method could be used to measure the times and amounts of both static and dynamic
precipitation. The peak strain is sensitive to both strain rate and temperature. In
situations where all other parameters are constant, the strain is a maximum in a given
material subject to precipitation soon after the initiation of flow (i.e dynamic
46
~ .. p,
To
(a)
T1
T2
x.,. -e
p -- ------ (b)
-
- To
T,
T2
A .x ,.
B
p Cc)
TIME ~
-
Change in resistance during precipitation.
(a) phase diagram (b) resistance for equilibrium at three temperatures
and for quenching from T0 to Ta followed by ageing at T 1 (c) general
form of resistanctHime curve for ageing
Figure 3.8 Change in resistance during precipitation(Willard et a1< 22 >)
47
precipitation). By determining the dependence of peak strain on strain rate and
temperature, the precipitation start time can be detected more sensitively than the
conventional techniques.
Figure 3.9 shows three flow curves obtained in a 0.018%Nb low carbon steel, after
successively longer ageing times. It is observed that by increasing the holding time
before deformation, a distinct change in Ep is observed.
A large holding time results in a small peak strain<23 >_ This corresponds to the increase
in the amount of static precipitation during the holding period and therefore decreasing
amount of dynamic precipitation during the work hardening interval. A decrease in the
amount of dynamic precipitation in tum decreases the amount of retardation of dynamic
recrystallisation and therefore the peak strain. In the absence of static precipitation, a
constant and maximum Ep is obtained associated with the maximum amount of
precipitate being available to inhibit nucleation of dynamic recrystallisation during the
rising portion of the flow curve. An increase in the static precipitation, leads to a
decrease in potential for dynamic precipitation, and therefore a decrease in Ep. Once
all the element has been precipitated out, before deformation, there is no further change
in Ep. Thus the end of the first plateau (marked in Figure 3.9) corresponds to the
precipitation start time and the beginning of the second corresponds to the precipitation
finish time. From this data a precipitation time-temperature diagram is constructed,
illustrated in Figure 3.10.
48
45
T•mp .• °C
• 875
+ 900
40 A 925
a 975
o 1025
35
...
"'"'
~ 30
:;;
"
,c
w
a. 25
l=
z
c
a: 20
:;;
15
0 .Q. Ooi-0-0- 0 0 - - -
~
10'-------'------:------'-----_.__ _ ___,
10 1 10 1 10 3 104 105 10'
HOLDING TIME, s
Figure 3.9 The peak strain as a function of the holding time at temperature before
deformation. The first plateau indicates precipitation start time and the second,
the finish time(Weiss and Jonas( 23>).
,o,ol /
/
/
,;
/
/
•/
/
.
u
1000
I
I
/
(
w
a: I
...=> I
p
\
<I 950 s P,
a:
\•
"':I
Q.
...w 900
\. "·"'."
850
\
·, UNDEFORMED
0 05-,. C , 0,035% Nb
800 I 2 3 4 5 6
10 10 10 10 10 10
TIME
Figure 3.10 A precipitation time -temperature diagram for as obtained from data
in figure 3.9 (Weiss and Jonas( 23 >).
49
It has been observed this method apparently indicated " faster kinetics" than other
techniques< 23 )_ However this was explained as due to the differences in the amount of
prestrains used, the alloying content and other factors. The Ps line for dynamic
precipitation as deduced by this method is 'C shaped' and is located well to the left of
the others indicating that the curve represents the limiting case for static process when
large prestrains are applied at high strain rates.
3.1.4.3 Hot Torsion Test:
This method is similar in approach to constant strain rate hot compression testing.
Torsion samples are austenitised and then cooled to the testing temperature. The
testing is commenced within a specific period of time which prevents initiation of static
precipitation of the carbide /nitride. The samples are tested at varying strain rates and
temperatures. The flow curves are plotted between equivalent stress and strain as
shown in Figure 3.11. The equivalent strain at the surface is given by
&eq = r I (3)112 = R 0 I (3)112------------------------------3.39
where y = surface strain, R = specimen gauge radius, 0 = angle of twist and L is the
gauge length.
The equivalent strain is given by
&eq - rI (3/12 ----------------------------------------3.40
and equivalent stress is given by
a eq = T (3)1 12------------------------------------------3.41
50
.084 Al - .016 N
f 150
-
~
Ill
6.10" 1
J.I0· I
Ill
lo.I
~ 100
Ill
I-
z
II.I
..J
<r
> ,o
3
0
II.I
T•9oo•c
0 0., 1.0
EQUIVALENT STRAIN
Figure 3.12 Flow curves in terms of equivalent stress versus equivalent surface
strain for a low carbon steel determined at 600 °C at nine strain rates (Michel and
Jonas<21>).
where -r is the surface shear stress such that
a eq = T (3/12 I 21rR3 ( J+m+n)-------------------------3.42
where T is the measured torque, m is the strain rate sensitivity index given by (8 ln TI
cS ln 0 )0 and n is the work hardening exponent given by ( cS ln T / cS ln 8)0
The flow curves in figure 3.11 indicated a peak in stress (indicative of dynamic
recrystallisation) and the peak strain increased with the strain rate and decreasing
temperature. Figure 3.12 represents the plots between peak strain as a function of strain
rate. Similar to the hot compression technique, the start and finish times of
precipitation can be obtained from the hot torsion tests.
51
./tl/
70
j
875 • C
..."'"'
60
//j
--·
0.05"/o C, 0.0!15Nt, ----·--
-·-1·-·
...
a::
"'
~
...
Q.
50 _,,,.,,,,.-•'• /•
/. EFFECT OF
/ SOLUTE
...
0
• EFFECT OF
z
:.i / FINlc: PPT'S /•
~ 40
"' _/ ./
!IO
----,·--
EFFECT OF /
/ 0.0 5 "1eC
COARSE PPT'S ~
20 ---~ j ------- .
-4 ,ciz
_,
10 10
STRAIN RATE i 1
fo)
Figure 3.12 Flow curves in terms of equivalent stress versus equivalent surface
strain for a low carbon steel determined at 600 °C at nine strain rates (Michel and
Jonas< 27>).
Following this chapter on the discussion of precipitation kinetics and the experimental
methods of measuring these kinetics, is Chapter 4, which will focus on strain ageing and
factors affecting the process.
52
Chapter 4 Strain ageing of low carbon steels
CHAPTER4
STRAIN AGEING OF LOW CARBON STEELS
53
STRAIN AGEING OF LOW CARBON STEELS
This chapter defines the process of strain ageing and the effects of strain ageing process
on the mechanical properties. Subsequently, discussion is focussed on the factors that
affect strain ageing, with special emphasis on the compositional effects.
4.1 GENERAL FEATURES
Strain ageing is associated with the yield point phenomenon in which the strength of a
cold worked material increases and the ductility decreases on heating or ageing at a
relatively low temperature after cold working<4. 6>. Features of this phenomenon are
summarised in Figure 4.1. If a sample is left at room temperature after it has been
loaded to a stress beyond its elastic limit, on further testing the sample would show an
increase in the strength properties while recording a decrease in the elongation. This is
the main manifestation of the strain ageing process. The occurrence of strain ageing is
due primarily to the locking up of dislocations by interstitial carbon and nitrogen
atmospheres; although, heterogeneously nucleated precipitates may also play a ro1e<29,

30-31)
Prior to describing the effects of strain ageing on mechanical properties, it is necessary
however to define a few of these mechanical properties. Deformation in materials can
be of two types - elastic and plastic. In elastic deformation, the material regains its
original shape after the load is removed. This type of deformation is called elastic
54
deformation (marked by OE in Figure 4.1). However there is an upper limit to loads
that can result in such elastic deformation. When loads beyond this limit are applied,
the material begins to undergo a permanent change in shape. This is plastic deformation
(all deformation beyond point E in Figure 4.1), which involves the large-scale
generation and movement of dislocations.
AY =chan1• in yield str•ss due to strain a1ln1

AU =chan1• in U.T.S. due to strain a1in1
AE - chanp in elonption due to strain a1in1
STRAIN
Figure 4.1 Stress-strain curve for a low carbon steel strained to point A, unloaded
and then restrained immediately-curve (a) and after ageing-curve(b)( Baird<29>).
Engineering stress is defined as the load borne per unit area.
cr - P/ A -------------------------------------------4. 1
55
where P is the applied load and A is the initial cross--sectional area of the stressed
material. Engineering strain is defined as the ratio of the change in dimensions of
the specimen, from its original length.
E= (lr-10 ) / 10 --·-----------------------4.2
where lo is the original length of the test specimen, lr is the final length of the
specimen. Strain is usually expressed as %elongation.
Ultimate tensile stress: This is the maximum stress that a material can withstand
without failure (marked as U in Figure 4.1 ).
Yield stress: This is the minimum stress at which the material starts to yield plastically
(i.e a permanent change in shape).
Work hardening exponent: This measures the capacity of the material to harden as
deformation proceeds beyond the plastic strain at yield stress. Strain hardening occurs
due to multiplication of dislocations, which eventually become entangled, therefore
causing a resistance to further deformation and thereby resulting in an increase in the
strength of the material.
Figure 4.2 shows the variation in the mechanical properties as ageing proceeds at room
temperature. It is observed that the yield-point elongation and yield stress increase
continually from the commencement of ageing, while there is little change in the tensile
strength or ductility even after ageing for a week<27-33 >_ Strain ageing leads to a general
rise in the level of the stress strain curve and an increase in the rate of work hardening
during the early stages of straining after ageing. The total strain at fracture (%reduction
in area), is reduced by the ageing process. Any process which affects the level (higher
56
stress values) of the stress-strain curve more than the work hardening rate leads to a
decrease in the absolute ductility as well as the uniform elongation<29-33 >_
Various experiments have proven that the effect of ageing on the mechanical properties
is quite dependent on the amount of working (i.e the amount of plastic strain) the steel
has been subjected to <4-6• 29•30• 31 • 33 >_ It has been observed that the changes in the tensile
strength and ductility in a more heavily worked steel was much more pronounced than
in the lightly worked steel(31)_ By contrast, the change in the yield stress and the yield
point elongation becomes less as the amount of working increases. The yield point
elongation is affected by the amount of working in a similar manner as the yield stress,
the maximum change occurring after a low degree of plastic working. A more detailed
discussion of the effect of strain ageing on mechanical properties is presented in section
4.4 of this chapter.
It has been generally observed that steel has a higher solubility for nitrogen than that for
carbon. Specifically, nitrogen solubility decreases from 83.9 ppm to 0.079 ppm at 300°
C and 25° C, respectively while carbon solubility decreases from 6.8 ppm at 300° C to
0.003 ppm at 25° c<2 - 6• 14• 29 -33 >_ As a result of a higher solubility of nitrogen coupled,
with a very slow and less complete nitride precipitation during cooling, nitrogen plays a
. the stram
greater ro1e than carbon m . agemg
. of plam
. carbon stee ls(2-6' 14 29-33)
' .
57
ZDAYS IWEEK IMOHTH 3MONTHS IVEU
TOTAL ELONGA"TION (2°G.L)

50
>
~---.---1--1---- f-x-1-l
5-40
~~
..,-
:,
0
30
.
1-1-1 X I
X
UNIPORM ILONGATICN
X
X .
I
x I x-l-:--it-l-4
X I
-g
! 201-----------------'
"'a
t;z
~
ULTIMATE TENSILE STRENGTH
;~.,. 195
19
I
l
1 - i - - x - - x.,..
YIELD
l ,._
t
POINT ELONGAT::.:-+-t
I
x
-·-~ I
u;,!.
~-
i-
l
I
/--x x x--x----1
X
x I
X
~
w 01----="---------...__,,_.,,.,,.
YIELD S T R E S ~ :
. '
X
JC X l
X/ X
•/x
. /.,_,,...
100
8 L------i......----..__ _ ____,,......~
0 100 1000 10,000
AGEING TIME (HOURS)
Figure 4.2 The effect of ageing on the properties of mild steel temper rolled
1.4% ( B.B Hundy <4>)
Strain ageing is an important phenomenon that needs to be controlled since it not only
increases the yield stress after ageing and results in a decrease in ductility, but it also
gives rise to stretcher strains or Luder bands due to localised heterogenous deformation.
The process is also responsible for the occurrence in the stress -strain curve of what is
termed the Portevin-LeChatelier effect or dynamic strain ageing. This is a
manifestation of the non- uniform character of plastic flow< 35 -49) and is described in
detail in section 4.5.6.
58
There are a number of theories to explain strain ageing, that are described in the
following section.
4.2 THEORIES OF STRAIN AGEING
Early theories of strain ageing assumed that the process was either due to some form of
strain-induced precipitation within grains or reformation of grain boundary films which
had ruptured during initial yielding<50• 51). However these early theories could not
account for all the observed changes that occur during strain ageing and therefore were
generally not accepted. A more applicable theory that was proposed later was the
formation of solute atmospheres around the dislocations pinning them, thus leading to
an increase in the yield stress. The kinetics for this atmosphere formation as suggested
by Cottrell and Bilby< 52) was based on an assumption that a driving force existed which
attracted the solute atoms towards a dislocation. The driving force, generally referred
to as the drift force, is associated with a decrease in the dilational energy of a solute
atom in sites near the tension side of an edge dislocation as represented schematically
in Figure 4.3. The decrease in the potential energy towards the core of the dislocation
gives rise to the drift force attracting the solute atoms towards the dislocation. It has
been shown by Nabarro and other workers, that a similar force would exist near a screw
dislocation also <50)_
The number of solute atoms that would reach a dislocation (edge or screw) in time t; Nt
is given by
N t = Tl o 3( 1t /2) 113 L (ADt/RT) 213 ---------------------4.3

59
where 110 is the average concentration of solute (atoms /unit volume); L is the
dislocation density; D is the diffusion coefficient of the solute atom and A defines the
magnitude of interaction between the solute atom and the dislocation.
'Sr----r~-r~----liliC-
>-
<.,
Ck:
w
z.___...,,,,
w ...../
,,.... Core region
I
I
I
Figure 4.3 Schematic diagram showing potential energy of a solute atom as a

function of the distance R from the centre of a dislocation (J.D Baird<50>).
The value of A has been estimated in the range of 1.4 to 3.0 x 10 ·20 dyne cm 2 for both
carbon and nitrogen in iron <50>. It was estimated by Cottrell -Bilby that a dislocation
would be saturated with carbon when 1-2 atoms of carbon per atom plane of dislocation
had segregated to it< 50, 52>. Useful information about dislocation densities L, can be
estimated from this equation, if the other parameters are known. Equation 4.3 can also
be used to estimate the atmosphere densities at various rates of strain ageing (rate of
strain ageing would be given by rate of increase in yield stress with time) if the
dislocation density can be measured experimentally. However, this equation is relevant
only at atmosphere densities below the saturation level as stated by Cottrell and Bilby
(52)
As saturation is approached, back diffusion from the core region tends to
counterbalance the inward flow of solute atoms to dislocations due to the drift force.
60
Chapter 4 Strain ageing of/ow carbon steels
Further, it has been suggested that relief of the dislocation stresses by the segregated
atoms may reduce the drift force <51 )_
Harper modified the above equation so as to accommodate the decrease in the
interstitial solute content surrounding the dislocations as strain ageing proceeds< 50, 51 ' 53 )_
Based on an assumption that the rate of segregation of interstitial solute atoms at a
particular time would be proportional to the solute concentration remaining in the
matrix between dislocations, the following equation was derived< 51 , 53 ),
W= N!Nt = 1-exp [ -3L {1t/2) 113 (ADt/kT) 213 ]--------------4.4

where W is the fraction of solute that has segregated to the dislocations, N is the number
of solute atoms that would reach a dislocation and N1 , the total number of solute atoms
present and the other terms are as in equation 4.4. Equation 4.4 can be restated as
In (1-W) = - (t /-c) 213 ------,---------4.5

where -c is a constant. The preceding two equations do not take into account the
saturation or back diffusion effects and therefore hold good only for low atmosphere
densities and the early stages of ageing.
The kinetics of the ageing process has been studied by a number of investigators by
measuring the change in the concentration of interstitial solute remaining in the ferrite
lattice. However, this is based on the assumption that all solute leaving the lattice
segregates to dislocations. The change in the solute concentration can be measured
either by the internal friction method (Snoek peak) or by electrical resistivity change.
The former technique has generally found to be more accurate <51 , 54 )_ Extensive work by
a number of investigators (listed in Table 4.1) revealed that the ageing kinetics
61
predicted by Cottrell- Bilby equation was satisfied only up to about 50% completion of
the total ageing process, while Harper's equation (equation 4.4) held good up to near
completion of the ageing process< 51 >. In general, the activation energy of the ageing
process was found to be equal to the activation energy for diffusion of the interstitial
solute present<Sl)_ Although several workers agree with the adequacy of the Cottrell -
Bilby and the Harper equations, one serious limitation is that these cannot be applied to
strain ageing situations with a high solute concentration <51 >. From Table 4.2, it is
evident that Carswell's studies on Fe-N alloys containing as much as 0.003% nitrogen
have shown that the Harper equation satisfactorily explained kinetics <50, 51 >. It is also
apparent from Table 4.2 that there is no mention of alloys containing more than 0.003%
of which successfully obey Harper equation <50, 51 >. This limitation is apparently due to
the fact that strain ageing can be associated with more than atmosphere formation.
Other theories therefore seek to explain strain ageing in two steps - the first step is
associated with atmosphere formation and the second, with precipitate formation
following atmosphere formation.
4.2.1 Atmosphere formation
A lack of knowledge of the exact equilibrium form of a solute atmosphere at the core of
a dislocation currently hinders the formulation of a satisfactory theory for the proposed
first stage of strain ageing <51 >. As a matter of approximation, the Maxwell - Boltzman
law gives the solute concentration at a few atomic spacings away from the dislocation
core.
C =C O exp ( - ~ /kT)------------------------------------4. 6
62
where C0 is the average concentration in the crystal and ~ is the interaction potential or
binding energy between the solute atom and the dislocation.
For an edge dislocation,
~ = A (sin 0 ) /R ---------------- ---4.7
where R and 0 are the polar coordinates of the solute atom with respect to the
dislocation line and A is the solute - dislocation interaction parameter. These equations
give an impossibly high solute concentration when R ~ 0< 51 >. It was suggested by
Cottrell and Bilby that the relief of dislocation stresses by segregated atoms would give
rise to a saturation condition in the core region {R<1OA0 ) when it contained one
solute atom per atom plane of the dislocation< 51 >. It was postulated that these atoms
would tend to arrange themselves in a line just below the extra half plane of an edge
dislocation to give a condensed atmosphere. Surrounding this, a dilute Maxwell -
Boltzmann type distribution of the solute would be present, containing one additional
solute atom per plane of dislocation.
However it was suggested by Beshers that the distribution of solute atoms near a
dislocation core follows a Fermi-Dirac distribution dictated by energy levels rather than
a Maxwell-Boltzmann type of distribution<51 >. This would imply that solute atoms have
various energy levels associated with them and arrange themselves around the
dislocation core in the lowest possible energy states. At higher temperatures some
atoms raise their energy levels due to the additional thermal energy supplied. A serious
limitation of this latter theory is that it is not sufficiently quantitative to calculate the
amount of solute atoms near a dislocation core with any confidence.
63
In the dislocation potential field, the interstitial solute atom acquires a drift velocity 'v'
that would allow for it to be attracted towards the dislocation.
v = - (DI RT) d~/ dR-------------------4.8
This will be the controlling step governing the early stages of strain ageing when the
concentration gradients arising due to segregation are negligible <51 >. In this case the
Cottrell - Bilby equation should be applicable. But with time, the solute atmosphere
would have attained an appreciable value, causing the onset of back diffusion. This
counteracts the drift flow, and at equilibrium, the two fluxes of solute atoms balance
each other. Further, atmosphere formation is results in the segregation of solute from
the matrix, thus causing the depletion of the interstitial solute from the matrix
(surrounding the dislocation). Cottrell - Bilby's equation does not account for this, thus
explaining the deviations from the equation in the early stages.
Bullough and Newman studied the deviations from the Cottrell-Bilby kinetics and came
up with a theory in which the potential field around a dislocation is considered to be
radially symmetrical, and not as described by the Maxwell - Boltzmann distribution<55 ,
56>. They also assumed that the interaction potential between a solute and a dislocation,
is not affected by the solute atoms that have already segregated to the core. They
showed that up to 30 - 40 % completion of the ageing process, the predicted kinetics
followed the Cottrell - Bilby equation<51 , 56>. In the early stages of the process, diffusion
assisted the segregation process by supplying solute to a depleted zone around the
dislocation, but in later stages, back diffusion from the core retarded strain ageing.
Therefore the overall kinetics of the strain ageing process did not obey the Cottrell-
Bilby equation.
64
Atmosphere formation was found to account for only a small fraction = 10% of the
solute which was predicted to segregate to the dislocations< 51 • 56 >. However, in most
strain ageing cases, experimentally it has been observed that 100% of the solute was
found to segregate. Therefore it was concluded by Bullough and Newman that
atmosphere formation, alone, was not responsible for strain ageing< 51 >. During the stage
of atmosphere formation, back diffusion from the core was found to be more
predominant than the depletion of the matrix surrounding the dislocation in slowing
down the rate of solute atom segregation with time. This meant that the correction to
the Cottrell-Bilby equation as postulated by Harper was not important in this case and
does not fully explain the observed kinetics of Bullough and Newman as evident from
Table 4.1. It was therefore believed that strain ageing occurs in two stages, the first
being atmosphere formation and the next, precipitation on dislocations.
4.2.2 Precipitation on dislocations
A review of literature shows that there is very little agreement between the predicted
and observed kinetics in the stage of atmosphere formation despite the initial success of
the Cottrell - Bilby equation. However, there appears to be a good agreement between
the observed and predicted kinetics in the precipitation stage of the ageing process.
The densities of solute atmospheres formed during strain ageing as experimentally
estimated by internal friction and electrical resistivity techniques are often well above
the saturation limit for atmospheres predicted by the Cottrell - Bilby equation< 51 >. In
65
Table 4.1 Measurements of strain ageing kinetics in quenched Fe-C and Fe-N alloys (J.D Baird<51 >)
.I .I •Asiq Solute Content (wt.%)

..
Calculated Dhlocatlon
. . ..
Demlq,ftf.Solllte
lnvestlptor !Method• I Preatrain % Temperature, 0 C. C N Dcmlty cmkm1 x 10-1• Atoma/Atom •·
Plane .,
H.\Jut!R lU ' I.F. 5 I 30
II 0·015 -- 7·7 13
-
i
10
15 i 30
39
0·009
0·013 - 10·2
15·7
6
6
DAHL AND Luca
!
E.R. 4·5 120 I 0·015 - . 0·82 75t
II
i 5·1 ISO 0·015 -- 1·67 45+
11st
;
5·3 90
I 0·018
I
0·95
THOMAS AND La.u:
I
I.F. 7 i
24-54 I - 0·015 I 7·7 11·5
---
IT
7 35-67 0·015 6·6 15·6
7 35-67 0·0095 I S·O 13·1
~
I 7 I 35-67 0·0055 4·0 9·-4
I
i
I -- II
PITSCH AND LOCJCB HI
I I.F. 4·8
4·8
I
I
90
120
0·01075
0·01575
2·6
2·2
-40•5
58
I
i
i
4·8
4·8
149
170
0·01835
0·01915
-- '
I 3·0
2·4
66
65·5
~CUN AND HBu.ml 111
i
I.F.
i
12·2
12·2
20-1-40
2~140
0-0203
0·0203
-- I 13·6
13·8
13
13
'
'
!
12·2 20-140 . 0·0127 - 13·2 9
12·2
12·2
5-2
20-140
20-140
20-140
0·017
0·0185
0·0185
--- 13·2
17·
11
11
10
15
WU.SON AND RUSSBLL ' E.R.
30·3
4
20-140
20 and 60
0·0185
0·01
-
0·004
36·4
10
4
12
I
KosTl!ll, BANGIRT AND HAHN 41 I

I
I.F. 33
I
40 0·018
- -..
- 30
-- -- ·- -. . ..
66
addition, the alloys that have been shown to exhibit strain ageing (Table 4.2) contained a
high concentration of carbon and nitrogen. Atmosphere formation alone could not
account for this solute content. Therefore it was assumed that the solute atoms, in
addition to the formation of atmospheres around the dislocations were also
heterogenously precipitating on dislocations. It was suggested by Bilby that the solute
atoms drawn into the dislocation core could diffuse along the core to feed the precipitate
particles spaced at intervals along the dislocations(51 • 52• 57>.
However the fact that atoms in the dislocation core could feed the precipitate particles,
was refuted by Bullough and Newman on the basis that the binding energy of a solute
atom to a dislocation is greater than that to a precipitate particle(53 >_ But this was
disproved by Harper, Thomas and others, who studied quenched alloys; and argued that
there are too many solute atoms to be accommodated in the low energy sites at the
dislocation cores. Therefore, once these energy sites are occupied, further atoms,
which diffuse to the dislocation due to the drift force, occupy higher energy sites. This
makes the situation energetically favourable for atoms in the higher energy sites to
diffuse along the dislocations to feed precipitate particles (lower energy).
67
( 'hapter 4 Strain ageing <~(low carbon steels
Table 4.2 Measurements of strain ageing kinetics in slowly cooled or quench-aged Fe-C and Fe-N alloys(J.D Baird<st >)
Solute Co11tent Calculated fJul ~ i ;·: ~ _,?

0 ~:: _·
IDwatlptor Method' I PrestraJn Heat Treatment I A,m1 (wt.%) DJalocadon of Sohate llatdill ·.. '.;
% Temperature, °C Dt111lty cm/ Atoma/Atom' fo8owl4 ·., ·.
C N cm1 X10-" Plant . , . ·•..
-----1---1---1
E.R.
-------!
Slow cooled to 200°c, I
1
1
20 and 60 - 0·0022 5•1

,, .-
"--"
0- - , ·• •
WIUON
Rusm.t'
AND4
aged anel then quenched.
Wet hydrogen treated
'"l
. . 1/
UllllaP ' , . '
nn,... · .,,
aAMIJ .. ....,;
4
8 hr, quenched from
500°C. .
20 and 60 0·0005 - ..... 4
~.·
aptoeG% ,·
CA;lswll.L" I.F. 3 Quench aged 180° 20 0·0031 9·6 N01 • } / , I
3 Quenclt aged 120° 20 I 0·001 JO N01

3 Quench aae<f 80° 20 0·0009 10·7 N~
Harper I
3 Quench aged 60° 20 I

I
0·00083 11·4 "'01 eqllldoa
2 Quench aged 120° 20 I 0·001 7·5 N~ ltfint..
2 Quench aged 80° 20 0·0009 8·0 ..,H
2 Quench aged 60° 20 1= 0·000831 8·6 NO~
IKosra, BANODT I.F. 33 Normalised. 40
j
j 0-0032 - I Harper
I
AND HAHN .. I equation
i
•E.R. •Electrical resistivity, I.F. ""'.Internal friction,
68
All of these workers have based their analysis on the kinetics of the precipitation on the
dislocations, assuming that the dislocation core is a cylindrical region in which the
diffusivity of carbon or nitrogen is sufficiently high to be taken as infinite<51 , 57 >_ While
Bullough and Newman assumed various rates of transfer of solute atoms across the
core - precipitate interface< 51 • 53 >, Ham assumed that the transfer of solute atoms from
the dislocation core into the precipitate was sufficiently fast for the dislocation core to
act as a sink for these atoms< 51 >. These two calculations agreed at higher rates of
transfer. Apart from the initial (small) time for atmosphere formation, the kinetics are
predicted to follow
In (1-W) = - (th )-------------------------------------4. 9

which again, however, does not agree with the observed kinetics.
Bullough and Newman further assumed that the drift flow is important in controlling
the kinetics of the ageing process, more importantly the rate of growth of precipitates
on dislocations. Accordingly, they set about finding a model of the precipitation that
would explain the observed kinetics. Rod- shaped precipitates were assumed to form
along the dislocations centered at the dislocation core <50, 51 >. The chemical binding
between the precipitate and its elastic interaction with the dislocation strain field was
assumed to stabilise the precipitate. In order to find the exact order of the time
constant, they also assumed that the transfer of solute atoms across the matrix-
precipitate interface was the rate-controlling step. This transfer also decreased as the
precipitate grew, possibly as result of an increasing hydrostatic pressure build up inside
the precipitate. These assumptions led to the observed kinetics following an equation
close to that developed by Harper. The above explanation by Bullough and Newman
69
assumes a high activation energy for the interface transfer process. However, without
this assumption the process kinetics would follow equation 4.9.
Equation 4.9 does not give the observed kinetics of the ageing process if a uniform
dislocation density is assumed. In practice, however, it has been observed by Keh, that
the dislocation density is not uniform throughout the materia1< 5s, 59 >_ Keh has shown
that in regions of clusters and cell walls, which is assumed to occupy one-fifth of the
volume, the dislocation density is about four times the average dislocation density.
Therefore, the density in the remaining four-fifths of the volume must be only about a
quarter of the average density. The time constant (i-) was found to be inversely
proportional to dislocation density <51 >. The overall rate of segregation m an
inhomogenous structure as predicted by Bullough and Newman can be given by
1 -W = 1/5 exp (- t / 't 1) + 4/5 exp (-t /16 't 1) ------------4.10
and a plot between log log (1 -W) and log ( t / 't 1 ) gives a reasonably good straight
line relationship.
Observations by Nacken and Heller showed that precipitates formed as a result of
segregation of the solute atoms on dislocations did not redissolve upon heating as easily
as those produced by quench ageing< 51 >. And overageing was found to be more rapid
and complete during quench ageing than during strain ageing. This indicates that during
the early stage of precipitation on dislocations, the solute atoms are more tightly bound
than if they were in the form of discrete particles formed during quench ageing. These
observations support Bullough and Newman's hypothesis that a dislocation - precipitate
is a specialised form, partly stabilised by interaction with the elastic strain field of the
70
dislocation. With these assumptions, they found that they could explain the kinetics as
shown by Harper's equation well.
Some deviations from the Harper equation were noticed, and these deviations were
attributed to the precipitation of solute between dislocations. Studies by Leslie et al,
confirmed this phenomenon by observations made in some commercial steels, where
fine precipitates were noticed between dislocations< 5B, 59 >_ This precipitation has been
observed to occur up to very high prestrains, especially in regions of low dislocation
density.
Hundy developed express10ns relating the time of strain agemg of steel at room
temperature to that at higher temperatures<4' 5>. Assuming that carbon causes strain
ageing, the equation is
Log 10 t r!t = 4400 (1/f r - 1/f) - log 10 Tff r·----- 4.11
While, for nitrogen, the equation is
Log 10 t r!t = 4000 (1/f r - 1/f) - log 10 Tff r ------------------4.12
In these equations, 'tr' is the ageing time at room temperature, Tr, and t is the time of
ageing at elevated temperature T. These equations are based on the assumption that the
number of solute atoms are the same at room and elevated temperatures, which has been
found to be true only up to about 200°C.
4.2.3 Effect of dislocation sources
Cottrell postulated that if a specimen is prestrained in one direction, all inclusions
capable of acting as dislocation sources under this stress system will be inactivated<60>.
71
This should help in achieving a return of the yield point in ageing, if restraining is in
the prestrain direction rather than in any other direction. Studies by Kennett and Owen
have revealed that inclusions elongated by rolling act as more efficient dislocation
sources during transverse tensile straining than by straining in the direction of
rolling< 61 >. However studies by Tipper showed no effect of rolling direction on the rate
of return of the yield point<35 >_ Experiments by Mura and co-workers revealed that a
steel aged at 30°C until it showed a yield point on testing at the same temperature, did
not show a sharp yield point when tested at -196 °C after the same ageing treatment<62>.
This could be explained by the fact that inclusions or precipitate particles may also give
rise to dislocations by thermal stresses when the temperature of the specimen is
changed.
Suggestions were made by Leslie and Keh that the stress required to activate grain-
boundary or inclusion sources may be raised during strain ageing by the segregation of
solute atoms<63 >_ This could be responsible for the slow secondary rise in yield point
extension that takes place on prolonged ageing after all types of prestrain.
4.2.4 Factors affecting strain ageing:
The factors that determine the magnitude of strain ageing are:
• the dislocation density
• the concentration of interstitial solutes namely, carbon and nitrogen
• the time available for diffusion to occur
• the temperature at which diffusion takes place.
72
Strain ageing can be of two types - static strain ageing and dynamic strain ageing<29).
Static strain ageing is referred to that process of ageing that occurs in a previously
strained material that is left exposed to some temperature (typically room temperature)
for a period of time. When this material is tested for mechanical properties after this
period, it is found to exhibit strain ageing (rise in strength or a decrease in ductility).
Dynamic strain ageing, on the other hand occurs during the process of straining itself.
The following sections describe the two phenomena.
4.2.5 Static Strain Ageing
Static ageing can be divided into four stages as described from the work of Wilson and
Russell< 56 ' 57 ), illustrated in Figure 4.4. Stage 1 of the process shows a rise in the yield
stress and the yield point elongation (Luders strain) while the other properties remain
unchanged. There is however a fall in the strain hardening exponent. During Stage 2
of the phenomenon, the yield stress continues to increase while the yield point
elongation remains constant. The flow stress rises while the rate of strain hardening
remains constant. In Stage 3, the strain hardening rate increases giving rise to an
increase in the ultimate tensile stress and a decrease in the elongation. However there
is a decrease in the uniform elongation. Stage 4 leads to an overageing effect, which
results in softening. Stage 1 is purely the yield point phenomenon while stages 2 and 3
reflect strain/age- hardening processes.
Wilson and Russell proposed that during Stage 1 of strain ageing, Cottrell atmospheres
were formed around the dislocations, which were sufficient to completely pin the
73
STAGE I STAGE II STAGEIII
~ 8
" 6
"I: 4
i LOWER YIELD STRESS
... 4
Q
.... 2
i 01----+----r
~
# 0
~ -5 ELONGATION
-10
TO FRACTURE
0·04
i--;---r--r-"===*=:::::::"1
,ao-02
0
10 10 IOI I~ 105
AGING TIME AT 6QOC,mln
Figure 4.4 Four different stages of static strain ageing (Wilson and
Russell <56 •57>)
dislocations< 56 • 57 >_ These atoms were dispersed on further straining, thus resulting in
the freeing of dislocations while the other properties remain unaltered. In stage 2 of the
process, the hardening that comes about was postulated to arise from the pinning of
dislocations by fine particles(29• 30• 33 >. It was further suggested that it was easier to
activate fresh dislocations on further straining rather than unpin the already strain aged
dislocations. This led to Luders strain achieving a constant value and marked the
beginning of the strain age hardening stages 2 and 3. The onset of stage 3 was
delineated as the point when the fine precipitates became sufficient in size to accelerate
74
strain hardening. During stage 4 of the process the increase in Luders strain was due to
the precipitates going into solution and segregation along grain boundaries leading to
an increase in the unpinning stress<64 • 65 >. The rate of ageing and the final yield and
tensile stresses increase with increasing solute content<29• 30>. The ageing index has
been defined as the difference in the tensile strengths or the yield strengths at room
temperature and the temperature of strain ageing< 4, 66>. Alternatively it could represent
the difference in the strength values at two different times, for example on receipt and
after storage at room temperature after a few days.
Static strain ageing has been found to be affected by the following factors< 4• 29• 30•
33).
o composition
o temperature
o pre-strain
o prior heat treatment
The effect of each of these parameters on strain ageing is discussed in the following
sections.
4.2.5.1 Effect of Composition
Solute alloying additions can contribute in two ways to strain ageing. There are solutes
which lock dislocations and diffuse quickly to produce strain ageing while there are
75
other solutes which can alter the concentration or mobility of those solute atoms that
directly produce strain ageing( 33 )_
The first class of solutes must have a high diffusion coefficient such as interstitial
alloying elements in ferrite, i.e, carbon, nitrogen, oxygen and hydrogen. While oxygen
and hydrogen do not appear to be the main elements causing strain ageing, carbon and
nitrogen have been proven to be very important<3, 33 )_ The effectiveness with which an
element influences or causes strain ageing in steel is based on
• its solubility in ferrite;
• its diffusion coefficient and
• the degree to which it locks the dislocations.
a) Nitrogen:
Steel has a very high propensity to absorb nitrogen at high temperatures from the
atmosphere during steelmaking<3, 33 • 66' 67 ). Once nitrogen is absorbed into the metal, it
is difficult to remove the element. Vacuum degassing removes only 10-20%<66' 67 ).
Figure 4.5 shows the Fe-N equilibrium diagram in the Fe-rich region< 3, 14). The
solubilities of the two main phases, Fe4N and Fe 16N 2 at various temperatures are shown.
The variation in the solubility of nitrogen in ferrite as a function of temperature, as
studied by Leslie is shown in Figure 4.6(3, 14). It is seen that for normal nitrogen contents
of 0.002 to 0.01 %, the solubility is only exceeded during cooling below about 300 °C.
However, below about I 50 °C, the mobility of nitrogen is quite low. The extrapolated
76
solubility of nitrogen at room temperature is 104 to 10-5 wt%. The higher equilibrium
solubility of nitrogen and the reduced rate of precipitation of nitrogen in the presence of
manganese results in an amount of nitrogen in solution which is at least one order of
magnitude higher than the amount of carbon in solution for most commercial grades of
steel 0 3>_
Studies using internal friction have revealed that peaks corresponding to nitrogen and
carbon disappear as strain ageing proceeds while a new peak appears at a higher
temperature, as shown in Figure 4.7. This new peak was found to be due to the carbon
and nitrogen atoms, which lock up the dislocations. It was believed that the
supersaturation of nitrogen was relieved by the presence of fresh dislocations.
However, later work by Thomas and Leak showed that the equilibrium solubility of
nitrogen is less in the presence of fresh dislocations than in their absence, as illustrated
in Figure 4.8< 69' 70>. It has been shown that the binding energy of a nitrogen atom to a
dislocation is about 0.75eV while the binding energy in the precipitates of Fe4N and
Fe16N 2 is 0.25 - 0.35 eV in the former and even less in the latter. Thus the N atoms are
more firmly bound to dislocations than to iron in nitride particles. This suggests that
during straining, the nitride precipitates dissociate, thus providing a steady source of
nitrogen for strain ageing. Support for this theory came from a study by Dijkstra who
found that the solubility of nitrogen in the presence of nitride particles was 0.012% at
300° C and 0.02 wt% at 400° C, while solubility in the presence of dislocations was
only 0.002% at 300° C and 0.006% at 400° c<68>.
77
N1tro9e"I la,. •1.1

C :;2 :>? '.)4 05
900
800
u 6GO
•..,, 0.0"
•~ 500
.,...
ci
f 400
~
1000~--,~-~~~..,._.....,,..~---~_,.......- - - J
002 o 04 006 ooa 010 o ,z o 14
N1tr09en ( wt%J
Figure 4.5 Ferrite field showin? equilibrium between Fe-N2 gas, Fe-Fe4N and Fe-
Fe16N2 (Bever cited by Leslie<3, 1 >)
IOO 0-IOO
-I
0050
0
i: 0025
z !z1£1
0-010
8-2
~ §
3
';t
e.,
I,) -3
9 0·00025
.4L,,__......__ _ _ ___,..,,.--~-~-=---="'==----=-O·OOOI
3·2 2·8 2·4 2·0 1•6 1·2 0·8 0·4
I xl01
i'
Figure 4.6 Solubility of carbon and nitrogen as a function of temperature

(Leslie<3>).
78
Freq. • I cp•.
DI&
.00
Temp. •c
Figure 4. 7 Internal friction curves of a dual solid solution of carbon and nitrogen
in ferrite vs temperature. Curves a and b are the internal nitrogen and carbon
peaks(122).
100 125 150

TEMPERATURE
250
:c
200
O•OI-..:.:;::.;::;...--=.::;.=,-~~--~;;;;.-.~.,-~,....,,..,
,,,,,
,
~ ,,,,,
,
0 ,,,,,
..... ,,,,,
,,,,,
z
,
~z
/
,,,,,
,
O•OOI ,,,,, _ _ 1N E0Ul.l8RIJM WITH
,,, ;
PIIECIPtTATED NITRIDE
/ IN EOUILIBRIJM
Q •0005 , ' ---- - WITH DISLOCATION
"" ATMOSPHERES
O •00O1'-.e=-"__2_.·..... s
6-~2""""".4~~2~-2-::---~26-::-o=--~,.
.
I ,c 10
T
Figure 4.8 Solubility of nitrogen in equilibrium with dislocations and precipitated
nitride as a function of temperature (Thomas and Leak(69>).
79
These results imply that the effect of nitrogen on strain agemg may not be very
dependent on the prior heat treatment used. The diffusivity of nitrogen in ferrite is
given by the equation<3>
DN = 6.6 x 10 ·3 exp (-77826/RT) cm2 sec·•-----------------------4.13
where DN is the diffusion coefficient for nitrogen, R is the gas constant and T, the
temperature. DN was calculated as being 1.5 x 10 · 16 cm2 sec· 1 at room temperature (as
shown in figure 4.9), which corresponds to one nitrogen atom making a jump every
three seconds and in one month the diffusion distance would approximately be equal to
the distance between dislocations< 59 , 63 , 69>.
To summarise, nitrogen was found to satisfy all the three criteria for the occurrence of
strain ageing. The nitrogen atoms have quite a high solubility in ferrite at room
temperature, high diffusion coefficient in ferrite at room temperature and a high binding
energy to dislocations.
Fast and co-workers studied the effect of nitrogen alone on the strain ageing in two iron
- nitrogen alloys, one containing 0.02% nitrogen and the other 4 x 104 % nitrogen< 29,
34)
Study of the hardness values after a 10% prestrain and ageing treatments of 2
hours at temperatures between 100°C and 700°C revealed higher hardness values in the
alloy containing higher nitrogen and therefore a higher degree of strain ageing. The
results are shown in Figure 4.10.
80
TEMPERATURE,°C
25 50 75 100 I 50 200 250
101
16'
-10
10
-I I0-11
s
s 10
N
2
o·
. 10-,,
-14
10
-15
10
3·0 2·6 2·2 1·8 1·4 l·O

+.·,o•
Figure 4.9 Diffusion coefficients of nitrogen and carbon (Leslie<3>)
150 _ _ _ _ _,Fc-0·02'YoN
zl40 - • ~
~130 ~
~120
~ Fc-0•040/oC
;,10 /0~~ •
i, --:::...-,- • "
90 F~-0·0001°/o~ "'-
80 ~
70~-------------'-------..;a
0 100 200 JOO 400 SOO 600 700
TEMPERATURE ,0 c
Figure 4.10 Strain ageing of iron -nitrogen and iron carbon alloys strained 10%
and aged for 2 hours at different temperatures (Fast cited by Baird<29>).
81
Figure 4.11 illustrates results of the experiments on iron nitrogen alloys, which show
the changes in mechanical properties at two temperatures of 51 °C and 42°c<29, 70>. The
changes in mechanical properties are well correlated with the amount of nitrogen
dissolved in ferrite as measured by the internal friction technique.
51°C
Figure 4.11 Strain ageing of 0.029% nitrogen-iron alloy followed by change in the
yield stress(upper curves) and solute content of ferrite as measured by internal
friction(Thomas and Leak cited by Baird<29>).
Josefsson and Backstrom studied the influence of varying nitrogen contents in three
carbon saturated low carbon steels containing (in weight%) 0.02%C, 0.003%N;
0.03%C, 0.006%N and 0.03%C, 0.008%N<71 >. The rate of strain ageing increased with
the total nitrogen content as illustrated in Figure 4.12. Figure 4.13 shows the
behaviour of the three grades of steels mentioned above at 60°C. The amount of ageing
apparently has undergone no change, but the ageing time has decreased.
82
80
70
60
..
E
50
e
";. 4 0
.,.
>-. .
<I
lO
0
2-0
1·0
I DAY 45 DAYS
4l 4' 41 ... ...
AGING TIME, m1n
Figure 4.12 Increase in the yield stress after prestraining 3% and 8% vs ageing
time at room temperature (Josefsson and Backstrom<11>) o-----o 0.02 C, 0.003 N ; •-
·•0.03C0.008N; /l-- /l0.03C0.008N. ----------0.002N(Wilson and Russell); _ __
_ 0.014%C+N(Wilson and Russell).
8·0
7·0
6·0
5·0
e
~...
,..
4·0
>-~
<I
5-0
2 ·0
;
IHR IDAY 45 DAYS
O·O
4·01 40 4' 4l 4l
•• 41
AGING TIME I m,n
41 47 41 4'
Figure 4.13 Increase in the yield stress after prestraining 3% vs ageing time at
60°C (Josefsson and Backstrom<71 > )-0-----0 0.02 C, 0.003 N; •--•0.03C0.008N; /l--
/l0.03C0.008N(water quenched from 250°C); ---0.002N(Wilson and Russell);-
_ _ _ _ _0.014 ¾C+N(Wilson and Russell).
83
Taheri and co-workers studied strain ageing in various grades of steels with carbon
contents in the range of 0.05 - 0.08 wt¾ and nitrogen contents between 0.003 and 0.43
wt%< 72 >_ Figure 4.14 compares the strain ageing susceptibilities of these steels which
were aged at 100 °C for 20 seconds after 6% strain. It is evident that as the level of
solute nitrogen content increases, strain ageing increases (flow stress increases). It was
also proved that N was responsible for the decrease in the ductility, by computing the
activation energy of the ageing process from the following equation.
In (t2/t1) = Q/R (1/f 1 - lff2) -------------------------4.14
where T1 and T2 are two different test temperatures of strain ageing and t 1 and ti are
times of strain ageing at these temperatures which produce the same degree of strain
ageing, Q is the activation energy and R, the gas constant. The activation energy was
calculated to be 67kJ/mol by Taheri et al.
10u rr====-===::::::"'-----------,
---hlN,med
.
..~·······~········~·-······
80 ---hlN,•1-
. ...
- - - ~ - lo N, nwd
. .
60
40 ........ :- ..... .
. .
20 • • • • • • • • .~ • • • • •. ·-.-!:- • • • • • - • -:-. • ---- -- ~.• • • - - ---
.. ....,_ _.,._ _ _..,_ .
0 ..,__ _...., _ __.,.·_ __.
0 50 100 150 200 251

Aglng temperature re)
Figure 4.14 Effect of nitrogen content on the flow stress of low carbon steel aged at
100°C for 20 seconds after 6% strain (Taheri et a1< 72 >).
84
Figure 4.15 shows the effect of nitrogen content on the decrease in total elongation due
to ageing.
I• S% ROLLINC REDUCTION
--
~ 30
AGED b MTHS AT ROOM TEMPERATURE
, "'
~
"'m:u
o 20
a JOf,IS t, OWEN • &ARNE TT ( 35)

• HUNO]
0-008 0·01 0-01 0-020

NITROGEN CONTENT( •k )
Figure 4.15 Effect of nitrogen content on decrease in total elongation due to ageing
(B.B Hundy<4> 1956).
• Carbon
The solubility of carbon in ferrite is given by the equation<3>
%C = 2.55 exp (-9700/RT------------4.15

while the diffusion coefficient is given by<3>
D c = 0.02 exp (-20,000/RT)---------------------------4.16
From Figure 4.6, it is seen that the equilibrium solubility of carbon decreases to below
10 -3 to 10 -4 wt% at a temperature just over 200°C. Above 200° C, the mobility of
carbon atoms is reasonably high and on slow cooling, equilibrium should be
approached if there are sufficient nuclei present for the precipitation to take place.
Studies using internal friction measurements indicate that it is easier for nitride
precipitates to dissociate than for carbides(Jo, 37 >_ However if carbon is held in
supersaturated solid solution by quenching or by slower cooling in the absence of

85
precipitate nuclei, then the excess carbon should result in strain ageing. At a
temperature greater than 200°C, enough carbon should be in solution at equilibrium to
give some ageing directly. It is also seen that the diffusion coefficient of carbon is
slightly lower than that of nitrogen at low temperatures while it rises above that of
nitrogen above 390°C as shown in Figure 4.9. Locking of dislocations by carbon is
slightly weaker than by nitrogen.
Fast and co-workers observed the change in hardness in a Fe-0.04% C alloy after
ageing for 2 - 40 hours at 50 °C- 200°C and a prestrain of 10%<29>_ It was noticed that
there was no appreciable increase in the hardness even after ageing at 50°C for about
40 hours. Two hours at 100°C produced a slight increase while two hours at 200 °C
produced the peak hardness. This was as compared to the fact that a Fe - 0.02% N
alloy showed maximum hardness after ageing for 2 hours at 50 °C. Similar studies
using the internal friction method by Butlei13> and Stephenson <74 >, after ageing low
carbon steels and irons to 100 °C for 1 hour after 7.5% and 10% prestrains revealed
rapid increases in the yield strength as dissolved carbon was increased from 0 to
0.0001 % (Butler) and 0 to 0.0026% (Stephenson) and a slower increase thereafter.
Figure 4.16 illustrates results of studies by Butler. Even with as low as 0.0005%C,
ageing indices of 5000psi (35 Mpa) are obtained. Carbon was found to be as effective
as nitrogen in producing strain ageing effects in polycrystals while to a lesser extent in
single crystals.
86
B BO
(G) NITROGEN
6 60
AY,
k 1 f/mm 1
4 ....-- -----------------------
,,":,_..-----·------------·-
~
«>
2
,..,-,,· 20
- ENRIETTO (30)
- - - - SEKINO I FUJI SHIMA (30
- - · - SEKINO & FUJI SHIMA (3~
10 100
8 BO
{b) CARBON
60
AV,
kcf/mm 1
6
4 ,,,,, ---·---
-------
_,,,.. ..
- · - · - - - - - - - - - - IIIN,_
.co
,.
2
•/ -
,~-STEPHENSON (28) 20
• - - - - BUTLER (;311)
0 __________ & FUJI
- - - SEKINO.._ SHIMA
__...._ (30 (3~
_ _.__~
0 2 3 4 5 . 6
o/o N °" o/oc x10,
Figure 4.16 Effects of (a) nitrogen level in solution and (b) carbon level in solution
on the change in yield stress, on prestraining and ageing for lhour at 100°C using
the following prestrains Stephenson 10%; Enrietto 12%; Seking, Fujishima, Butler
7.5%. Dissolved carbon and nitrogen were determined by internal friction (Baird
(33)).
• Other alloying additions
The elements, which directly do not themselves produce strain ageing can be divided
into four categories <33 >:
i) Elements that interact weakly or not at all with nitrogen and carbon
ii) Nitride formers
iii) Carbide formers
iv) Nitride and carbide formers
87
i) Elements that interact weakly with nitrogen and carbon:
Manganese and Phosphorus, Copper and Nickel are elements which tend to go into
solid solution in ferrite with little or no affinity for either nitrogen or carbon and this is
reflected in their effects on strain ageing. Edwards and co-workers have studied the
effects of copper and nickel and have found that they only increase strain ageing to a
very marginal extent in a 0.025%C-Fe alloy at 250°c<33 >_ Therefore copper and nickel
will not be considered further.
• Manganese
Manganese has been known to interact weakly with nitrogen in solid solution. Effect of
manganese content on strain ageing rate is shown in Figure 4.17. Bergh et al suggested
that the variation in the ageing rates of rimmed steels was as a result of a variation in
the manganese content in steels<75 >. It has been shown that the activation energies for
strain ageing increase with increasing manganese content from 18 kcal /mol in pure
iron to 22 kcal/mol in a 1.2 % Manganese steel. This higher activation energy for strain
ageing in steels containing higher manganese is related to a decreased mobility of
nitrogen in the presence of manganese<33 >_ Internal friction studies by Fast <34 > and
Sladek <68 > show that nitrogen atoms prefer sites beside manganese atoms rather than
iron sites. Manganese has also been known to slow down the precipitation of carbon
and nitrogen during quench ageing <34• 76>.
• Phosphorus
Phosphorus has been shown to reduce the strain ageing especially at low nitrogen levels
(0.001 %) while at high nitrogen levels it apparently has no effed33 >.
88
4.----.----.-----.-------,.-~~
.. --~::::::::::=:
-~ ~ 50
INCREASE
INYIELO
s /0/ -------· 40
MN/•&
sTAess
/
30
2 /
•
61-------'"'1'-,A
,,,,-·
I
{6Y) 1
ton1'-/in 2 Mn IN SOLID SOLUTIOH 1 9/e 20
/ K 0·04
./t,. 0 0•11
10
6 • 0•18
6 0•26
5 10 15 20
AGEING TIME,DAYS AT 2o•c
Figure 4.17 Effect of level of manganese in solid solution on the rate of strain
ageing of commercial rimmed steels prestrained 10% in tension (Baird<33>).
ii) Nitride formers
Since nitrogen accounts for a major portion of strain ageing that takes place below 100
°ሥ
C, this process can be reduced by the addition of nitride forming elements. However it
is essential that an earlier heat treatment is employed, which allows full precipitation of
nitrogen as alloy nitrides and carbon as carbides on final cooling <33 >_
• Aluminium
Aluminium is a strong nitride former and the compound AlN, is an extremely stable
product. Leslie at al studied the effect of prior heat treatments on strain ageing of
aluminium killed stee1s< 14>_ It was noted that in the absence of silicon, low temperature
strain ageing can be reduced by aluminium additions but not completely eliminated.
Aluminium is most effective when low austenitising temperatures are used so that AlN
89
does not dissociate, and also in situations when subsequent cooling is slow. Aluminium
is slow to precipitate during cooling, unless the cooling rates employed are
considerably lower than that used for commercial rod< 77 , 78 ' 79>_ Additions of aluminium
therefore would not prove useful on commercial scale due to the fact that AlN
precipitates during isothermal treatment at relatively low temperature but not during the
billet reheating temperatures. Another disadvantage of using aluminium killed steels is
the poor surface finish as a result of the presence of aluminium oxide inclusions<18>.
Laxar and co-workers studied the effects of various aluminium contents on the strain
ageing of low carbon stee1< 79>_ Small additions upto 0.08% decreased strain ageing
while additions over 0.3% increased strain ageing. The effect of aluminium on the
strain ageing of low carbon steel, as studied by Epstein et a1< 29> is illustrated in Figure
4.18.
The influence of Al/N ratio on the solute nitrogen content after continuous annealing is
Internal friction studies have proved that the effect of aluminium was to slow down
diffusion and hence the precipitation of carbon during cooling<29>_ The observed ageing
was therefore due to a supersaturation with carbon. Aluminium can also form a
reasonably stable carbide Al4C3 but Richardson proved that the association of Al and C
in steel is made less favourable thermodynamically by the strong affinity of iron and
aluminium< 80 >.
90
ALUMINIUM-Kil.LEO NON-AGING STEEL
IO 20 30 40 10 20 30 40
ELONGATION ON 2in, OJ,,
Figure 4.18 Stress strain curves at 20°C and 205°C for (b) rimmed steel which
showed pronounced strain ageing and (c) aluminium killed steel which showed no
strain ageing (Epstein et al cited by Baird <29>May 1963).
20
COIL TEMP.
E 0 C.R. 6SO°c 7'1Jlc
8:
.:::
0
II)
15 0
l2°c/s
500c/s
•
0
•
6
z \.I i
6~
-
UJ
§ 5
0~
~- -- i.i...
0 .. 2 3
~
......... 8
a
E---,.l...
•
5
.6.
6
- 7 8 9
•
lii,.
0
AUN
Figure 4.19 Influence of Al/N ratio on the solute nitrogen after continuous
annealing at 825°C (Meissen and Leroy<81 >).
• Silicon
Silicon combines with nitrogen m ferrite during tempering in the range of 600 -
6S0°c<29, 33 >_ It was postulated that the product SiN being similar in structure to AIN
would precipitate on AlN particles on cooling. This makes combinations of aluminium
and silicon more effective in suppressing strain ageing than aluminium alone. Silicon
91
also forms a stable carbide but the strong affinity between Fe and Si prevents formation
of these carbides.
• Boron
Boron is an interstitial element and a strong nitride former. Boron has an atomic radius
of 0.97A0 , compared with carbon 0.77A0 and nitrogen 0.71A0 <61 >. Figure 4.20 is a
portion of the Fe-B equilibrium phase diagram. Boron is soluble in austenite to the
order of 0.001 % at 915°C and 0.02% at 1165°C, while the maximum solid solubility of
boron in ferrite is 0.002%<82>.
The diffusion coefficients of boron in austenite and ferrite are given by the following
equations< 83 >:
Austenite, D = 2*10"3 e·210001RT _ _ _ _ _ _ _ _ ,_____4_J5
. D-
Ferrite, _ 106 e -62000/RT ----------------------------------,.
"]6
The above equations suggest that boron forms an interstitial solid solution in austenite,
while in ferrite, boron forms a substitutional solid solution. This was confirmed by
McBride on the basis of relative solubilities, atom diameter and the size of the
interstitial hole in austenite and ferrite< 84>_ The diffusion rate of boron in austenite is ten
times faster than aluminium and similar to that of nitrogen as shown in Figure 4.21 <67 >.
Boron is adsorbed in austenite and tends to segregate at the austenite grain boundaries.
It also has a positive temperature coefficient meaning boron segregates in increasing
amount with increasing temperatures<67>. Boron as already stated, is a strong nitride
former. The effect of boron on the solubility of nitrogen in iron was investigated by
Fountain and Chipman<S 5) and Maitrepierre cited by Franks and Kirkcaldy<86>.

92
ATOMIC PER CENT BORON x 10-'

0 25 50 7 100 125 150
8
1400
-=--------- ---~-=:::.=.
8+y
1300
Y+L
I
I
800o~-5~-,~o-~,s--2..._0
I
_ _2_._s_ __,_30_ __,35
WEIGHT PER CENT BORON x 10 3
Figure 4.20 Fe- B Phase diagram (M.E Nicholson<82>).
The solubility of boron nitride in austenite is given by the equation<82>
Log [B] [N] = -13970ff + 5.24---------------------------------4.J 7
where [B] and [N] are the boron and nitrogen concentrations in steel.
It was reported by Franks and Kirkcaldy <86> that in a steel containing 0.009% N and
0.007%B, at a billet reheating temperature of 1100°C, 0.004%B and 0.0052% N will
redissolve and the balance remains as BN in the austenite. The redissolved nitride
should precipitate out on cooling after rod rolling, however this process will depend
entirely on the kinetic factors like time<86' 87>. Boron has a strong affinity for nitrogen
in the temperature range of 1100°C -850 °c<61 >. In the Fe-N-B system, there are only
93
two precipitates of boron, BN and Fe2B. The identity of the precipitate depends on the
relative amounts of boron and nitrogen in the steel.
I
I
I
I
I
I
I
I
I
I
I
- 15-0
I
I
I
I
I
- 15·5
- ll•O ,_ _.....,_ __.._ _""'---"'---~---

3 •3 3·1 2·9 2•7
1,000/7' (T tn ° R.)
Figure 4.21 Diffusion coefficient of boron (firm line) as compared to carbon

(dotted line) (Busby cs3>).
Based on the above equation, Sugimoto derived an equilibrium phase diagram as shown
in Figure 4.2i 67 >. This diagram shows that at 850°C and 4 ppm boron, the free nitrogen
is reduced to 2 ppm and in a steel containing 80 ppm boron, when cooled from 1000°C
to 850°C, the free nitrogen content decreases from 100 ppm to about 5ppm.
94
Chapter 4 Strain ageing oflow carbon steels
100 i:::- ·· · ·- - ·-
~ I-
I
IZ
11r
,-
I-
y
0.5
0
5 10 SO 100
B • [BJ (wt.ppm)
figure 4.22 Equilibrium phase diagram calculated for Fe-B-N system (Sugimoto-
faulrig<67~.
rhe solubility product ofBN in ferrite is given by<86>
log [B] [N] = -13680/f + 4.63-------------------------- 4.18
Watanabe and co-workers have calculated based on the solubility product data that in
alloys containing a total of 20 ppm boron, 0.07% soluble aluminium and 30 ppm total
nitrogen, 40% of boron (i.e 8 ppm) precipitates as BN at 1000°C<88• 89>. And in an
alloy containing a total boron of 20 ppm, soluble aluminium 0.07%, I 00 ppm
nitrogen, 60% of the total boron, (12 ppm) precipitates as BN at 1000°C. Table 4.3
shows the results of distribution of boron atoms obtained under various heat
treatments. It has been summarised that the segregation behaviour of boron atoms is
determined by
(a) body diffusion of boron atoms
(b) grain boundary diffusion of boron atoms, and
(c) the sweeping velocity of recrystallising austenite grain boundaries.
95
Table 4.3 Distribution of boron atoms as observed by Watanabe et al <88 • 89>
Hot rolling and heat treatment Distribution of B atoms
I 300 °C xI h WQ I. Segregate to r grain boundaries.
I. Segregate to r grain boundaries.

I000°Cx I h WQ
2. Random distribution of precipitates.
I. Precipitate on prior ,- grain (at 1300 °C) boundaries. The intensity of fission
tracks of these precipitates in high Nsteel is stronger than that in low Nsteel.
! 300°Cx I h WQt930°Cx20min WQ
. 2. Segregate to newly formed r grain (at 930 °C) boundaries in low Nsteel while
in high N steel they do not segregate.
I. Segregate to newly formed r grain (at 930 cc) boundaries.

I 000°Cxl h WQt930°Cx20min WQ
2. Random distribution of precipitates.
I. Reduction of the intensity and density of fission tracks of precipitates on prior

1300°Cxlh WQtl000°Cx20min WQ grain boundaries.
2. Segregate to newly formed r grain (at I 000 cc) boundaries.
96
Experiments by Watanabe and Ohtani on steels containing 0.0107 - 0.0326% N and
0.0025 - 0.0096% B revealed hexagonal BN precipitates as shown in Figure 4.23<S9)_
During cooling from 1300°C, boron and nitrogen atoms segregate to the austenite
grain boundaries and concentration exceeds the solubility product causing precipitation
of BN. While aluminium atoms distribute homogenously and do not affect the
precipitation process at this stage. However, when the cooling rate is very low like in
furnace cooling, Al atoms migrate to the grain boundaries and precipitate on the
surface of the BN particles in a dendritic form. When the alloy is heated at 1000°C,
AlN also is found to precipitate and grow acicularly on BN. Based on only solubility
data, BN should precipitate in preference to AlN as shown in figure 4.24, since BN is
100 times less soluble in austenite than AlN<61>. However, thermodynamically BN has
been shown to be less stable than AlN. This discrepancy between solubility and
thermodynamic data is due to the difference in diffusion rates. BN precipitates rapidly
due to the small size of the boron atom, and its interstitial location in the austenite
lattice and therefore rapid diffusion rate. In contrast aluminium diffuses faster in
ferrite than in austenite. However even in ferrite the diffusion rate of aluminium is
quite slow as compared to that of boron<61 >. Figure 4.25 shows the type of precipitate
formed under steelmaking conditions. Boron also precipitates as M23 (CB)6. However,
it has been found that BN is more stable that the M23(CB)6 especially above the Ac3
temperatures. Figure 4.26 is a schematic illustration of the precipitation behaviour of
boron in the manufacturing process.
97
Figure 4.23 Typical spherulite morphology of BN in steel (Watanabe and

Ohtani<89>).
Steels with boron contents in the range of 0.007 to 0.02% showed a reduced ageing at
both room temperature and at 100°C after a box annealing treatmentcss, 89>. With
0.025% or more, strain ageing begins to increase, probably because of the formation of
boron oxides. Sufficient boron can be added to steel so as to prevent strain ageing and
at the same time not destroy the rimming action in steel. Boron being an interstitial
solute diffuses quickly at low temperatures and precipitates nitride under most cooling
conditions. Boron is also capable of combining with oxygen, which renders part of the
boron addition ineffective in reducing free nitrogen.
98
..
'""":1/~~ ..,•.,..
. . -~ -.. ·~... -:·; ~f
A .· ,. ' .
:<,~ ":1.:..~· ·. ·. e~--:~.·· ·.·-
··.. .
a Al
b SN
Figure 4.24 Precipitates in a furnace cooled steel from 800°C after heating at
1300°C for one hour and hot rolling. AlN grows radially on BN (Watanabe and
Ohtani(S9>).
99
o'tx1hr heating rate: 15°c/min
Figure 4.25 Schematic illustration of precipitation behaviour during the

manufacturing process(Watanabe and Ohtani(S9>).
600 700 BOO 900 1000 1100 c•

1110 1290 1470 1650 1830 2000 f•
PRECIPITATION TEMPERATURE
Figure 4.26 Type of precipitate formed under steelmaking conditions

(Faulring(67>).
100
According to data published by Derge, a boron content of 0.02% could exist in
equilibrium in molten steel with only 0.022% oxygen<90). Unfortunately this
composition steel does not rim very well. A low carbon steel (0.06%) will rim well
when it contains an oxygen content of 0.045% free oxygen <91 ). This amount of oxygen
should exist in equilibrium with only 0.007% boron<90 l_ This means that additions of
0.007% boron would not combine with oxygen affecting the rimming action. Normally,
to fix all the nitrogen available the amount of boron required will be equal to 0.7 - 0.85
nitrogen<91 )_ A study by Franks and Kirkcaldy revealed that on reheating of billets to
around 1100°C, a significant proportion of boron nitride dissolves back into
austenite<86>.
An advantage of boron is the lack of precipitate strengthening <92>. The major reason
for this is the size and shape of the boron nitride particles formed in steel i.e spherulites
of about 2000AO in diamete/67 ). However it was noted that the ductility of boron steels
dropped with an increase in the amount of free boron remaining after nitride formation,
especially at high nitrogen leve1s<92). Free boron segregates at the austenite grain
boundaries affecting the ductility <33 )_ Further it was also shown by Nicholson et al that
boron and boron nitride have a tendency to dissolve in iron carbide<82>. This
phenomenon accounts for the fact that those steels that contained boron exhibited a
greater amount of carbide and no precipitates of iron boride.
Morgan and Shyne, as early as 1957 have evaluated the effect of boron on the strain
ageing properties of steels< 93 , 94 >_ Their experimental alloys encompassed steels of 0.06-
0.07% carbon, nitrogen contents ranging from 0.003%-0.007% and boron from zero to
101
0.03%. Table 4.4 lists the details of compositions used for test. The alloys were chill
cast and then hot rolled at 982°C. Subsequently they were machined to size and then
box annealed at 705°C for 15 hours. Samples were then prestrained to 7 .5% and then
tensile tested after ageing at various temperatures as indicated in Table 4.5, which also
shows the mechanical properties obtained in these alloys after being subjected to
different ageing temperatures. It is evident that boron additions have reduced the
ageing index. The boron containing steels did not exhibit any yield point, and on this
basis the researchers proposed that steels containing between 0.007% and 0.02% boron
be termed as 'non-ageing' grades, when used in drawing operations after prolonged
storage. Boron was also found to increase ductility in these steels. It was therefore
concluded based on this set of experiments that from the viewpoint of ageing alone,
boron additions should optimally be in the range of 0.007-0.02%. However, the
distinct tendency of boron to segregate, its natural affinity for oxygen and the economy
of the process will dictate the actual additions to be made.
Studies by Yamanaka and Ohmofi<95 ) on boron containing steels revealed an increase in
the grain size with an increase in the boron content from 5 to 95 ppm and an increase in
the austenitising temperature from 900 to 1200°c<91 ). This increased grain size coupled
with the fixing of free nitrogen has resulted in a decrease in the yield and tensile
strengths and improvements in ductility. The effect of BIN ratio on elongation is
102
Table 4.4 Typical steel compositions studied by Morgan and Shyne <93>_
Allo.y Pet·c Peto Pot.N ...

Otller.
C
CN
CHAI.
0.08 ·
0.0'1
0.08
0.001•
0.0088
0.0088
0.0001
o.oou
O.OMO
-
-
Al, O.ON
CNV 0.08
0.07
0.0013 0.0038
. 0.0057
v. 0.039
CNBi • 0.0008 B. 0.0:,0
CNBt O.O'l 0.0105 o.oou B. o.oao
CNTi 0.06 0.008• · 0.006• Ti; 0.'8
CB 0.06 0.0026 0.0001 .B. o.ooa
• Assumed values; not actually analyzecl.
103
Table 4.5 Mechanical properties of the steels listed in Table 4.4 (Morgan and Shyne<94>) •
Allor ll-rop•r&l,- .AAQeal•• a&SPO

"a'.Da79· aODa7•
af.aa•o
......
---··..-o_
..
......
100-C
~
C %30 8,220 8320 . 15"1'SO &&SO

CN 200 8100 9230 8840 8800
CNA1 A.gin&
230 1090 1'720 1310 11530
CNV
CNBi
CNBs
CNTt
J.ndex,
ps:I.
0
180
160
0 580
1500
1490
490
200
2930
2950
500
-
480
2530
340
-60
1750
240
CB
C. 36930
o· 15100
38050
6580
39370
-
39470
-
39400
CN 3'7760 44290 4.4540. 43740 43100
CNAl 38360 38780 .. · 3'1800 38480 38000
Ui-tun.a-t;e 40290 39860 40800- 40140 40030
CNV
CNB1
CNs.
a-t.re:n~.
psi 37400
37270
38810
36710
3'1-400
38840 3~0
-
38830
•1seo
CNTl·
. ea
C
CN
4::LBOO
52.1 - .
.42080
{ """:_..'. --:=.o ,:ta;•

420G().
30200
'8.4
38.8
-
41700
48.8. ·
40.8 .·
48.1
43:. .
CNA.I. ,.53. 7 .. &52.8 53-0 . 54..2 53.!'"
CKV TotaJ.- 51.2 .48.'1. 50.4 ·s1.o 151;
Cl'f"B.1
CND.,;
eloncation.
pct~:J..tn.
6e.O
55.0
155.IJ
~-3
G5.1
55.6
-52.9 -56.7
~Ti. 52.2. 5 .2 ~2.3. 152.1 52.'1
CB 55.2 50.8 4,8.6
104
Chapter 4 Strain Ageing of low carbon steels
0 1 2 3 4
BIN (WT. % RATIO)
Figure 4.27 Influence of BIN ratio on the elongation (Faulring<67>).
iii) Carbide formers
Molybdenum is not a strong nitride former, however it does form carbides in steel.
Molybdenum contents if the range of 0.3 - 1.98% have had no effect on strain ageing at
250 °C <33 >. Further studies have indicated that elements that form only carbides but not
nitrides will not reduce either low temperature or high temperature ageing.
iv) Nitride and Carbide formers
Chromium, vanadium, niobium, titanium and zirconium are elements which can form
nitrides, carbides or carbonitrides. Thermodynamically nitride formation is more
favourable. Where a separate nitride forms, all nitrogen present has to be fixed before
any carbon is removed from the solution. But elements like vanadium, niobium and
titanium, which result in the formation of a carbonitride may contain carbon at
equilibrium.
105
• Chromium
Chromium behaves in a similar manner to manganese in that it is the weakest nitride
and carbide former amongst the above stated elements. Edwards and co-workers
studied the effect of various chromium contents on the strain ageing characteristics<96).
It was found that low carbon steels containing 6.10% Chromium do not show any strain
ageing, indicative of fixation of all nitrogen and carbon by chromium. Several others
have investigated effect of upto 0.44 % Chromium in low carbon stee1s<97>_ Increase in
Cr contents apparently decreased strain ageing at 100 °C, and at 0.44% indicate that Cr
fixes nitrogen in solution with a resulting decrease in the migration of nitrogen to
dislocations<97>.
• Vanadium
Vanadium is a stronger nitride and carbide former than chromium, however its
reactions are kinetically retarded resulting in the formation of non-stoichiometric
products<33 >_ As a result there is removal of only one-fourth of available nitrogen from
the matrix. It has been shown that 0.26% vanadium decreases strain ageing at 250 °C
while 0.69 % completely eliminated it<97 - 101 >. Considerably less vanadium (0.02 -
0.03%) is required to prevent low temperature strain ageing. A V/N ratio of 7 to 9 has
been found essential to combine all free nitrogen to form VN<97 - 101 >. Vanadium in
excess of this combines with carbon to form vanadium carbide resulting in undesirable
precipitation hardening effects. Another advantage of using vanadium as a nitrogen
fixer is that it is not a strong deoxidiser, therefore the steel need not be fully killed
before nitrogen can be fixed by vanadium<9&J_ Experiments by Epstein et al have
shown that non-ageing rimming steels can be made by adding vanadium<97 >_ The
amount required depends on the nitrogen content. In steels with high nitrogen content,
106
it could affect the rimming action seriously. However in lower nitrogen containing
steels the amount of vanadium needed would be 0.03%. Vanadium nitride that forms
takes away available nitrogen from the matrix preventing strain ageing. This nitride is
unstable at temperatures above 700° C and steels annealed above these temperatures
would be susceptible to strain ageing again. Figure 4.28 shows the strain ageing
behaviour of a 0.21% carbon steel containing 0.006% nitrogen, (a) and the same grade
also containing 0.06% vanadium (b). It is evident that strain ageing is almost
eliminated(IO))_ Beyond 0.06% vanadium, there is a possibility of some precipitation
hardening effects. The degree of extra strength provided by a given amount of
vanadium becomes greater as the carbon content is increased. In order to avoid
unacceptably high levels of strength it is necessary to control the composition to
comply with the limit( 33 >(also shown in Figure 4.28)
[V] *[CJ< 0.0026-------------------4.19
The effectiveness of vanadium in stabilising the nitrogen appears to be independent of
the aluminium content( 101 >. There also appears to be only a minimal refinement in the
grain size with vanadium additions of upto 0.1 %. It is therefore logical to conclude
that vanadium additions are less effective that titanium in eliminating strain ageing
together with achieving optimum mechanical properties. However one advantage is
that vanadium can be added to semikilled steels or steel grades to be continuously cast
while titanium has to be added only to killed grades.
107
Chapter 4 Strain Ageing of/ow carbon steels
500 lb)
(al
400
.........
Ii
:z
:It 300
.,;
"'
!!!
ij;
200
100
pre-strain
0 0 10 20 30
Strain, •;.
fa)
SOO
400
""e 300
%
z
::r~ 200
in (al lbl
100
pre-strain
0 L....1'-------"1------,10~------,2:!:o:----='30::-
straain • •.,.
(b)
Figure 4.28 Stress strain curves for (a) low carbon steel 0.005% nitrogen and (b)
addition of 0.06% vanadium (Erasmus et al <101 >).
• Niobium
Niobium appears to form more stable carbides and nitrides than vanadium<33 >_ 0.28%
niobium reduces strain ageing at 250 °C while 0.36% completely eliminated both the
yield point and strain ageing<97 )_ However, the extent of strain ageing depends largely
on the balance between carbide and nitride formation, which is particularly of
importance in niobium bearing steels. It has also been observed by Mandry that the
strain ageing index of niobium containing steels is sensitive to austenitising time and
temperature, first rising to a maximum as the temperature is increased and falling as the
carbonitride is taken into solution and precipitated out on cooling as a nitride rich
108
carbonitride<33 >. The general trend is that the lower the temperature at which
carbonitride is formed, the higher is the proportion of nitride it contains.
• Titanium
Titanium is one of the strongest carbide and nitride forming elementscso, 102>. Because
of the greater stability of the nitride, there is a tendency for the nitride to first
precipitate from steel <102, 103 ' 104>. This precipitation takes place at temperatures at
which the elements can diffuse quite rapidly and therefore stabilising effect of titanium
is not dependent on the prior heat treatment. At high temperatures, titanium reacts
easily with oxygen, sulphur, nitrogen and carbon to form their compoundsoos, 106>. The
precipitation temperature ranges for these compounds are shown in Figure 4.29. The
temperatures of oxide, sulphide and nitride formation are relatively high and
accordingly these compounds precipitate in the casting and billet making stage.
However, the precipitation temperature of the carbide is low and depends strongly on
the rod rolling/cooling conditionsC 105 ' 106>. Although titanium is one of the strongest
carbide formers, the optimum amount of titanium that can completely fix the solute
carbon in ferrite is yet to be determined. The amount of titanium that is available to
combine with carbon to form TiC is given by the following equation< 105 , 106>.
[Ti available] = [Ti] - (2*48/32)[S] - 48/14 [N]--------------4.20
where [Ti], [S] and [N] are the weight percent of each element in the steel. The ratio
of the stoichiometric amount of titanium required to fix carbon as carbide to the amount
of titanium available is given by
Ti ratio= [Ti available]/ (48/12 *[C])---------------4.21
where [C] denotes the carbon content of the stee1< 105 , 106>.
109
2000
1800 mp Oxides ITixOyJ

Nitride {TiNJ
!
1600
____s_ul-fid_e_s_(T-ix_s_v1_ _ _ _ r
;:!
I! 1400
I
•
~
Carbide (TiCJ in austenite
1200 A2 ......,_ _ _ _ _ __,,......,.,.,.,.,.,.,...,..
1000
800
Ea~ili 1~:~~i
Figure 4.29 Precipitation temperatures of titanium compounds (Ochiai<105~.
Studies on two batches of steels, one with a carbon content of 0.005% and the other
with a carbon content of 0.02% with additions of titanium in the range of 0.03 to 0.19
% revealed that the mechanical properties of the rods varied as shown in Figure 4.30.
Figure 4.31 shows the influence of titanium additions on the ageing index. The ageing
index was found to decrease with an increase in the titanium ratio. However the
decreasing tendency was found to be strongly dependent on the carbon content of the
rod. The low carbon grades showed a gradual decrease in the ageing index with
increasing Ti ratios and even at a very high ratio of 2.91, the steels exhibited an ageing
index of 8 Mpa. While the high carbon grades showed an abrupt decrease in the ageing
index when the Ti ratio exceeds 0.96 and at a ratio of 2.07, the index falls to a value of
2 Mpa. Titanium carbide was found to precipitate below the A3 temperature in the low
carbon grade steels while the precipitation commenced in the austenite stage itself for
the high carbon grade steels. These precipitates form nuclei for further precipitation in
the ferrite phase.
110
400,----------~
TS
150
1001-------------J
C (mass%)
0 0.0050--0.0057
ii. 0.017 -0.022
800:::----+,----,!2,---.....J
Ti-ratio 3
Figure 4.30 Mechanical properties of rods containing titanium (Ochiai< 105>).
C lmass 'lit/
O 0.0050-0.0057
e. 0.017 --0.022
)(
.g 40
-=Q
C
"cii20
c(
1 2 3
Ti-ratio
Figure 4.31 Effect of titanium additions on the ageing index of the wire
(Ochiai< 105>).
It has been stated by Ochiai and co-workers that to make a 0.005% carbon steel non-
ageing, the titanium ratio should be increased to a value over three< 105, 106>. However in
order to obtain a non-ageing steel with a lower Ti ratio, the cooling rate should be
decreased further. This becomes industrially impossible in low carbon grades where
the cooling rate has to be very low to achieve the best possible decrease in the ageing
index. It is therefore necessary to increase the carbon and titanium contents so as to
introduce precipitation nuclei during rolling in the austenite region or to accelerate

111
strain induced precipitation by rolling at a temperature very near the nose of the
isothermal precipitation curve for TiC.
In a steel with carbon content of 0.025%, 0.21 % Ti is enough to eliminate both the
initial yield point and strain ageing at 250°C, while the same level of titanium
associated with higher carbon i.e 0.085% gave rise to strain ageing. Increasing the
titanium content to beyond 1% did not eliminate strain ageing. Titanium or any other
alloying element must be added in such a way that precipitation hardening is avoided
(33)
The maximum titanium content recommended in order to avoid precipitation hardening
is given by the following equation <33 , 105>
% Ti - 3.4% N (total)< 0.07---------4,22
The effect of excess titanium on tensile strength is shown in figure 4.32.
Titanium has an additional advantage of reducing the soluble carbon to extremely low
levels and is used to produce "Interstitial Free" steels. Titanium, however is a very
strong deoxidiser, and therefore the steel has to be fully killed before it can be ensured
that nitrogen can be fixed by titanium< 102, 105 - 106>. Smail, Keown and Erasmus have
confirmed that additions of 0.02-0.03% titanium to a 0.005-0.006% nitrogen steel have
completely eliminated strain ageing< 102>.
112
470
N
'e
420 I
X
I
~ 370
320-._ __..._ _ __.__ _ _........__ _ _.,_,

0 0-025 0·050 0·075 0-01
•1. Ti
-3·4•/.Nr
Figure 4.32 Effect of excess titanium on the tensile strength of low carbon steel
(Erasmus 102>).
However it is clear that the effectiveness in preventing strain ageing increases with an
affinity for carbon and nitrogen in an increasing order of manganese, chromium,
vanadium, niobium and titanium <33 >_ A larger amount of any of these carbide /nitride
formers is required for eliminating strain ageing at 250°C than that needed to offset the
process below 100°C. But because most of these elements combine with both carbon
and nitrogen, a larger amount is required to eliminate lo" temperature ageing than that
needed for a strong nitride former alone.
The exact mechanisms of the effects of carbide and nitride formers is not well known in
many cases. In some studies of internal friction have revealed interactions between
nitrogen and molybdenum, vanadium, chromium and manganese in solid solution,
while this is not true with carbon.
113
4.2.5.2 Effect of Prestrain
If the directions of straining are different before and after ageing, or when the
prestraining is by rolling, the discontinuous yield behaviour returns slowly<30). The
presence of a drop in the yield strength and subsequent yielding by Luders band
propagation begins at a low density of free / mobile dislocations which are at a
sufficient stress to move dislocations over large distances. Quick multiplication of
these mobile dislocations, which have formed in the prestrain stage, takes place. As a
result, dislocations will have to move at a lower velocity to give the applied strain rate.
Since the dislocation velocity is stress sensitive, the yield strength drops on initial
yielding which then propagates at the lower yield stress by the movement of Luder
band fronts< 30). New dislocations are created at these bands by the stress concentration
existing there.
Stretching in tension to a strain less than the lower yield point elongation divides the
specimen into regions yielded and unyielded separated by Luders bands formed at
approximately the lower yield stress. Until all unyielded regions have been consumed
deformation will continue by the propagation of Luders bands.
A reduction of less than 3% rolling also divides the specimen into yielded and
unyielded zones. But as observed by Hundy (4), Butler 173 ) and Wilson< 107• IOS) , the
zones alternate over short distances so that the availabk strain is widely distributed
throughout the specimen. This type of deformation gives rise to alternate bands of
deformed and undeformed material meeting the surface at perpendicular angles to the
114
rolling direction and running into the centre of planes of maximum shear stress. Butler
and Wilson have shown that after ageing, yielding begins at boundaries between the
yielded and unyielded bands. This suggests that yielding may be initiated with the help
of microstresses existing at these boundaries. After light strain ageing, yielding begins
at several points within the specimen but on prolonged ageing it gets confined to the
Luders bands. Butler and Wilson were able to show that the directionality of the yield
point return was as a result of directionality of the deformation introduced by rolling.
At greater than 3% temper rolling reductions, this directionality is reversed. This
suggests that for initial suppression of the yield point, the available strain should be
dispersed as evenly as possible throughout the specimen, such that no region is far from
a source of fresh dislocations(3o, 109).
Studies by Wilson and Ogram (l IO) on tubular specimens tested in torsion, aged and
restrained in same or reverse directions revealed that the return of the yield point was
not due to residual microstresses but because of strain ageing. It was observed that in a
specimen strained in tension and restrained in the same direction, most of the mobile
dislocations will not be able to move far since they will be pressed against obstacles
like grain boundaries, precipitates etc. So only a few isolated dislocations need to be
locked up to produce a return of the sharp yield point. While if the restraining is done
in any other direction other than the prestrain, the stress \\ill act to move dislocations
away from the obstacles. Only isolated dislocations may be locked up before those
stopped by obstacles. This is especially true at low solute contents. This explains the
different rates of the yield point return.
115
Observations by others have revealed that the rate of increase of the upper yield point in
specimens strained in the same direction before and after ageing is greater, the higher
the forward stress that is maintained during ageing. This stress keeps dislocations in
regions of unfavourable internal stress field and helps delay unlocking and subsequent
restraining. If a compression prestrain is applied on then material then it was found that
the yield point returned slowly as compared to when the prestrain was applied in
tension() 11 >. This was made use of commercially by using rolling as a method of
compression prestrain that would retard the return of the lower yield point <11 n_ Similar
results are achieved when a tensile prestrain is employed in a transverse direction. The
difference on behaviour with a change in the prestrain modes was said to have been
caused by residual microstresses.
The change in properties like ultimate tensile strength, elongation and hardness are not
affected by the mode of prestrain, while a higher amount of prestrain does not result in
a greater lower yield point elongation and a greater increase in the ultimate tensile
strength and an increase in the rate of work hardening<30l.
It has also been noted that while an increase in the amount of rolling reduction does
tend to delay the return of the yield point, the ductility of the material is severely
reduced after rolling and ageing.
Hundy et al have also studied that the cumulative effect of straining in increments and
ageing between stages of straining is much more than when the strain is applied in a
single step<6l. Experiments by Nakada et al revealed that as long as the ageing period
116
did not extend beyond the first stage of ageing, the ageing behaviour was insensitive to
the amount of prestrain.
4.2.5.3 Effect of Temperature
There is considerable evidence that in steels containing nitride formers the ageing
below 100 °C, which is believed to be as a result of nitrogen is negligible<29>_ Above
100 °C, solubility of carbon is sufficient enough to cause ageing. The predominant
effect of increasing the ageing temperature is to accelerate the ageing process. The
activation energies for strain ageing at a particular temperature are found to be
comparable to those needed for the diffusion of these interstitials at that temperature<29>
4.2.5.4 Effect of Prior Heat Treatment
It is obvious that effects of various heat treatments would have to be correlated with
various compositions of the steels <30 >. However a generalisation can be made on the
basis that any heat treatment that results in an increase in the carbon and nitrogen in the
matrix also increases strain ageing susceptibility.
It was earlier believed that removal of free carbon, nitrogen atoms in the matrix by
precipitation occurs during slow cooling. However, work done by Cottrell <112>, Morgan
<113> and co-workers have indicated the precipitates formed during slow cooling rates
would be too widely spaced for carbon and nitrogen atoms to be removed by diffusion.
It was suggested that quench ageing would be a better alternative to fix carbon and
nitrogen. This process gives rise to a higher density of nuclei at temperatures of 100 -
117
200°C and thus decreases the amount of carbon in solution(30 >. At temperatures below
these, the precipitates that form would be too small to be physically stable. These can
easily redissolve on restraining.
Further, it was also proved by Butler that the carbide distribution that forms during
cooling through the transition range affects the degree of carbon strain ageing<73 >_
Faster cooling rates in quenching or normalising would produce a ferritic structure
supersaturated with carbon. Heating to the annealing tern perature would produce a
fine, uniform dispersion of spheroidal carbides, while lower cooling rates like annealing
would result in the formation of pearlite colonies or grain boundary carbide films. The
grain size and hence the grain boundary carbide separation increases with decreasing
cooling rate. Slow cooling from the annealing temperature would allow carbon to
diffuse to existing carbide particles. As the temperature decreases further diffusion of
carbon becomes sluggish and carbon atom movement is limited to short distances. In
this respect steels containing a fine and closely distributed carbides would prove more
effective in removing carbon from the solution than steels containing a coarse
distribution of carbides.
With a steel containing nitride or carbide formers, an optimum heat treatment is one
that employs temperatures sufficiently low to give a low equilibrium solubility of
carbon and nitrogen and sufficiently high to allow precipitation of these elements. The
effectiveness of a given alloying element in inhibiting strain ageing will depend on how
closely this condition is approached.
118
As already mentioned earlier, strain ageing can be of two types : static strain ageing and
dynamic strain ageing. The next section contains an account of the process of dynamic
strain ageing and the factors that affect this process.
4.2.6 Dynamic Strain Ageing
This denotes the ageing processes, which occur simultaneously with plastic strain <3549>_
As a result, the effective strain rate is the most important parameter governing the
extent of ageing in steel. The ageing process can occur at room temperature in slow
tensile deformation (10 "6 sec · 1) and may also be effective in raising the room
temperature fatigue strength in many cases <35 -49 >_ At normal tensile deformation rates
i.e 10 4 sec · 1, dynamic strain ageing occurs in the range of 100 - 300 ° C <37>_ If the
interstitial solute levels are very high then effects of the ageing process may extend to
room temperature. At high strain rates - 10 1 to 300 sec -I (impact deformation), the
effects occur at 400 - 670 ° C. In the temperature range or 125 - 300 ° C, most low
carbon steel grades show a pronounced increase in work hardening rate and a decrease
in the ductility. The stress - strain curve changes from a smooth one to a serrated
shape. This blue brittleness phenomenon has been attributed to nitrogen and carbon.
Experiments by Baird and J~eson(I 10> have shown that in steels free of nitrogen and
carbon, the tensile properties exhibited a smooth behaviour. While in steels containing
carbon and nitrogen, serrated yielding was found in the range 175 - 225 ° C and jerky
flow in the range of 125 - 250 ° C. The appearance of serrated/ jerky flow may occur
during tensile, compressive or torsional loading conditions and is characteristic of
deformation during a specific regime of temperature, strain and strain rate<9&-I09>_ This
119
flow was first observed by Le - Chatelier in mild steels and was further investigated in
Aluminium alloy by both Portevin and Le Chatelier. It is also called the Portevin- Le
Chatelier or the PLC effect. These curves depict dynamic strain ageing which occur
when the rate of straining is such that the interstitials can diffuse and pin the mobile
dislocations and serrations occur because of a rapid generation of new dislocations
which are needed to sustain flow< 104 >_ In this region the probability of freeing
immobilised dislocations is very low. In the process of generating new dislocations the
stress increases.
While serrated flow curves are the most commonly observed macroscopic
manifestations of dynamic strain ageing, there are other phenomena. Bands of localised
deformation, known as PLC bands are also observed on the surface of a deforming
specimen producing a serrated curve< 100- 109 l_ The occurrence of intensified acoustic
emissions concurrent with the process has also been noted. However two important
features are associated with the process i.e. the peak in the flow stress variation with
temperature and the negative strain rate sensitivity of the flow stress< 111 >. The peak in
the flow stress is generally observed to occur at temperatures of - 0.3 Tm· Figure 4.33
shows the general cr - E curve for a pure metal and corresponding curves for an alloy
exhibiting dynamic strain ageing as a function of temperature. Strain localisation may
occur spontaneously as a result of the negative strain rate sensitivity arising as a result
of the process.
120
~-...,,,,,,--
,,,, I
\
i
1'. : ,............~
,••,,,- l
..
/ '
.,
<C
~
2
2
/ I
,// I I
I NO JERKS
I
0 I
z I
,so" 200°
Figure 4.33 A normal stress - strain curve (20°C) and corresponding curves
illustrating dynamic strain ageing as a function of temperature.
The solute responsible for dynamic strain ageing is considered to diffuse sufficiently
fast to slow down freely moving dislocations by forming an atmosphere around
them<93>, The solute atoms exert maximum drag on the dislocations when they move at
some critical speed v c, given by
vc - 4D I h -------------------------------------------4.23
where Dis the diffusion coefficient of the solute, his the effective radius of the solute
atmosphere.
The critical strain rate, Ee is given by
Ee = b p V = {4 p b/h} D------------ ---------4.24
where p is the mobile dislocation density.
D -0.12 Cv exp (-EIRT)-----------------------------------4.25
where E is the effective activation energy for the exchange of vacancies and
Cv is the vacancy concentration which increases with the amo unt of strain.
Cv - B & 111 -------------------------------4.26
121
Therefore
&c = 10 B exp (-E /RT) &cm _________________________________ 4.27
where Ee is the strain rate to the first serration. Further it was proposed by Ham and
Jaffrey that the variation in the dislocation density be taken into account<9 S) •
p- N !3 ----------------------------------------4.28
and therefore
- /. ,1 (m+/i) ,I 29
& - 1consta11t1 &c -----------------------------,.
Figure 4.34 shows the force-velocity diagram for a mobile dislocation. The motion of
dislocations through a metal in the absence of a solute atmosphere is retarded by lattice
friction< 9S)_ The retarding force increases as the velocity of dislocations increases (line
1)° 7). When the velocity of the dislocations is compatible with the diffusion rate of the
solute atoms, a cloud of these atoms will be attracted to the strain field of the
dislocations. As dislocations move, they effectively tow a cloud of solute atoms
through the lattice. The force required to drag the solute atoms increases rapidly with
velocity (Curve 2). As the velocity increases, the concentration of the solute atoms
around the dislocations is reduced, (curve 3). The solute concentration drop has the
effect of reducing the drag force.
Provided that the velocity of a given dislocation does not exceed a critical value Vm ,
the solute atmosphere will remain in the stress field of the dislocation as it moves
through the lattice. At dislocation velocities beyond V111 , the atmosphere can no longer
keep with the moving dislocation. This threshold velocity is a function of temperature,
species of solute and the bulk solute concernration. When a dislocation is suddenly
relieved of the drag force created by the solute atmosphere, it will accelerate up to the
122
next stable velocity V3• At this velocity, the dislocation encounters obstacles that will
slow its speed i.e precipitates, grain boundaries, dislocation substructures caused by
prior cold work. The dislocation is slowed to a point that the solute atmosphere can
once again keep up with the dislocation. The cloud of solute atoms once more
surrounds the dislocation and the cycle continuesC 17 >_
Force
,+-- (2) Solute drag force
I
1/
\ I (3) Concentration of
dift"using solut.e atoms
I ~
I \
I
I ~'~--~----------:i-r
:•
I
I
I • ··~
::
:
··~ '
'- •••
I
I
v. Velocity
SOLUTE i INSTABILITY1 LATTICE ....
DRAG i l FRICTION
Figure 4.34 Force-velocity diagram for a mobile dislocation (McCallum 17).
4.2.6.1 Effect of Carbon and nitrogen
Nitrogen produces a greater effect than carbon as in tl1-: case of static strain ageing,
due to its higher solubilityc 37 , 98 ) . A number of work1:L, hc1, e shown that as nitrogen
levels increase, the blue brittleness strengthening effects increase. Increasing the
123
Chapter 4 Strain. lgeing of low carbon steels
nitrogen levels raises the rate up to 10% strain and also extends the range of rapid
strain hardening induced by dynamic strain ageing. This occurs by increase in the
strain at which the supply of nitrogen to pin freshly generated dislocations becomes
exhausted. Local exhaustion manifests itself as coarse, localised bands of
deformation in which nitrogen is exhausted( 37 , 112 ) . If the material in these bands
cannot work harden sufficiently to compensate for the reduction in area of the test
piece in the band, the specimen breaks ,vithin the band with a low elongation.
Increasing the nitrogen level increases the strain at which 1his occurs, thus increasing
the elongation to failure< 37 >_ However at sufficienlly high nitrogen levels the
elongation to fracture returns to the same value as when the steel was free of nitrogen
i.e embrittlement effects are zero<37).
4.2.6.2 Effect of substitutional alloying elements
The effect of substitutional alloying elements in solid snlution on static strain ageing
normally is to slow down the rate of ageing. In the case uf dynamic strain ageing,
elements like manganese, chromium, molybdenum, tungsten and copper give rise to
strain hardening during tensile deformation of steel at temperature considerably above
the normal blue brittleness range< 93>_ Several of these elements also tended to decrease
the intensity of carbon- nitrogen effect at around 200 ° C. Presence of substitutional
solutes with an affinity for carbon or nitrogen extends tb\..· blue brittleness peaks to
high temperatures <37 , 98 >. Chromium produces a similar effect to manganese and
molybdenum extends this blue brittleness to higher temperatures.
-------------------- - - - ------------
124
Chapter -I- Strain Ageing of/ow carbon steels
Similar to the effects on static strain ageing, substitutionai alloying elements like nickel
which have no affinity for carbon and nitrogen appear to havl' little or no effect on the
dynamic strain ageing. The effects of carbide and nitride formers appear to be
qualitatively similar to those obtained in static strain ageini 981 .
4.2.7 Strain dependence of Static and Dynamic ageing
Both, static strain ageing and dynamic strain ageing are strain dependent. The physical
basis of dynamic ageing is an increase in the effective dislocation glide resistance due
'l' of so lute atoms above a certam
tothe mo b11ty . temperatur~ (I0"-104)
- . Stat1c
. stram
.agemg
.
occurs as a result of the segregation of solute atoms at dislocations at room
temperatures or slightly above room temperature. There have been several models that
predict the strain dependence of static and dynamic strain ageing on strain. In earlier
models it was assumed that mobile solutes vverc interacting with moving
dislocations<93)_ However, it was later realised that the dislocation movement was
always jerky and the effect of solute mobility on the glide resistance will not take place
during the actual movement of the dislocations but when the dislocations are waiting at
obstacles. It was postulated that the strain rate sensitivit) index of the flow stress
affected the behaviour of the materia1° 02 - 1041 . It was also assumed that any solute
mobility that affects the total strain rate sensiti\·ity negati\ ely and that this contribution
increases with strain. When the total strain rate scnsiti\ 1ty becomes negative, then
plastic flow becomes jerky or unstable. This is supported by the experimental
observations that the point of time when the llmv becornl's _jerky after a certain amount
125
Chapter 4 Strom Ageing of low carbon steels
of critical prestrain, occurs at approximately at the same point at which the strain rate
sensitivity becomes negative<9 S)_
Different models have however explained the dependence of the rate sensitivity
differently. Van den Beukel believed that the diffusion coefficient of the solute is strain
dependent which follows from the fact that there is a known increase in the vacancy
concentration with deformation< 106' 107 )_ This applies to substitutional alloys only. The
mobile dislocation density was also found to depend on the strain as indicated from the
relation between the strain rate and the time. This applies tu all the alloys. Another
model by Mulford and Kocks proposed that the strain rate sensitivity in normal alloys is
better described in terms of the flow stress than the strai1/! 8). It was also stated that this
model was only applicable to the dynamic strain ageing process. They concluded that
the solute mobility affects the strain hardening component of the flow stress rather than
the friction stress.
Both models are incomplete in that they do not explain strain (kpendent diffusion or the
dependence of mobile dislocation density on strain.
This comprehensive literature review as presented in Chapters 2, 3 and 4 is followed by
Chapters 5, 6, 7, 8 and 9 which contain information pcrt:1ini11g to the current research
study. The next chapter outlines the main objectives of the current research.
126
Chapter 5 Research Objectives
CHAPTERS
RESEARCH OBJECTIVES
127
5. RESEARCH OBJECTIVE
BHP Long Product Division at Newcastle have been supplying low carbon steel rod
grades for wire drawing applications. Several instances of difficulties in drawing these
rods to wires were encountered and detailed investigations of these cases pinpointed the
cause to strain ageing. It was therefore felt necessary that a detailed study of this
phenomenon of strain ageing be carried out in the low carbon steel grades under various
conditions of testing.
The primary aim of the project was to evaluate the strain ageing behaviour of low
carbon steel wire grades used for structural applications and produced at BHP,
Newcastle. The specific objectives were:
• To evaluate the strain ageing behaviour through the use of hot torsion tests
under specific parameters:
Initially hot tension tests were attempted for this purpose. However these
proved less suitable to simulate industrial drawing conditions when
compared to hot torsion, as explained in section 7.5. Hot torsion tests have
been used as the closest possible simulation of the hot rolling/drawing
processes, which allow the material to be formed under a triaxial state of
stress. Other researchers< 27 > have used the hot torsion test to study behaviour
of materials under rolling/drawing conditions.
• Study the strain ageing behaviour as a function of steel nitrogen content: As
indicated extensively in literature, nitrogen is found to be the main cause for
strain ageing. It was therefore considered appropriate to study the impact of

128
vanous nitrogen contents on the strain ageing behaviour of low carbon
steels.
• Study the impact of boron addition on the strain ageing behaviour of the
above grades of steel:
Literature has described the various remedial methods that have been used
to alleviate strain ageing. One of the more common and successful ways
have been to fix free nitrogen and carbon in the steel with the deliberate
addition of strong nitride/carbide formers to the steel. As already
summarised in the literature in section 4.1.4.1, initial studies on boron have
revealed an appreciable effect of boron on strain ageing. However, as
mentioned earlier, the exact amount of boron that needs to be added and the
nature and kinetics of precipitation of the boron nitride needs to be studied.
• Study the effect of drawing temperature and time held in between drawing
stages on the strain ageing behaviour:
Temperature and time have been proven to have a significant effect on the
strain ageing phenomenon. During actual manufacturing processes, often,
there are delays between stages, as a result of which the material may be
held soaking at a particular temperature for a certain period of time. This
could have deleterious effect on the mechanical properties in terms of strain
ageing. It was therefore considered necessary to study the effect of these
parameters on various steel compositions.
• Correlate the above hot torsion results with steel microstructures using the
transmission electron microscope:
129
As mentioned earlier, one of the more popular methods of combating strain
ageing is to fix the free nitrogen/carbon with the addition of suitable alloying
elements to form nitrides or carbides, which would be distributed in the steel
microstructure. Therefore characterisation of the steel microstructures was
of paramount importance as this would yield useful information that could
explain the trend in mechanical properties.
The next Chapter describes the experimental procedure that was adopted in the current
research project.
130
Chapter 6 Experimental Methods
CHAPTER6
EXPERIMENTAL METHODS
131
EXPERIMENTAL METHODS
6.1 STEEL COMPOSITION AND PROCESSING:
Four low carbon steel grades used for structural applications were chosen for study.
These steels were produced at the BHP steel Newcastle works. Table 6.1 lists the
chemical compositions as determined by conventional wet analysis and atomic
spectrometer methods, of these four steels. Two of these steels were production steels
produced by the conventional "Basic Oxygen Steelmaking" (BOS) process, where
oxygen is blown through the steel. One of the BOS steels had a low nitrogen content
(0.002 wt%), while the other contained more nitrogen, 0.008 wt%. The third grade, an
experimental steel chosen for the current study was produced by the electric arc (EAF)
process and had 0.008 wt% nitrogen with deliberate additions of 0.001 % boron. The
other steel was also an experimental steel, prepared by the Basic Oxygen process and
had 0.006 wt% nitrogen and 0.004% boron, added with an intention of scavenging the
nitrogen.
6.2 ROOM TEMPERATURE MECHANICAL PROPERTIES:
The steels were tension tested for their mechanical properties at room temperature using
an Instron machine (model 1185 manufactured in U.K) using a conventional strain rate
of 10 -I /sec to Australian Standard AS 1391 using a 5mm diameter test piece.
6.3 MICROSTRUCTURAL CHARACTERISATION:
6.3.1 Optical microscope:
Samples cut from as-rolled rods of the four steel grades were metallographically
polished using different grades of silicon carbide papers and diamond paste polishing
cloth. These were then etched with a solution of 2% Nital. The microstructures were
132
examined by bright field optical microscopy with the objective of characterising the
different phases present on an Olympus PMG3 microscope.
Table 6.1 Chemical compositions of the four grades of plain carbon steels used for
test.
MATERIAL C Mn Si Ti V Cr Al Mo N B
BOSLowN 0.07 0.32 0.158 0.001 0.001 0.03 0.004 0.01 0.002 0
BOS HighN 0.08 0.33 0.17 0.001 0.002 0.02 0.003 0.01 0.008 0
EAF 0.05 0.49 0.144 0.001 0.003 0.05 0.003 0.01 0.008 0.0012
(LOWB)
BOS (N+B) 0.08 0.36 0.174 0.02 0.006 0.01 0.006 0.0038
(HIGH B)
MATERIAL TOTAL SOLUTE TOTAL INTERSTITIAL

CONTENT CONTENT
BOS LOWN 0.596 0.072
BOSHIGHN 0.624 0.088
EAFLOWB 0.7602 0.0592
BOSHIGHB 0.6598 0.0918
6.3.2 Transmission electron microscope characterisation (TEM)
Sections of as-rolled rod samples of the four steels were sliced, electro-discharge
machined to the required 3mm disc size and mechanically polished to 0.1mm thickness.
These thin sections were then electropolished using a solution of 5% perchloric acid in
acetic acid to electron transparent thickness suitable for transmission electron
microscopy. The samples were then examined under a Phillips 200 transmission
electron microscope.
133
6.4 ELECTRICAL RESISTIVITY
Initially it was intended that the sequence of the strain ageing behaviour be studied by
electrical resistivity measurements. This meant that a thermal simulation of rod rolling
and wire drawing steps be carried out coupled with sensitive electrical resistance
measurements. Initial tests on studying quench ageing behaviour on these low carbon
steels did not provide very consistent data, as a result of the low sensitivity of the
experimental apparatus used to measure the resistivity. Therefore this technique was
discarded.
6.5 HOT TENSION TESTS
Initially, hot tension tests were carried out on a limited number of samples in an attempt
to evaluate the strain ageing behaviour. The materials, which were received as 5 mm
rods were tested in the as received condition for this test. A fixed length of 40 mm
from the as received rods served as the test piece. A small resistance-heating furnace
was loaded onto an Instron tensile testing machine. The sample holders, together with
the sample, were fixed in such a way that the sample was held in the hot zone of the
furnace throughout the test duration. The material rods were heated to a temperature of
either 130°C or 200°C and soaked for a period of 5 minutes for temperature uniformity.
Uniaxial loads were then applied on the samples at a strain rate of 0.3/second. After an
initial prestrains varying between 0.1 - 0.2, the load was removed and the sample
soaked at this temperature for either 30 seconds or 600 seconds. Subsequently, the
samples were tested to failure at this temperature.
134
6.6 HOT TORSION TESTS
The torsion test has been used over a long period of time to assess the hot workability of
.
vanous . 1sc212s111-119)Th
matena ' ' . e advantages ofhh · test me
t e ot torsion · Id
u e
• in-situ simulation of strain ageing which incorporates simulation of rod rolling and
wire drawing stages.
• capability of generating very high strains and strain rates which would be a closer
simulation of the actual wire drawing process<27)_
A hot torsion facility was designed and constructed by BHP Melbourne Research
Laboratories. This equipment previously had been extensively used for this type of
testing in other studies in which the test method and results were validated. All hot
torsion tests mentioned in the current study were carried out initially at BHP Research
Laboratories, Melbourne. Before completion of this research work, this laboratory had
closed and the hot torsion equipment was moved to Deakin University, where the
remaining experiments were completed.
The steels were received in bar form, 20 mm in diameter. To facilitate hot torsion tests,
these bars were machined to fabricate specimens of dimensions as shown in Figure 6.1.
The hot torsion rig used for the current study was capable of working up to temperatures
of 1000 °c and at strain rates as high as 350/sec. The rig was horizontal type with the
specimen bolted onto its heads, one movable and the other fixed. The brake was a
pneumatically operated clutch brake, which was capable of stopping the twisting in a
very short time. The efficiency and consistency of this rig was extensively evaluated
before actual tests 011 -119 )_
135
Prior to testing, the steels were austenitised at 1100°C for 30 minutes and then cooled to
950 °C at the rate of 2°C/sec. The steel specimens were then torqued to an initial strain
of 1.05, in an attempt to simulate the rod-rolling step. The specimens were then cooled
to 600°C at a rate of 3°C/sec and then to room temperature at the rate of 1-2°C/sec and
baked at 170°C for 40 minutes. This cooling sequence was an exact replication of the
cooling sequence used in the actual production sequence. Following this, the specimens
were heated to the wire drawing temperature of either 130° or 200°C and then torqued
to a strain of 0.33, the nearest experimentally possible simulation of the wire drawing
step. The temperatures chosen are again the temperatures commonly used during wire
drawing. The specimens were held after the initial strain for a period of either 30
seconds or 600 seconds and then torqued to failure. The delay time chosen represent the
extremes that would probably be encountered in the actual production sequence. This
procedure is illustrated in Figure 6.2. The stress-strain data was then determined and
plotted from the hot torsion tests through a software package, which converted surface
strain and torsion stress to true stress and strain.
Results of the tests that are described in this Chapter are outlined in the next Chapter.
136
Chapter 6 Experimental lvlethods
k<----------1~0 .. ~ - - - - - - - - - - - 1
?.
t kl,..,.. i-----4•- ~3.,.,,r, ~
•'II
.,. ~ ~
?
'"°' ,.... l
."
·----- - - - --lM y ••1
--=t---l----·-·--
'Ji: ... h --
.,:,
"'&...
r"
~
~
~
'Q. 'Q.
(S ~ ~
~
,,c
1
l
0
1-1
.)
"Q.
0
-~ 3 3 )
I
1
·!
' It
in
i
I :S>
~
%.
Figure 6.1 Typical specimen geometry of a hot torsion test sample.
137
<.__-:hapter 6 Experimental lvlethod.r;;
t .30 rn.i0u.-le.s
1-oi.bal s-lt-a..i..n I· 05
9BOc
u
"'
1-!J
et.
::)
I-
~
C::
\JJ
Cl.
t
l-~ 0c/sQ.c
I. \
~co c .sfro..in 0·33
0
~ ~ ' hald ~ ro rnc._n or

0
l':70 C
o-~ nun
40 .
~ - - - \ 130°c. slra.in 0·33
ha.ld ~ to min. m-
e, s ,.,..,'-".
t 0,9,UJl.d U> f'o.i.lurQ. .
Figure 6.2 Test schedule used for bot torsion tests
138
Chapter7 Results
CHAPTER 7
RESULTS
139
Chapter 7 Results
This chapter describes the results obtained in various tests on the four steels. Section
7.1 shows the results of the optical microscopic examination of sections cut from the as-
rolled rods of the four steels. Section 7.2 describes the results of the measurements of
free nitrogen content in the four grades of steels. Results of room temperature
mechanical tests on the steels are described in Section 7.3, while section 7.4 shows the
TEM photographs of the sections of as-rolled steels. Sections 7.5 and 7.6 show the
results obtained from hot tension and hot torsion tests respectively.
7.1 OPTICAL MICROSCOPIC EXAMINATION:
Figures 7 .1 - 7.4 show the microstructures of the four grades of steel m the "as
received" condition i.e " as rolled" condition.
Figure 7.1 Optical microstructure of BOS low nitrogen steel
140
Chapter7 Results
Figure 7.2 Optical microstructure of BOS high nitrogen steel
Figure 7.3 Optical microstructure of EAF low boron steel
141
Chapter7 Results
Figure 7.4 Optical microstructure of BOS high boron steel
Table 7.1 Image analysis
PROPERTY BOS LOWN BOSHIGHN EAFLOWB EAF HIGH
GRAIN SIZE ASTM8 ASTM8 ASTM8 ASTM6-7

( 18-~~ ,Ull') (i8-Q~_?l'I) G s - oRQ µm) ( Qq-uoµm
Volume 6.7 7.1 8.1 8.8
%PEARLITE
The microstructures were characterised using an image analysis system (Quantimet).

Table 7.1 summarises the image analysis results of these microstructures. It is obvious
from the above microstructures and the image analysis results that the BOS low and
high nitrogen grades and the EAF low boron grade appear to show a similar grain size.
However, the microstructure in the BOS high boron steel grade shows a slight coarser
grain size. The amount of pearlite seems marginally greater in the boron containing
grades. It is to be noted that the dark spots that appear on these micrographs are not
142
Chapter7 Results
precipitates or second phase particles, but are polishing and etching artefacts that have
resulted due to the softness of the steel grades.
7.2 DETERMINATION OF "FREE NITROGEN"CONTENT IN THE STEEL GRADES
The hydrogen hot extraction method was used to determine the amount of free nitrogen
in the samples, according to the procedure outlined in reference (120). The steel
samples were cut into pieces of an approximate size of2-3 mm which were used for this
experiment. These chips were placed in a silica crucible and annealed in a stream of
99.9 % pure hydrogen at 450°C under a gas flow rate of 200 cc/minute for a period of
one hour. The samples were then cooled and analysed for nitrogen content using
LECO TC 436 instrument. Samples of the original material were also analysed using
the LECO analyser for total N content. Results are tabulated below. All values are in
wt%.
Table 7.2 N·t

1 roeen anaw . of steel era des aft er hot ex tracf10n w1·th
l sis hlYd roeen.
Material Total Total Total N N content Difference
N B (LECO) after hot (A-B)
(A) extraction attributed to
(B) free nitroeen
BOSLowN 0.002 - 0.003 nd nd
BOSHiehN 0.008 - 0.008 nd nd
EAFLowB 0.008 0.0012 0.0078 0.0024 0.0054
BOS Hieb B 0.006 0.0038 0.0069 0.0026 0.0043
Nd- not determined
7.3 ROOM TEMPERATURE MECHANICAL PROPERTIES:
Rods from the four steel grades were tested for room temperature mechanical properties
using an Instron machine. These results are tabulated in the following table7.3.
143
Chapter7 Results
Table 7.3 R oom t empera t ure mec h amca

. I properties of stee s used"m current stu dy
MATERIAL 0.2% ULTIMATE %
PROOF TENSILE ELONGATION
STRESS (MPa) STRENGTH (MPa)
BOS LOWN 30.9 40.3 53.9
BOSHIGHN 32.1 42.9 53.4
BOSHIGHB 22.8 34.5 61%
EAFLOWB 32.3 42.6 50.9
7.4 TRANSMISSION ELECTRON MICROSCOPIC EXAMINATION:
Some typical features in the four steel compositions in the as-rolled condition as
observed under the TEM are shown below. No distinct differences were observed in
these steel grades.
Figure 7.5 (a) TEM micrograph of a BOS grade high nitrogen steel
144
Chapter? Results
Figure 7.5 (b) TEM micrograph of a BOS high boron steel
7.5 HOT TENSILE TESTS:
Figure 7.6 shows the stress strain curves obtained from hot tension for the BOS low N
grade steel. Similar results are shown in Appendix A. Problems encountered during the
test were
• the inability to apply a consistent prestrain with the present set-up.
• Temperature control was within± 15 °C and
• Total prestrain that could be applied was very small as compared to actual
strains achieved during wire drawing. The order of strains used in drawing operations
are of the order of a minimum of 0.5 and above. However in a hot tension test a
maximum strain of approximately 0.06 can be applied. Moreover, the strain rates used
in hot tension are also only a fraction of the actual strain rate used in wire drawing.
Therefore hot tension was not a close simulation of the drawing process and this testing
was not pursued further.
145
Chapter7 Results
Stress strain curve at 130 C - 47757(1) - increasing

prestrain - 10 minutes
(BOS Low N)
50
45 0.14 prestrain
40
Stl35
es30 0.1 prestrain
~i?5
a)20
15
10
5
0
0 0.2 0.4 0.6
Strain
Figure 7.6 Consistency in hot tension tests
7.6 HOT TORSION TESTS
Figure 7.7 shows a typical true stress strain curve derived from engineering stress- strain
values obtained from a hot torsion test. X-axis values are true normal strain values and
the true normal stress values in megapascals are plotted on the y-axis. As already stated
earlier, the two different parts of the curve are labelled in the Figure 7.7. The initial part
of the curve labelled as A is the prestrain and the subsequent part is the stress-strain
behaviour when tested to failure after holding for a period of time following initial
prestrain for a period of either 30 seconds or 600 seconds.
146
700
600
-
CU
D.
500
-
:al:: 400
en
en
W 300
a::
I-
en
200
100
0
0 0.5 1 1.5 2 2.5 3
STRAIN
Figure 7.7 A typical true stress-strain curve derived from the hot torsion data.
147
Chapter 7 Results
7.6.1 Consistency of hot torsion tests
The consistency of the stress-strain data is illustrated in Figure 7.8. The figure shows
the stress-strain curves obtained on repeat runs on a specific steel composition under the
same parameters of temperature, prestrain and time of holding after prestrain. An
important point to note is that the level of prestrain is consistent in all tests. The values
of flow stress appear fairly consistent with a scatter of± 10 Mpa (a percentage error of
5%). However the strains to failure show a larger scatter in the range of 0.2(8% error).
The magnitude of these errors were taken into account when interpreting test results.
Figure 7.9 shows the stress strain curves obtained on repeat runs on the same
composition of steel tested under the same parameters with a superimposed error band.
The stress-strain values have been compared only when the difference in the absolute
readings consistently exceed the error limits specified.
7.6.2 Hot torsion test results:
The true stress - strain curves of samples tested under hot torsion are shown in
Appendix B. These curves show the variation of true stress as a function of true strain.
148
Chapter 7 Results
This page has been intentionally left blank
149
700
600
_ 500
CU
a.
6 400
en
en
w 300
0:::
..,_
en 200
100
0
0 0.5 1 1.5 2
STRAIN
Figure 7.8 Consistency of hot torsion results on EAF steel containing low boron and high nitrogen, when tested at 200°C and a
150
700 , - - - - - - - - - - - - - - - - - - - - - - - - - - -
600
-ea 500
D.
~ 400
en
en
W 300
0::
I-
en 200
100
o---------------.-------- -.--.....a.---------------
0 0.5 1 1.5 2 2.5 3
STRAIN
Figure 7.9 (a) Error band calculated for the stress values.
151
700 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
600
ci 500
D.
~ 400
en
en
W 300
0:::
I-
en 200
100
0 -L----.....--------.-----~~~5'-----,--------,----~
0 0.5 1 1.5 2 2.5 3
STRAIN
Figure 7.9 (b) Error band calculated for the strain values.
152
Chapter 7 Results
7.6.2.1 Influence of temperature on the stress-strain behaviour of the four steel
compositions:
Figures 7 .10 to 7.17 compare the stress strain curves of the four steels as a function of
test temperature. It is evident that the nature of the curves in the region of the initial
prestrain are different. At the higher test temperature of 200°C, the initial part of the
curve (during prestrain) appears to have a higher slope. After the initial prestrain, the
curves show a similar behaviour in the strain to failure region. This trend is evident in
all the four steel compositions and for both the delay times. The flow curves at 200°C
appear more serrated than those at 130°C, probably indicative of more dynamic strain
ageing at 200°C than at 130°C.
153
700 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -....
600 0
@130 C Aging index= 71.SMPa
•
@200 C Aging index =24.6 Mpa
500
'ii
D. 400
:a:
ui
rn
w
~
I- 300
m
200
100
o ....
0
-----...-------...-------...---------...-------...-----------1
0.5 1.5 2 2.5 3
STRAIN
Figure 7.10 Stress strain curves of BOS low N steel as a function of test temperature tested after a delay time of 30 seconds after
prestrain.
154
700
600 0
@130 C Aging index= 83.1 Mpa
0
@ 200 C Aging index =38.2 Mpa
500
'j 400
:iii:
'ii,
Ill
,,,i 300
200
100
0
0 0.5 1 1.5.
S tram 2 2.5 3
Figure 7.11 Stress strain curves of BOS high N tested as a function of temperature tested after a delay time of 30 seconds after
prestrain.
155
700 - - . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
Cl>
600 @130 C Aging index =21.4 Mpa

C>
@ 200 C Aging index =85.2 MPa
500
-CIS
400
-
CL
:E
0
-
0
f!! 300
en
200
100
0+---------,------,------~ -------,.------,---------1
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.12 Stress strain curves of EAF low B steel as a function of temperature tested after a delay time of 30 seconds after
prestrain.
156
700
@ 130'\: Aging index = 69.9 MPa
0
@ 200 C Aging index = 54.2 MPa
600
200C
500
l::E: 400
'in
II)
i
en
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.13 Stress strain curves of BOS high N+B steel as a function of temperature tested after a delay time of 30 seconds after
prestrain.
157
700
0
@ 130 C Aging index= 67.7 MPa
600 •
500
-C'II
o.. 400
-
:::!!:
U)
-
U)
f 300
tn
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.14 Stress strain curves of BOS low N steel as function of temperature tested after a delay time of 600 seconds after
prestrain.
158
700 - . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
0
600 ~
200 C
500 130 C
-"'
a. 400
-
:E
I ll
-
Ill
~ 300
u,
200
100
0 +-------...--------,------~--------,--------,----------'I
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.15 Stress strain curves of EAF low B steel as a function of temperature tested after a delay of 600 seconds after
prestrain.
159
700 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
0
600 0
@200 C Aging index =31.8 Mpa
500
'i:!!: 400
U)
en
-
! 300
u,
200
100
0 - - - - - - - - - - - -.........- - - - - - - - - - - - - - . . . . - - - - - -
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.16 Stress strain curves of BOS high N steel as a function of temperature tested after a delay time of 600 seconds after
prestrain.
160
700 - . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
•
@ 130 C Ageing index =116.4 MPa
600 •
500
'ii 200C
ll. 400
:E
I2!
-
en
300
200
100
0 -!----------,---------,------ --r----------r------.......,:i --....- - ~

0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.17 Stress strain curves of BOS high N+B steel as a function of temperature tested after a delay of 600 seconds after
prestrain.
161
Chapter 7 Results
7.6.2.2 Influence of delay time after prestrain on the stress strain behaviour of the
four steel compositions:
Figures 7.18 to 7.25 compare the stress strain curves of the four different steels as a
function of delay times after prestrain. There seems to be no major difference in the
behaviour of the materials at different times of delay except for a slight difference in the
total strain to failure in several samples. These variations in strain to failure are
believed to be due to random experimental errors, and they are not considered to be
significant. There seems to be no appreciable difference in the stress levels or the
nature of the curves at the two delay times.
162
700
@30 SECONDS Aging index= 71.SMPa
600 @ 600 SECONDS Aging index= 67.7 MPa
600SECONDS
500
'ii 30SECONDS
a.. 400
!!.
Ill
Ill
-~
u,
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.18 Stress strain curves of BOS low N steel as a function of delay time after prestrain tested at 130°C.
163
700 @ 30 SECONDS Aging index=83.1 MPa
600 @ 600 SECONDS Aging index =85.5 MPa
500
-
ns
a. 400
600SECONDS
-
:iE
,n
,n
-
f 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.19 Stress strain curves of BOS high N steel as a function of delay time tested at 130°C.
164
700
@ 30 SECONDS Aging index =85.2 MPa
600
@ 600 SECONDS Aging index= 149.9 Mpa
500
-
CU
400
-
0.
:iE
,n
,n
-
f 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.20 Stress strain curves of EAF low B steel as a function of delay time tested at 130°C.
165
700 • @ 30 SECONDS Aging index = 69.9 MPa 1
@600 SECONDS Aging index=116.4 MPa

600
600 seconds
500
-CG
a. 400
30 seconds
-
:::E:
,n
,n
-! 300
u,
200
100
-----,-------,-------,-------,------~-----!
0 .....
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.21 Stress strain curves of BOS high N+B steel as a function of delay time after prestrain tested at 130°C.
166
700
@ 30 SECONDS Aging index= 24.63 MPa
500
-
CU
a. 400
30 SECONDS
-
:E
U)
-
U)
f 300
U)
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.22 Stress strain curves of BOS low N steel as a function of delay time after prestrain tested at 200°C.
167
700
600SECONDS
-I
ea
500 30SECONDS
-i
en
400
-
...
en
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.23 Stress strain curves of BOS high N steel as a function of delay time after prestrain tested at 200°C.
168
700
@ 30 SECONDS Aging index =21.4 Mpa
600
500 I
-ns
400
4 30SECONDS
-!
ll.
:ii!:
I I)
-
en
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.24 Stress strain curves of EAF low B steel as a function of delay time after prestrain tested at 200°C.
169
700
@ 30 SECONDS Aging index = 54.2 Mpa
30 SECONDS
500
600 SECONDS
-
:._ 400
-t
:ii:
,n
,n
300
u,
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.25 Stress strain curves of BOS high N+B steel as a function of delay time after prestrain tested at 200°C.
170
Chapter 7 Results
7.6.2.3 Influence of material composition on the stress strain behaviour of the
four steel compositions:
Figures 7.26 to 7.29 depict the stress strain curves of the four different material
compositions at different test temperatures and delay times after prestrain. It is
important to note that in general, a very similar trend is exhibited by the materials at
various test parameters. There is no significant difference in the behaviour of the BOS
high N and the EAF low boron grade, as observed in Figures 7.26, 7.27 and 7.28. The
highest value of total strain to failure is exhibited by BOS high N+B material, followed
by BOS low N, EAF low Band lastly BOS high N. This is true for all combinations of
test temperatures and delay times as observed in Figures 7.26-7.29. In addition, BOS
high N+ B grade appears to show an appreciable decrease in the stress values as
compared to the other steel grades as observed in Figures 7.26-7.29.
In general as observed from figures 7.26-7 .29, the level of the stress-strain curves
follow a definite order - BOS high N+ B is the lowest followed by BOS low N and then
by BOS high N and EAF low B.
The slope of the stress-strain curves in the prestrain region, which is indicative of work
hardening appears to be approximately the same and relatively a higher value for BOS
high N and EAF low B steels at both the test temperatures and delay times. This is
followed by the BOS Low N steel and then the BOS high N+ B steel. A similar trend is
noticed in the strain to failure region for the four grades at all combinations of test
temperatures and times.
171
650
600
550
500
ii
a.
450
:ii: BOS High N
ui 400 SLowN
tfj
~
-
UJ 350
BOS Hidh N+B
300
250
200
150
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.26 Stress strain curves of the four material compositions tested at 130°C and 30 seconds delay time after prestrain.
172
650
600 l __ t\..z) eat EAFLowB

550
500
'i_ 450 i 1.........-- BOS High NI I I BOS High NtB

:E
wtn
400
Cl)
a..
I NII L I IBOS Low N
u, 350
300
250
200
150
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.27 Stress strain curves of the four material compositions tested at 130°C and a delay time of 600 seconds after prestrain.
173
650
600
550
500
-ns 450
0..
:E: BOS Hidh N + B
BOS High N
;; 400
U)
G)
b 350
Cl)
BOS Low N
300
250
200
150
0 0.5 1 1.5 2 2.5 3
Strain
Figure 7.28 Stress strain curves of the four material compositions tested at 200°C and a delay time of 30 seconds after prestrain.
174
650 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
EAF LowB
600
550
500
ci 450
D. BOS High N+B
:il:
"; 400 BOS High N
VI
f
u; 350
300 BOS LowN
250
200
150 __.,_-----+------.--------,.--+----.....--+----.1.------,-------+---------l
0 0.5 1 1.5 2 2.5 3

Strain
Figure 7.29 Stress strain curves of four material compositions tested at 200°C and a delay time of 600 seconds after prestrain.
175
Chapter 7 Results
7.6.3 Results of transmission electron microscopic examination:
Sections parallel to the fracture surface of the hot torsion samples were prepared for
examination under the transmission electron microscope according to the procedure
described in section 7.4. Several micrographs are shown in Figures 7.30. to 7.35.
From the micrographs it is evident that there are no precipitates, small or large, that
are present in any of the samples examined of the four different material compositions
or under any combination of test parameters. The ferrite matrix does not contain any
evidence of any BN or any other nitride or carbide precipitates. Selected area
diffraction patterns were observed and confirmed the above findings. They were
however not included in the thesis as they were not of a very high photographic
standard.
Figure 7.30 Transmission electron micrograph showing a very high density of

dislocations and a matrix devoid of precipitates in BOS low nitrogen grade of steel
tested at 200°C after a delay of 600 seconds.
176
Chapter 7 Results

dislocations and a matrix devoid of precipitates in BOS high nitrogen grade of steel
0.2µm
-
dislocations and a matrix devoid of precipitates in EAF low boron grade of steel
177
Chapter 7 Results

dislocations and a matrix devoid of precipitates in BOS high nitrogen + boron
grade of steel tested at 130°C after a delay of 600 seconds.
Figure 7.34 Transmission electron micrograph showing a very high density

of dislocations and a matrix devoid of precipitates in BOS high nitrogen +
boron grade of steel tested at 200°C after a delay of 30 seconds.
178
Chapter 7 Results

dislocations and a matrix devoid of precipitates in BOS high nitrogen + boron
grade of steel tested at 200°C after a delay of 600 seconds.
179
Chapter 8 Discussion
CHAPTERS
DISCUSSION
180
8.1 OPTICAL MICROSCOPY EXAMINATION
The optical microstructures of the BOS low and high grades of steel and the EAF low
boron steel grade do not show much difference in the grain size. This is most probably
due to the very minor difference in the compositions of the grain refiners like Al. The
BOS low N and the EAF low B grades contain 0.003% Al as compared to 0.004% in
BOS high N grade. Although the EAF grade contains an addition of boron which can
form fine precipitates that can restrict grain growth [Franks and Kirkaldy< 73 >; Clark and
Vamey< 8>], the amount added is so small as to not make any appreciable effect. In
contrast, the BOS high boron steel shows a marginally coarser grain size, although it
contains a marginally higher amount of Al (0.006%). This is attributed to the fact that
boron has not been able to form grain growth restricting precipitates like BN. This
conclusion is supported by evidence from transmission electron microscopic
observations as shown in section 7.6.2. However it must be noted that the increase in
grain size is only marginal and is discussed here on the basis of the observations made
by Takahashi and Shibata-Faulring<54>_
8.2 ROOM TEMPERATURE MECHANICAL PROPERTIES
The room temperature mechanical properties of the BOS low and high nitrogen grades
and the EAF low boron grade appear similar. This is despite the fact that two of these
grades contain high nitrogen, which is known to increase work hardening (there is only
a marginal increase in the strength values). However the BOS high nitrogen and high
boron grade do show a decrease in the strength values (both yield and ultimate tensile
stress) and an increase in the elongation. This could be attributed in part to the increase
in grain size observed in the high boron grade steel.
181
8.3 HOT TORSION PROPERTIES
8.3.1 Influence of temperature on the stress - strain behaviour of the four steel
compositions:
8.3.1.1 Work hardening exponent
The nature of the stress strain curve at 200°C is very different from that exhibited at the
lower temperature of 130°C. In the prestrain region, the 200°C curve appears to have a
higher slope. The slope of a true stress-strain curve indicates the work hardening
exponent. Therefore, the work hardening exponents have been computed, as shown
Figures C-1 to C-31, Appendix C and the exponents are listed in Table 8.1. It may be
noted however that the current study is under triaxial stress states and values of work
hardening exponents computed may not necessarily be the same as in uniaxial tension
state. The work hardening exponent has been computed for both the prestrain region
and the strain to failure region separately. In order to minimise errors in comparison,
stress values at fixed values of strain (0.35 and 1.08) have been used to calculate the
exponent for all materials and test parameters. Figures C-1 to C-15 show the calculation
of the exponent in the prestrain region. Figures C-16 to C-31 show the calculation of
the exponent in the strain to failure region. For ease of comparison, these values have
been shown on a bar chart in Figures 8.1 and 8.2. It is evident from the bar charts that
at both 30 and 600 seconds, the work hardening exponents at higher temperature of
200°C are higher as compared to the exponent values at the lower temperature of 130°C.
This is attributed to the occurrence of dynamic strain ageing at higher temperatures
where both interstitial carbon and nitrogen have diffusion coefficients sufficiently high
in order to pin the dislocations dynamically during straining itself. A comparison of the
diffusion coefficients at l 30°C and 200°C indicate that the coefficient at 200°C is
approximately 125 times higher than at the lower temperature (De 20ocl De 130c = 30, as
182
per equation 4.14). This trend is generally observed in all the four steel compositions.
However the actual values of the exponents differ from material to material. This
observation is explained in section 8.3.3.
Table 8.1 Values of work hardening exponents of the four different steel
Material Work hardenin2 exponent

130°C 30 seconds 130°C 600 seconds
Prestrain Strain to Prestrain Strain to
failure failure
BOSLowN 0.28 0.17 0.27 0.17
BOSHi2hN 0.30 0.15 0.24 0.15
EAFLowB 0.24 0.15 0.25 0.16
BOS High 0.23 0.07 0.17 0.06
N+B
Material Work hardenin2 exponent

200°C 30 seconds 200°C 600 seconds
Prestrain Strain to Prestrain Strain to
failure failure
BOSLowN 0.30 0.12 0.30 0.12
BOSHi2hN 0.31 0.13 0.34 0.13
EAFLowB 0.35 0.12 0.35 0.13
BOS High 0.30 0.03 0.30 0.01
N+B
183
0.400 -~ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
D130C
0.350
•2ooc
~ 0.300
a,
C
0
a. 0.250
X
(l)
Cl
-~ 0.200
C
a,
...
"O
1 0.150
...
.:,i:
0
~ 0.100
0.050
0.000
BOS Low N BOS High N EAF Low B BOS High B
Material
Figure 8.1 Comparison of work hardening exponents in the prestrain region as a function of temperature tested at 30 seconds delay after
prestrain.
184
0.400
0.350 0130 C
• 600 seconds
cC1)
o.300
C:
0
~ 0.250
Cl)
i.J1
C:
"i: 0.200
Cl)
.::,
,._
~ 0.1 50
.:,::
,._
0
S: 0.100
0.050 _,
0.000
Material
Figure 8.2 Comparison of work hardening exponents obtained in the prestrain region as a function of temperature after 600 seconds
delay after prestrain.
185
Chapter 8 Discussions
8.3.1.2 Maximum stress m/ues
Figures 8.3 to 8.10 compare the stress strain behaviour of the four materials as a
function of temperature. Figures 8.11 to 8. 13 show the maximum stress values obtained
after prestrain alone and after 30 and 600 seconds delay after prestrain respectively. It
is observed in Figure 8.11 that the values of maximum stress obtained at 200°C are
higher than obtained at 130''C. This is due to the occurrence of dynamic strain ageing at
200°C (Figures 8.1 and 8.2).
In the strain to failure region (Figures 8.12 and 8.13), there does not seem to be a
significant difference in the maximum stress values. Generally the curve at 200°C is
marginally higher than that exhibited at 130°C.
It appears that the test temperature has a greater effect in the prestrain region than in
the strain to failure region.
186
700
0
@ 130 C Aging index= 149.8 Mpa
600 •
@ 200 C Aging index = 26.5 Mpa
500
-ea
D. 400
-
:!:
I ll
Ill
-~ 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.3 Stress strain behaviour as a function of temperature BOS Low N tested at 30 seconds delay after prestrain.
187
700
@ 13o"C Aging index= 83.1 Mpa
@200°C Aging index =38.2 Mpa
600
500
-C'tl
a. 400
-
~
f/J
-
f/J
f 300
V,
200
100
0 -,
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.4 Stress strain behaviour as a function of temperature of BOS High N steel tested at 30 seconds delay after prestrain.
188
700
0
600 0
500
- 400 -
ns
a.
-
::i!:
1/)
1/)
-
f 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.5 Stress strain behaviour as a function of temperature of EAF low B steel tested at 30 seconds delay after prestrain.
189
700 . . . . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
0
600
@ 200•C Ag!!!g index = 54.2 MPa
200C --__L=
500
130 C
-
~ 400
-"'
:iE
I I)
~ 300
en
200
100
0 + - - - - - - - - - , - - - - - - - - - . - - - - - - , - - - - - - - , - - - - - - - - , -.......- - - - - - - 1
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.6 Stress strain behaviour as a function of temperature of BOS high N+B steel tested at 30 seconds delay after prestrain.
190
700
0
600 @ 200°c Aging index= 20.3 MPa
500
-
~ 400
-
~
I ll
Ill
-~ 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.6 Stress strain behaviour as a function of temperature of BOS Low N steel tested at 600 seconds delay after prestrain.
191
700
0
600 0
500
-C'G
~ 400
-en
en
~ 300
I-
en
200
100
0
0 0.5 1 1.5 2 2.5 3
STRAIN
Figure 8.8 Stress strain behaviour as a function of temperature of BOS high N steel tested at 600 seconds delay after prestrain.
192
700
0
@ 130 C Aging index= 149.8 Mpa
600 0
@ 200 C Aging index = 26.5 Mpa
500
-
:_ 400
-
:::i!1:
I I)
II)
-~ 300
Cl)
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.9 Stress strain behaviour as a function of temperature of EAF Low B steel tested at 600 seconds delay after prestrain.
193
700
@ 13o•c Ageing index =116.4 MPa
600 @ 200•C Aging index= 84.2 MPa
500
-ea
a. 400
-
:E
I ll
Ill
....~
u,
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.10 Stress strain behaviour as a function of temperature of BOS high N+B steel tested at 600 seconds delay after
prestrain.
194
700 -
D 130°C
0
600 •2ooc
500 ~
-n:s
a. 400 -
-
:E
1/J
1/J
....~
Cl)
300
200
100
0 ~

Material
Figure 8.llComparison of maximum stress values obtained in the prestrain region as a function of temperature.
195
700 D 130°C
•
•2ooc
600 -
500 -
-
I ll
a. 400 -
-e
~
I ll
Ill
...
Cl)
300
200 -
100
0 _____.__ _
BOS LowN BOS High N EAF LowB BOS High B

Material
Figure 8.12 Comparison of maximum stress values in the strain to failure region as a function of temperature after a delay of 30 seconds
after prestrain.
196
700
013o·c
•200°c
600
500 -
-
~ 400
-
:E
1 /)
1/)
...e 300 -
Cl)
200
100
0
Material
Figure 8.13 Comparison of maximum stress values as a function of temperature after a delay of 600 seconds after prestrain.
197
Table 8.2 Values of maximum stress obtained in the four different compositions in the prestrain and strain to failure regions
under various test parameters
Material Maximum Maximum stress Maximum stress Maximum stress Maximum stress
stress at at 130°C and 30 at 130°C and 600 at 200°C and 30 at 200°C and 600
prestrain seconds delay seconds delay seconds delay seconds delay
(MPa)
BOSLowN 373.48 565.1 550.97 572.95 575.65
BOS High N 399.46 590.81 582.15 594.87 609.75
EAFLowN 406.5 586.48 616.25 615.44 632.22
BOS High N+B 345.5 552.86 563.74 554.21 557.45
198
8.3.1.3 Total strain to failure
Table 8.3, Figures 8.13 and 8.14 compare the values of total strain as a function of
temperature. It is evident from these figures that there appears to be a very marginal
difference in the strain values at the two temperatures. Most of the differences in the
strain values between the two test temperatures fall within the random experimental
limits specified in section 7.6.1. Therefore it is seen that temperature appears to have
little or no effect on total strain.
199
Table 8.3 Values of total strain to failure of different steel compositions under various test parameters.
Material Total strain to failure

13o·c 30 seconds 13o•c 600 seconds 200•C 30 seconds 2oo·c 600 seconds
delay delay delay delay
BOSLowN 1.68 1.79 1.75 1.79
BOSHiehN 1.32 1.35 1.32 1.14
EAFLowB 1.48 1.47 1.43 1.64
BOS Hieb N+B 2.6 2.68 2.58 2.55
200
;,s~--------------------------------------
ID13<Tcl
l•200°c j
2.5
2
C:
...
ns
.....
Cl) 1.5
.....ns
0
I-
1 _,
0.5
0 _ ___.__ _
BOS Low N BOS High N EAF Low B BOS High N+B

Material
Figure 8.13 Comparison of total strains to failure as a function of temperature tested at 30 seconds delay after prestrain.
201
3---.----------------------------------,
013o·c
•2oo·c
2.5
2
C
...nl
-I I)
1.5
-nl
0
I-
1
0.5
0 ·-··
Material
Figure 8.14 Comparison of total strains to failure as a function of temperature tested at 600 seconds delay after prestrain.
202
8.3.1.4 Ageing indices
Ageing index is defined as the difference in the value of stress before and after
prestrain. In order to provide a consistent measure of the difference in stress and
minimise errors in calculation of the ageing index, values of stress at a constant value of
prestrain (0.3) and stress at a constant value of strain after prestrain (0.35) have been
noted. The difference in these values has been assigned as the ageing index for the
material tested under a certain parameter.
Tables 8.4 and 8.5 list the values of ageing indices and Figures 8.15 and 8.16 compare
the indices on a bar chart. It is evident from the table and figures that the ageing index
is higher at 130°C than at 200°C. This is due to the occurrence of more dynamic strain
ageing at 200°C, which raises the level of the stress - strain curve in the prestrain
region. This in turn results in a lower ageing index. This behaviour is observed in
results obtained at both 30 and 600 seconds delay time after prestrain.
203
Table 8.4 Values of strain ageing indices in samples tested at 130 and 200°C after a time delay of 30 seconds after prestrain
TEMPERATURE STRESS AT INITIAL STRESS AFTER A STRAIN

MATERIAL OF TEST PRESTRAIN (MPa) DELAY TIME OF 30 AGEING
S1 SECONDS AFTER INDEX=
PRESTRAIN(MPa) S2 S2 - S1
BOS LOWN 130 C 373.48 444.93 71.45
BOS LOWN 200C 438.98 463.61 24.63
BOS HIGHN 130 C 399.46 482.55 83.09
BOSHIGHN 200C 471.73 509.81 38.16
EAF LOW BORON 130 C 406.3 491.48 85.18
EAF LOW BORON 200C 488.78 510.16 21.38
BOSHIGHN+B 130 C 345.64 415.52 69.88
BOSHIGHN+B 200C 423.89 478.12 54.23
204
Table 8.5 Values of strain ageing indices in samples tested at 130 and 200°C after a time delay of 600 seconds after prestrain.
MATERIAL TEMPERATURE STRESS AT INITIAL STRESS AFTER A STRAIN

OF TEST PRESTRAIN (MPa) DELAY TIME OF 600 AGEING
S1 SECONDS AFTER INDEX=
PRESTRAIN(MPa) S2 S2 - S1
BOS LOWN 130 C 361.85 421.51 67.66
BOS LOWN 200C 430.86 451.16 20.3
BOSHIGHN 130 C 410.29 483.36 85.52
BOS HIGHN 200C 486.88 518.68 31.8
EAF LOW BORON 130 C 320.26 470.1 149.84
EAF LOW BORON 200C 474.43 500.96 26.53
BOSHIGHN+B 130 C 360.21 476.62 116.41
BOSHIGHN+B 200C 394.48 478.66 84.18
205
90
13o·c o
80 · 2oo·c •
70
60
f
~
50
1/)
1/)
e 40
..,
Cf)
30
20
10
0
Material
Figure 8.15 Comparison of ageing indices as a function of temperature tested at 30 seconds delay after prestrain.
206
160 -
130•C 0
140 200°c •
120
-
nl
c..
~
100
VI
VI
80
-...
Q)
Cl)
60
40
20
0
Material
Figure 8.16 Comparison of ageing indices as a function of temperature at 600 seconds delay after prestrain.
207
8.3.2 Influence of delay time after prestrain on the stress - strain behaviour of
the four steel compositions:
8.3.2.1 Work hardening exponents:
Table 8.6 lists the values of the work hardening exponents and Figures 8.17 and 8.18
compare the values of the work hardening exponent obtained in the four steel
compositions as a function of delay time. These exponents have been computed in the
portion of the stress-strain curve after the time delay has occurred. There seems to be
no significant change in the value of the exponent with an increase in the delay time
after prestrain. The only significant variation is in the high boron + high nitrogen grade
which shows a marked decrease at the higher temperature of 200°C as the delay time is
increased from 30 seconds to 600 seconds.
Table 8.6 Work hardening exponents of the four grades of steels as a function of
delay time.
MATERIAL WORK HARDENING EXPONENT
130 °C 130 °C 200 °C 200°c
30 seconds 600 seconds 30 seconds 600 seconds
BOS LOWN 0.173 0.173 0.118 0.117
BOS HIGH 0.145 0.149 0.127 0.132
EAFLOWB 0.153 0.16 0.116 0.128
BOS HIGH 0.068 0.06 0.028 0.005

N+B
208
0.2
C30 seconds
0.18
•soo seconds
0.16 -
i: 0.14
Cl>
C
0
~ 0.12
Cl>
C")
C
C 0.1
a,
,._
-0
1 0.08
,._
~
0
~ 0.06
0.04
0.02
0 7
BOS Low N BOS high N EAF low B BOS high N+B

Material
Figure 8.17 Comparison of work hardening exponents in the prestrain region as a function of delay time after prestrain at 130°C.
209
0.14 ~ - - - -- - - - - - - - - - - -- - - - - - - -- - - - - - ~
030 seconds
• 600 seconds
0.12
0.1
i:
Q)
C:
0
c.
~ 0.08
Cl
.:C:
Q)
"O
~ 0 .06
.s::
-"'-
0
s:
0.04
0.02
O +-~ - ~
BOS Low N BOS high N EAF low B BOS high N+B
Material
Figure 8.18 Comparison of work hardening exponents in the prestrain region as a function of delay time after prestrain at 200°C.
210
8.3.2.2 Maximum stress values:
Figures 8.19 to 8.26 show the stress strain behaviour of the four steel compositions as
a function of delay time. Figures 8.27 and 8.28 compare the maximum stress values
obtained at both delay times. There appears to be no significant difference in the
maximum stress values obtained in the strain to failure region as a function of delay
time. This proves that all the solute has segregated to the dislocations within the first 30
seconds and no further addition is made to the amount of solute segregated at times
greater than 30 seconds.
8.3.2.3 Total strain to failure:
Figures 8.30 and 8.31 compare the values of total strain to failure as a function of delay
times. It is very evident that there is no, or very little difference in the strain values with
a variation in the delay time. This further strengthens the interpretation that there is no
addition in the amount of solute that has segregated to the dislocations with an increase
in the delay time.
211
700
@ 30 SECONDS Aging index= 71.SMPa
600
@ 600 SECONDS Aging index= 67.7 MPa
500
-
:_ 400
-
:!E
en
en
-e
Cl)
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.19 Stress strain behaviour of BOS low N as a function of delay time after prestrain tested at 130°C.
212
700 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
@ 30 SECONDS Aging index=83.1 MPa

600

500 600 SECONDS
'i_ 400
-
::E
fl)
-
fl)
~ 300
en
200
100 ~
0 -------------,-----.....---------,--------,------
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.20 Stress strain behaviour of BOS high N as a function of delay time after prestrain tested at 130°C.
213
700
600
30 SECONDS @ 600 SECONDS Aging index= 149.8 Mpa
500
-
C'CI
c.. 400
600 SECONDS
-
~
,n
,n
-
e
en
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.21 Stress strain behaviour of EAF low B steel as a function of delay time tested at 130°C.
214
700
@ 30 SECONDS Aging index = 69.9 MPa
600 600 seconds @ 600 SECONDS Aging index=116.4 MPa
500
-CU
o.. 400 30 seconds
-...,,,
:E
-: 300
u,
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.22 Stress strain behaviour of BOS High N+B steel as a function of delay time after prestrain tested at 130°C.
215
700
@ 30 SECONDS Aging index = 24.63 MPa
500
-
n,
a.. 400
-
:E
u,
u,
-
f 300
en
200 -
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.23 Stress strain behaviour of BOS Low N as a function of delay time after prestrain tested at 200°C.
216
700
-ea
~ 400
500
30 SECONDS
-u,
~ 300
.......
"' 200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.24 Stress strain behaviour of BOS High N as a function of delay time after prestrain tested at 200°C.
217
700
600
500
-"'
c.. 400 -
-"'
~
30 SECONDS
600 SECONDS
-"'
~
tn
300
200 -
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.25 Stress strain behaviour of EAF low B steel as a function of delay time after prestrain tested at 200°C.
218
700
@ 30 SECONDS Aging index = 54.23 Mpa
600 @600 SECONDS Aging index= 84.18 MPa

30 SECONDS
500
600 SECONDS
-
CU
a. 400
-
~
I ll
Ill
-
f 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure 8.26 Stress strain behaviour of BOS high N+B steel as a function of delay time after prestrain tested at 200°C.
219
700
rD 30 seconds-
600 • 600 seconds
500 -
-113
n.. 400
~
en
en
~ 300
....,
(/)
00
100
0
Material
Figure 8.27 Comparison of maximum stress values in the strain to failure region as a function of delay time after prestrain tested
at 130°C.
220
700
a30 seconds
• 600 seconds
600
500 _,
('0
a.. 400
2
"'"'e 300
~
200
100
0 r

Material
Figure 8.28 Comparison of maximum stress values in the strain to failure region as a function of delay time after prestrain tested at
200°C.
221
3
030 seconds
2.5
2 -
C
....ro
....,
(/)
1.5
ro
....,
0
I-
1
0.5
0
Material
Figure 8.29 Comparison of values of total strain to failure as a function of delay time after prestrain tested at 130°C.
222
3 ---.---------------------
_ -_ -_ -_- - - - - - - - - ,
ID 30 seconds
~ 600 seconds
2.5
2
C:
...."'...
1/) 1.5
...."'0
I-
0.5
0
Material
Figure 8.30Comparison of values of total strain to failure as a function of delay time after prestrain tested at 200°C
223
Figure 8.31 and 8.32 compare the ageing indices obtained at 30 and 600 seconds. A
significant difference in the index is observed in EAF low B and BOS high N+B with
an increase in the delay time after prestrain. However there is no significant difference
in the index with an increase in the delay time in BOS low and high N steels. This
could be attributed to the possibility of boron adding to strain ageing with the entire
amount boron not being fixed as BN. This is corroborated by the absence of BN
precipitates observed in the BOS high N+B steel under the transmission electron
microscope.
224
160
030 seconds
140 • 600 seconds
120
100
ro
a..
2
1/)
1/)
80
-
Q)
I,..
CJ)
60
40
20
0
Material
Figure 8.31 Comparison of ageing indices as a function of delay time after prestrain tested at 130°C.
225
160
030 seconds
140 • 600 seconds
120
-
n:s
a.. 100
--
~
><
Q)
"O
C
80
-
0)
C
Q) 60
0)
<(
40
20
0
Material
Figure 8.32 Comparison of ageing indices as a function of delay time after prestrain tested at 200°C.
226
8.3.3 Influence of material composition:
Figures 8.33 to 8.36 compare the stress strain behaviour of the four different steel
compositions under various test parameters. It is important to note that in general, a
very similar trend is exhibited by the materials at various test parameters. There is no
significant difference in the behaviour of the BOS high N and the EAF low boron grade,
as observed in Figures 8.34 - 8.35. The highest value of total strain to failure is
exhibited by BOS high N+B material, followed by BOS low N, EAF low B and lastly
BOS high N. This is true for all combinations of test temperatures and delay times as
observed in Figures 8.33 - 8.36. In addition, BOS high N+ B grade appears to
show an appreciable decrease in the stress values as compared to the other steel grades
as observed in Figures 8.34 - 8.37.
In general as observed from figures 8.33 - 8.36, the level of the stress-strain curves
follow a definite order- BOS high N+ B is the lowest followed by BOS low N and then
by BOS high N and EAF low B.
The slope of the stress-strain curves in the prestrain region, which is indicative of work
hardening appears to be approximately the same and relatively a higher value for BOS
high N and EAF low B steels at both the test temperatures and delay times. This is
then followed by the BOS Low N steel and then the BOS high N+ B steel. A similar
trend is noticed in the strain to failure region for the four grades at all combinations of
test temperatures and times
227
700 - --· ~-~- --- ---·~ -.----· --~~ ----
600
500
ii
c. 400
:ii:
en
en
~ 300 t.F t BOS High N I

l ,OS Low N
200 -- BOS Hiilh N+B
100
0
0 0.5 1 1.5 2 2.5 3
STRAIN
Figure 8.33 Stress strain behaviour of the four different steel compositions tested at 130°C and 30 seconds delay after prestrain.
228
700 - --· -· - - -=···-·----- -- - - - - - - - ---··-- ---··-·- --------------·
600
500
-
C'IS
a. 400
EAF LowB
-
:!:
en
en
w
BOS high N+B
o::: 300
I-
en BOS High
200 BOS LowN
100
0 + - - - - - - - - , - - - - - - - - - - . . - - - - - - - , - - - - - - - - - -...- - - - - J
0 0.5 1 1.5 2 2.5 3
STRAIN
Figure 8.34 Stress strain behaviour of the four steel compositions tested at 130°C and 600 seconds delay after prestrain.
229
'
700 r--··--·-·---· ·-------· - •o-- - - - - - •• --·-~-·-----· - - ·--· ·--~-·- ·---~-~,~~----·
600
500
ii BOS High N
a.
~ 400
en B@S High B
en
w Fllow B
a:: 300
I-
C/)
BOS LowN
200
100
0 ....
0 0.5 1 1.5 2 2.5 3
STRAIN
Figure 8.35 Stress strain behaviour of the four steel compositions tested at 200°C and 30 seconds delay after prestrain.
230
700 - - . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
600
500
'i::ii: 400 BOS High N
-
en
en
w
BOS High B
o::: 300 EAFLowB
t-
en
BOS LowN
200
100
0 ~
0 0.5 1 1.5 2 2.5 3

STRAIN
Figure 8.36 Stress strain behaviour of the four steel compositions tested at 200°C and 600 seconds after prestrain.
231
8.3.3.1 Work hardening exponents
Table 8.7 lists the values of the work hardening exponents obtained at vanous
combinations of the test parameters.
Figures 8.37 - 8.40 illustrate the variations in the work hardening exponent which may
be related to a variation in the interstitial content for the four steel compositions as listed
in Table 8.7. The variation in the work hardening exponent for the four steels tested at
130°C and 30 seconds, as shown in Figure 8.38, shows a marginal increase with an
increase in the interstitial content for BOS low and high nitrogen grades and the EAF
low boron grade. This is to be expected since the exponent depends very strongly on
the interstitials, which are very mobile and are capable of pinning the dislocations.
However an exception to this trend is noticed in the BOS high N+B grade wherein,
despite an interstitial content almost equal to the BOS high nitrogen grade, the exponent
is marginally lower (0.23 as compared to 0.30 for the BOS high N steel). The marginal
difference of 0.07 in the value of the work hardening exponent could be attributed to a
slightly lower content of nitrogen and fixing of some nitrogen by boron as indicated in
the "free nitrogen"analysis in Table. 7.2. In this context, the 'fixing' of free nitrogen
could be due to solute interaction between boron and nitrogen in solution, which could
explain the observed absence of precipitates, section 7.6.3. It must be noted that at the
lower temperature of 130°C, diffusion of nitrogen is higher than that of carbon. At
130°C and 600 seconds (Figure 8.39), the exponents for the BOS low N, BOS high N
and the EAF low B appear to be almost at the same value, while that of the BOS high
N+B steel is marginally lower (0.17 as against 0.24 - 0.27 for the other
232
Table 8. 7 Variation in work hardening exponents with the interstitial content for the four steel compositions.
Material Total solute Interstitial Work Hardening exponent

content content (C+N)
130°c 30 130°c 600 200°c 30 200°c 600
SECONDS SECONDS SECONDS SECONDS
BOS LOW 0.596 0.072 0.284 0.269 0.298 0.297

N
BOS HIGH 0.624 0.088 0.303 0.237 0.312 0.340
N
EAF LOW 0.760 0.058 0.244 0.250 0.354 0.353
B
BOS HIGH 0.660 0.086 0.228 0.173 0.295 0.295
B+N
233
0.15 0.400
I- Interstitial content ·!
+ 0.380
0.13 + 1-+-Work Hardening exponent
ca,
j
1
0.360
ca, 0.11 0.340
C
&,
+,I
C ><
0.320 a,
8 0.09 en
-:.::;ns o.3oo ·c
C
a,
:.::; 0.07
...a,
rn 0.280 "E
ns
+,I .c
C 0.05 0.260 ~ ...0
0.240 3:
0.03
0.220
0.01 0.200
Material
Figure 8.38 Variation of work hardening exponents (prestrain region) and interstitial content for the four different steel
compositions tested at 130°C and 30 seconds
234
0.15
. -Interstitial content
0.14 I-+- Work Hardening exponent
~
0.13
0.12
0.360
-C
a,
C
0
s§ 0.11
c.
0.310 ><
a,
.
-
CJ
t'G
f? 0.09
0.1
0.260 'E
C)
-
C
C
a,
s t'G
.c
.i.::
C 0.08 I.
0
0.07 0.210 ~
0.06
0.05 - - - - - - - - - - - - - - - - - - - - - - 0.160
Material
Figure 8.39 Variation of work hardening exponents (prestrain) and interstitial content for the different steel compositions tested at
130°C and 600 seconds
235
0.15 - Interstitial content
0.14 -+-Work Hardening exponent
0.360 ~
0.13 a,
~ C
0
; 0.12 a.
~
C ><
0.310 a,
o(.) 0.11 C')
ci 0.1 ·-ca,:
C:
;;
...a,
:;; 0.09 0.260 .
"C
ea
.c
~ 0.08
- 0.07 0.210 ~
~
...
0.06
0.05 -+------.---+--------+-----,-------+- 0.160
Material
Figure 8.40 Variation of work hardening exponents (prestrain) and interstitial content of four different steel compositions tested
at 200°C 30 seconds.
236
0.15
- Interstitial content
0.14 -+-Work Hardening exponent
0.360 c
..., 0.13
G)
C
0
...,; 0.12 c.
C
o(.) 0.11 0.310 ><
a,
C,
ci 0.1 ·-cC
E G)
1n
... 0.09 0.260 ...ea
-c
G)
c o.oa .c
...
- 0.07 0.210 ~
~
0.06
0.05 -+------+-------+-----+------+- 0.160
Material
Figure 8.41 Variation of work hardening exponents (prestrain) and interstitial content of the four steel compositions tested at
200°C and 600 seconds.
237
At the higher temperature of 200°C, the exponents have similar values at both the times
(Table 8.7). However, the exponent of the BOS high N+B grade appears to be the same
as that for the BOS low N grade. However, in the strain to failure region, there is an
appreciable difference in the exponents among the steel grades. BOS high B+N grade
shows the lowest values of the exponents at both the temperatures and times, possibly
due to the fixing of some amount of nitrogen in the steel.
In general these results agree with the results of Frank and Kirkcaldy< 73 ) who have
reported a lower work hardening rate in boron treated rods. Studies on two 0.06%
carbon EAF grade steels, one without boron and the other treated with 0.007 % boron
revealed a lower rate of work hardening below 50% reduction in area in the boron
treated steel.
Gladman et a1< 119> have derived the following equation on the influence of alloying
elements on the flow stress at room temperature.
a = 355 + 601(%C)+ 86(%Mn)+ 201(%Si)-741(%S) +880(%P)+200 (%Sn)
+114(%Cr)+4478(%N)+27.8d-112------------------------8.J
where d = grain size.
Using this equation, values of flow stress for the four grades of steel was calculated at a
true strain of 0.8. Table 8.8 compares the values obtained by calculation. Since the
actual hot torsion tests have been carried out at slightly elevated temperatures, the
values of flow stress at these temperatures, is expected to be lower. These calculations
also do not take into account the effect of Sn and the grain size, therefore adding to the
238
difference in the values of the calculated and measured flow stress. It is also noted that
the flow stress values obtained from the hot torsion data show similar results for the
BOS low N and BOS high N+ B steels, while those for the BOS high N and EAF low B
grades are about 60 MPa higher. This trend is in accordance with the results of Franks
and Kirkcaldy< 73 ) who have reported that the difference between the boron treated and
non-boron treated grades can be as high as 200 MPa. This phenomenon has been
attributed to the combination of nitrogen with boron restricting dynamic strain ageing.
However in the current investigation, the smaller difference in the flow stress values
between the boron and non-boron grades would be due to the incomplete fixing of all
nitrogen by boron as confirmed by the "free nitrogen" analysis. In this context, the
'fixing'of free nitrogen could be due to solute interaction between boron and nitrogen
in solution, which could explain the observed absence of precipitates, section 7.6.3.
Another observation to be made is the dependence of the Gladman's equation on the
grain size. As reported earlier, the grain size in the BOS boron treated high nitrogen
grade steel was found slightly higher (ASTM 6-7 as against ASTM 8 in the other
grades). This could also have resulted in a higher flow stress in the BOS boron treated
high nitrogen grade steel.
239
Table 8.8 Comparison of calculated values (using Gladman's equation) of flow stress and measured values of flow stress at a true
strain of 0.8
MATERIAL FLOW STRESS USING FLOW STRESS FROM

GLAD MAN'S HOT TORSION
EQUATION(MPa) CURVE(MPa)
BOS LOWN 474.30 496.6
BOSHIGHN 509.36 549.94
EAFLOWB 503.26 549.13
BOSHIGHN+B 503.76 487.84
240
8.3.3.2 Maximum stress
The maximum stress levels obtained at constant strain of 1.08, as shown in Figures 5.42
to 5.45 and Table 8.9, indicate high values for BOS high N and EAF low B. This is
attributable to the high interstitial content and total solute content (corroborated by high
values of work hardening exponent-Table 5.6). BOS Low N and BOS High N+B show
almost the same levels of stress, although the work hardening exponent for the former is
much higher than that for the latter (0.17 against 0.07 for BOS high N+B steel). These
results indicate the incomplete action of the boron additions in fixing all free nitrogen
and this is corroborated by the results of the free nitrogen analysis in these samples
(Table 7.2). This behaviour is exhibited at all combinations of parameters.
241
Table 8.9 Values of maximum stress obtained for the four different steel compositions under various test parameters.
MATERIAL MAXIMUM STRESS

130°C 30 130°C 600 200°c 30 200°c 600
SECONDS SECONDS SECONDS SECONDS
BOS LOWN 565.1 550.97 572.95 575.65
BOSHIGHN 590.81 582.15 . 594.87 609.75
EAFLOWB 586.48 616.25 615.44 632.22
BOS HIGH 552.86 563.74 554.21 557.45
N+B
242
600
590
580
-
ea
a. 570
-
~
( /)
-
(/)
f 560
en
550
540
530
Material
Figure 8.42 Maximum stress at constant strain (1.08) for the four steels at 130°C and 30 seconds.
243
640 ~ - -- -- - - - - - - - - - -- - - - - -- ----,
620
600
-~ 580
:!!:
u,
1/)
-f! 560
( /')
540
520
500 -+-- - ' - - - - - - - ' - - ~ - _ _ . __ _...___~_ _.___ __.__---,-- ~ - - - ' - - -

Material
Figure 8.43 Maximum stress at constant strain (1.08) for the four steels at 130°C and 600 seconds.
244
600 . . . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
580
560 -
cu
a.
~
in 540
Ill
-
~
en
520
500
480 --------------........-------.__-....,...._ ___._____..__---,-_ _.________

Material
Figure 8.44 Maximum stress at constant strain (1.08) for the four steels at 200°C and 30 seconds
245
600 - . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
580
560
i:i: 540
u,
If)
t
Cl)
520
500
480
460 • -
Material
Figure 8.45 Maximum stress at constant strain (1.08) for the four steels at 200°C and 600 seconds
246
8.3.3.3 Total strain to failure
Table 8.10 shows that variation in the values of total strain to failure for the four
different compositions. BOS Low N and EAF low B steels show similar values, while
BOS high N shows a marginally lower value of strain to failure- (higher N and C
content). BOS high N+ B steel shows a distinct increase in the total strain to failure
(corroborates with the reduced values of the work hardening exponent, thus resulting in
a larger total strain to failure). This agrees with results obtained by Franks and
Kirkaldy< 73 ) who have reported a lower work hardening rate and higher drawability in
boron treated rods. A similar trend is observed at all test parameters. Although this
phenomenon has been atrributed to the fixing of nitrogen in boron<73 ), in the current
study due to clear evidence that boron has not completely fixed free nitrogen present,
this phenomenon could not be explained under the constraints of the research project.
However a slightly coarser grain size could be one of the factors influencing the total
strain to failure.
247
Table 8.10 Variation of total strain to failure as a function of steel composition.
Material Total strain to failure

130°C 30 seconds 130°C 600 seconds 200°C 30 seconds 200°C 600 seconds
delay delay delay delay
BOSLowN 1.68 1.79 1.75 1.79
BOSHi2h N 1.32 1.35 1.32 1.14
EAFLowB 1.48 1.47 1.43 1.64
BOS High N+B 2.6 2.68 2.58 ·2.ss
248
8.3.3.4 Ageing index
Table 8.11 lists the values of ageing index obtained for different test parameters.
Figures 8.46 to 8.49 indicate the variation in the ageing index and the interstitial
content for the steel compositions. The values of the ageing index for the four
compositions show similar values at 130°C and 30 seconds (variation is within
experimental error). This indicates the ineffectiveness of boron additions. This is
further confirmed by the index results exhibited by the four steels tested at the
remaining three combinations of parameters. The index values for the EAF low B
steel and the BOS high N+B steel are definitely higher than that obtained in BOS low
N. At the higher temperature of 200°C, due to dynamic strain ageing, the indices are
lower as compared to those at 130°C. However, the same trend of a marginal
difference in the index as a function of composition is maintained. BOS high N+B
steel still shows a high ageing index, indicating ineffective role of boron additions to
these steels.
249
Table 8.11 Variation in the ageing index, interstitial content (C+N) and the boron content, in the four steel compositions.
Material Interstitial Boron content Ageing index (MPa)

C+N content (wt%)
(wt%)
130°c 30 130°c 600 200°c 30 200°c 600
seconds seconds seconds seconds
BOS LOWN 0.072 0 71.45 67.66 24.63 20.3
BOSHIGHN 0.088 0 83.09 85.52 38.16 31.8
EAFLOWB 0.058 0.0012 85.18 149.84 21.38 26.53
BOS HIGH 0.086 0.0038 69.88 116.41 54.23 84.18
N+B
250
0.12 190
0.11
-interstitial content I
-+- Ageing index
+170
I
150
-f
C
0.1
0.09
130 ><
G)
0
u 110 ~
ea o.os
.::;
C,
C
.::; 90 G)
--
fG) 0.07 C,
<(
C 70
0.06 50
0.05 30
0.04 10
Material
Figure 8.46 Variation of interstitial content and ageing index for the four steel compositions tested at 130°C and 30 seconds.
251
0.12 190
..,
0.11
0.1
t
I
~
- Interstitial content
I -+-Ageing index t170
150
C
..,Cl) ><
130 Cl)
5 0.09 "CS
CJ 110 .5
ea o.os C)
~
~
90 ·-C
Cl)
fCl) 0.07 C)
.., 70 <C
C 0.06 • 50
0.05 30
0.04 10
Material
Figure 8.47 Variation of interstitial content and ageing index for the four steel compositions tested at 130°C and 600 seconds
252
0.12 190
- Interstitial content I
0.11 + I -+-Ageing index
+ 170
I
.... 150
C 0.1
....
Cl)
C
><
130 Cl)
"CS
8 0.09 110 .5
-CU C,
~ 0.08 90 ·-
C
Cl)
C,
fCl) 70 <(
c: 0.07 '
I
- 50
0.06 + _______.____ v~ I 30
0.05 10
Material
Figure 8.48 Variation of interstitial content and ageing index for the four steel compositions tested at 200°C and 30 seconds.
253
0.12 190
- interstitial content 1 + 170
0.11 t I
-+- A gemg
. .m d ex
..., 0.1 I
+ 150
C
...,Q) ><
130 Cl)
§ 0.09 "C
c., 110 .5
ea o.oa C)
+i
+i 90 ·-C
/
Cl)
r? 0.07 C)
...,Q) 70 <(
C 0.06 50
0.05 30
0.04 10
Material
Figure 8.49 Variation in the interstitial content and ageing index for the four steel compositions tested at 200°C and 600 seconds.
254
8.4 TRANSMISSION ELECTRON MICROSCOPIC EXAMINATION:
Extensive examination under the TEM did not reveal the presence of any BN
precipitates in any of the steel grades under the current experimental conditions.
This would mean that the kinetic factors of temperature and time combinations
were not favourable for BN precipitation in these compositions. Experiments by
Watanabe and Ohtani(S 9) on steels containing 0.0096% boron, 0.0326%nitrogen
and 0.001 % aluminium (BIN ratio= 0.29) revealed BN precipitates when cooled
from a hot rolling temperature of 1300°C at the rate of 300°C /minute. A slower
cooling rate of 0.67°C/minute gave a mix of BN and AlN precipitates. The
cooling rate employed in the current study is of the order of water quenching
followed by a cooling rate of 2°C/sec or 120°C/minute from 900°C, which is in
between the two cooling rates stated in Watanabe's study. For BN to precipitate,
it should do so, either, during watet quenching or when cooled from 900°C at a
slower rate. However, it must be noted that the austenitising temperature used in
Watanabe's study was 1300°C as against 1100°C followed by water quenching to
900°C in the current study from where a cooling rate of 2°C/sec was employed.
More importantly, a boron content of 0.0096% was used by Watanabe, against a
maximum of 0.0038% used in the current study. No precipitation in the matrix
or on the dislocations was noticed., leading to the conclusion that the strain ageing
phenomenon in these steels was due to atmosphere formation around dislocations.
The second stage of precipitation on dislocations was not reached even though
enough number of sites were available for heterogenous nucleation and sufficient
driving force in the form of solute available in excess of the equilibrium solubility
at the lower drawing temperatures of 130°C and 200°C, was available.
255
Chapter 9 Conclusions
CHAPTER9
CONCLUSIONS
256
This research project has generated varied data on the phenomenon of strain ageing in
low carbon steel wire rods supplied by BHP, Newcastle. The analysis of data has led to
several important conclusions as stated below. It must however be mentioned that the
project has been formulated and researched under several constraints, namely limited
availability of industrial and experimental steel grades and relatively high testing costs.
The conclusions are as follows:
9.1 USE OF HOT TORSION TESTING AS A SIMULATION OF THE WIRE DRAWING
PROCESS.
As mentioned in Chapters 2 and 3, hot torsion has been used successfully by several
researchers to simulate the wire drawing processes. Extensive hot torsion testing on the
BHP-developed hot torsion rig and subsequent analysis of data during the current
research project has confirmed the consistency and suitability of the test method for
such studies.
9.2 INFLUENCE OF VARIOUS PARAMETERS ON THE STRAIN AGEING BEHAVIOUR:
9.2.1 Influence of temperature:
• Work hardening rate
The work hardening exponents (in the prestrain region) at the testing temperature of
200°C are higher as compared to the exponent values at the lower temperature of 130°C.
This is attributed to the occurrence of dynamic strain ageing at higher temperatures
where both interstitial carbon and nitrogen have high diffusion coefficients sufficiently
high in order to pin the dislocations dynamically during straining itself. The diffusion
257
coefficient of nitrogen and carbon at 200°C is approximately 125 times higher than at
the lower temperature (De 20ocl De 130c = 125). This trend is generally observed in all
the four steel compositions. The work hardening exponents in the strain to failure
region (0.005 - 0.173) of the stress-strain curve are generally lower than the prestrain
values(0.173 - 0.354), indicative of the onset of plastic strains in the strain to failure
region. At a higher temperature of 200°C, the work hardening rates (0.295 - 0.354 in
the prestrain region) show generally higher values as compared to those obtained at
130°C (0.173 - 0.303 in the prestrain region). This is a result of increased interstitial
diffusion rates at 200°C leading to a higher dynamic strain ageing.
• Maximum Stress
The levels of the maximum stress show a very distinct increase at 200°C (a maximum of
25 MPa) as compared to those obtained at 130°C in both the prestrain and the strain to
failure regions of the stress-strain curves. This is attributed to increased dynamic strain
effects in both regions of the stress-strain curve, specifically higher during the prestrain
region. At the higher temperature, there is increased diffusion of the interstitials to the
dislocations causing an increase in the dynamic strain ageing effects. In the strain to
failure region, due to the onset of plastic deformation, the rise in the level of the stress-
strain curve is lower.
• Total strain to failure
Testing temperature does not have a significant effect on the total strain to failure. This
could be possibly due to the smaller difference between the drawing temperatures and
the fact that the two test temperatures are generally in the cold working range for all the
material compositions.
258
• Ageing index
The ageing index is observed to be higher at 130°C than at 200°C. This is due to the
occurrence of dynamic strain ageing at 200°C, which raises the level of the stress -
strain curve in the prestrain region. This in tum results in a lower ageing index. This
behaviour is observed in results obtained at both 30 and 600 seconds delay time after
prestrain.
9.2.2 Influence of delay time between prestrain and strain to failure:
• Work hardening rates
There seems to be no significant change in the value of the exponent with an increase
in the delay time after prestrain. This is possibly due to the fact that all interstitials
have migrated during prestrain and the first 30 seconds of holding time. No further
diffusion of interstitials has taken place beyond 30 seconds, thus leading to a negligible
effect of holding time on dynamic strain ageing and therefore, on the work hardening
exponent.
• Maximum stress
There appears to be no significant difference in the maximum stress values obtained in
the strain to failure region as a function of delay time. This leads to conclusion that all
the solute has segregated to the dislocations within the first 30 seconds and no further
addition is made to the amount of solute segregated at times greater than 30 seconds.
The delay time between prestrain and strain to failure does not affect the total strain to
failure. This phenomenon is observed at both the testing temperatures.
259
• Ageing index
A significant difference in the index is observed in EAF low B (149MPa for 600
seconds delay as against 89 MPa for the 30 seconds delay) and BOS high N+B(l 16
MPa at 600 seconds delay as against 70 MPa for the 30 seconds delay) with an increase
in the delay time after prestrain. However there is no significant difference in the index
with an increase in the delay time in BOS low and high N steels. It must also be
mentioned that it may be possible that the delay time of 600 seconds may not be enough
for interstitial diffusion at the low temperatures
9.2.3 Influence of material composition:
• Work hardening rates
Among the four grades of steels, BOS high B+N shows a marginally lower value of
work hardening rate in the prestrain region (0.228 as compared to 0.284 (BOS low N);
0.303 (BOS high N) and 0.244 in the EAF N+B grade at 130°C and 30 seconds; 0.295
as compared to 0.298 (BOS low N); 0.312 (BOS high N) and 0.354 in the EAF N+B
grade at 200°C and 30 seconds). This agrees with the results of Franks and Kirkcaldy< 73 >
who have reported lower work hardening rates in boron steels. The reasons for this
behaviour are the fixing of some of the free N by boron (confirmed by 'free nitrogen
analysis) and a coarser grain size. The values of the work hardening exponent are
definitely low for BOS high B+N grade in the strain to failure region (0.068 as
compared to 0.173 (BOS low N); 0.145 (BOS high N) and 0.153 in the EAF N+B grade
at 200°C and 30 seconds; and 0.028 as compared to 0.118 (BOS low N); 0.127 (BOS
high N) and 0.116 in the EAF N+B grade at 200°C and 30 seconds).
• Maximum stress
260
The maximum stress levels in the BOS high B +N steel are comparable to the BOS Low
N steel, although the work hardening rates are generally much lower in the former
material. The elongation in the BOS high B+N steel is also much higher as compared to
the BOS low N grade. The effect on maximum stress levels coupled with the high total
strain to failure in the high boron grade leads to a conclusion that some solid solution
strengthening is occurring in the BOS high N steel grade. A comparison of the
compositions indicates an appreciable difference in the boron levels between the two
grades, leading to a possibility of boron strengthening ferrite, having not fully
precipitated as BN. The other elements which could lead to ferrite strengthening are
almost the same level in the two steels.
The value of the total strain to failure for the BOS low N is slightly higher (0.3 units
higher) as compared to the BOS high N and the EAF low B grades. This is expected
due to the higher interstitial content in the latter grades, although it is to be noted that
the work hardening rates are similar or even slightly higher for the BOS low N grade.
The BOS High B+N grade exhibits the highest value of strain. As reported in literature
this is expected to be due to the fixing of all free nitrogen by boron. However, in the
current study it has been observed that all free nitrogen has not been fixed by boron. It
is therefore inferred that the high value of total strain to failure is due to a combination
of the fixation of some free nitrogen as well as a coarser grain size, resulting in higher
drawability.
• Ageing index
The values of ageing index for the four compositions show similar values at l 30°C and
30 seconds (variation is within experimental error). This indicates that boron additions
261
to the BOS and the EAF grade steels have not resulted in an additional advantage as far
as reducing strain ageing is concerned. This is further confirmed by the ageing index
results exhibited by the four steels tested at the remaining three combinations of
parameters, namely, 130°C-600 seconds, 200°C-30 seconds and 200°C- 600 seconds.
The index values for the EAF low boron steel and the BOS high N+B steel are
definitely higher than that obtained for the BOS low N steel. At the higher temperature
of 200°C, due to dynamic strain ageing, the indices are lower as compared to those at
130°C. However, the same trend of a marginal difference in the index as a function of
composition is maintained. BOS high N+B still shows a high ageing index indicating
incomplete effects of boron additions to these steels.
From the results of hot torsion and free nitrogen analysis studies, it has been observed
that BN has not completely precipitated in either the low boron steel (0.0012%boron
and 0.008% nitrogen, 0.003%aluminium, BIN ratio=0.15) or the high boron steel
(0.0038% boron, 0.006% nitrogen,. 0.006%aluminium, BIN = 0.63). However, both
these steel compositions have exceeded the equilibrium solubility limit of BN in
austenite. Absence of precipitation under these conditions could only mean that the
kinetic factors of temperature and time combinations were not favourable for BN
precipitation in these compositions. It has been reported that during the current
investigation, rods were quenched to the rod rolling temperature (from 1100°C to about
900°C) at BHP Newcastle. Experiments by Watanabe and Ohtani<S9) on steels
containing 0.0096% boron, 0.0326%nitrogen and 0.001% aluminium (BIN ratio= 0.29)
revealed BN precipitates when cooled from a hot rolling temperature of 1300°C at the
rate of 300°C /minute. A slower cooling rate of 0.67°C/minute gave a mix of BN and
262
AlN precipitates. The cooling rate employed in the current study is of the order of
water quenching followed by a cooling rate of 2°C/sec or 120°C/minute from 900°C,
which is in between the two cooling rates stated in Watanabe's study. For BN to
precipitate, it should do so either, during water quenching or when cooled from 900°C at
a slower rate. However, it must be also be stated that the austenitising temperature used
in Watanabe's study was 1300°C as against 1100 °C from where it was water quenched
and then 900°C in the current study from where a cooling rate of 2°C/sec was employed.
More importantly, a boron content of 0.0096% was used by Watanabe, as against a
maximum of 0.0038% used in the current study.
Besides this, another observation made is that due to a high degree of working of the
materials at 900°C, it is expected that enough number of dislocation sites are available
for heterogenous nucleation of BN in the boron containing grades. However, it has
been confirmed by 'free nitrogen' analysis results that a very small quantity of boron
has fixed nitrogen. This is further corroborated by the results of ageing indices as
discussed in earlier Chapters 7 and 8, where the BOS high N+B grade does not show a
marked and consistent improvement in the value of the ageing index as expected. In
view of the above arguments, it can be concluded that boron additions of 0.0012wt%
and 0.0038wt% to steels of 0.006-0.008 wt% N have not been effective in fixing all free
nitrogen under the cooling conditions of water quenching from 1100°C to 900°C and
subsequent cooling to room temperature at a cooling rate of 2°C/s.
This definitely leads to the conclusion that although thermodynamically, BN has
exceeded the equilibrium solubility· limits at the austenitising temperature, the driving
force due to supersaturation is not sufficient to cause precipitation during quenching
263
from this temperature. Further this supersaturation is not sufficient to facilitate
heterogenous BN precipitation during rolling.
It is also important to note that extensive transmission electron microscopic examination
of the four grades of steel tested at various combinations of time and temperature, did
not reveal any type of precipitation in the matrix or on the dislocations. This leads to the
conclusion that the strain ageing phenomenon in these steels was due to atmosphere
formation around dislocations. The second stage of precipitation on dislocations was
not reached even though enough number of sites were available for heterogenous
nucleation and sufficient driving force in the form of solute available in excess of the
equilibrium solubility at the lower drawing temperatures of 130°C and 200°C, was
available.
264
References
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265
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274
AppendixA
APPENDIX A
275
AppendixA
500
450
400
-
~ 300
350
-
:il:
tn
tn
250
i
en
200
150
100
50
0
0 0.2 0.4 0.6 0.8 1 1.2
Strain
Figure A-1 Hot tensile curves ofEAF Low B steel tested at 130°C after a delay of 600 seconds.
276
AppendixA
500
450
400
350
-
~
::E
300
";; 250
U)
Cl) 0.27 prestrain
b 200
en
150
100
50
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Strain
Figure A-2 Hot tensile curves of EAF low B steel tested at 130°C after a delay of 30 minutes.
277
AppendixA
500
450
400
0.18 prestrain
350
-
~ 300
:E
-; 250
u,
a,
.b 200
u,
150
100
50
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Strain
Figure A-3 Hot tensile curves of BOS high N tested at 130°C after a delay of 30 minutes.
278
AppendixB
APPENDIXB
HOT TORSION - TRUE STRESS STRAIN
CURVES
279
Appendix B
The true stress-strain plots for all the four grades of steel tested under varied
combinations of temperature and delay time are included in this Appendix B. The
various parts of the curve are explained in the first figure, Figure B-1. The initial part of
the curve labelled as A is the prestrain and the subsequent part is the stress-strain
behaviour when tested to failure after holding for a period of time following initial
prestrain for a period of either 30 seconds or 600 seconds. A point to note is that the
prestrain is consistent in all the stress-strain plots, indicative of the consistency and
reproducibility of the hot torsion test rig.
280
700
600
500
f:!!: 400
-U)
U)
"'-
l!! 300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-1 Stress-strain curve of BOS Low N tested at 130°C for a delay time of 30 seconds after prestrain.
281
700
600
500
-
~ 400
-
:::i:
I I)
-
II)
! 300
U)
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-2 Stress strain curve of BOS Low N steel tested at 130°C after a delay time of 600 seconds after prestrain
282
700
600
500
-
C,_ 400
-
:!!:
1/)
1/)
....f
u,
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-3 Stress strain curve for a BOS Low N steel tested at 200°C and 30 seconds after prestrain.
283
700
600
500
ci
400
-
D.
:iii:
I ll
Ill
- f 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-4 Stress strain curve of a BOS Low N steel tested at 200°C after a delay time of 600 seconds after prestrain.
284
700
600
500
-
CU
400
-e
D.
:I:
t /)
t/)
.... 300
u,
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-5 Stress strain curve of a BOS High N steel tested at 130°C after a time delay of 30 seconds after
prestrain
285
700 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
600
500
l:::.ii: 400
'iii'
Ill
i 300
"'
200
100
0-------------.----------,---------,--------,-------
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-6 Stress strain curve of a BOS high N steel tested at 130°C after a time delay of 600 seconds after prestrain.
286
700 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
600
500 ·
"i:iii 400
-e
u,
u,
-
en
300
200
100
o-------------------------------
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-7 Stress strain curve of a BOS high N steel tested at 200°C after a delay time of 30 seconds after prestrain
287
700 - - . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
600
500
-
~ 400
-
:!!:
I ll
Ill
-f 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-8 Stress strain curve of a BOS high N steel tested at 200°C after 600 seconds delay after prestrain
288
700
600
500
-
~ 400
-
:E
0
-
0
2! 300
C/J
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-9 Stress strain curve of an EAF low B steel tested at 130°C after a time delay of 30 seconds after prestrain.
289
700
600
500
-ea
a. 400
-
:ii:
t l)
-
tl)
f 300
u,
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-10 Stress strain curve of an EAF low B steel tested at 130°C after a time delay of 600 seconds after prestrain.
290
700
600
500
'ii
o.. 400
-
::iil:
u,
u,
w
0:: 300
I-
u,
200
100
0
0 0.5 1 1.5 2 2.5 3
STRAIN
Figure B-12 Stress strain curve of an EAF low N+B steel tested at 200°C after a time delay of 30 seconds after prestrain.
291
700
600
500
-
I'll
a. 400
-
:ii:
f l)
fl)
...f
u,
300
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-12 Stress strain curve of an EAF low N+B steel tested at 200°C after a time delay of 600 seconds after prestrain.
292
700
600
500
f 400
-
:ii:
1/j
-
1/j
f 300
U)
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-13 Stress strain curve of a BOS high N+B steel tested at 130°C after a delay time of 30 seconds after prestrain.
293
700
600
500
-ea
a.. 400
-
:E
,n
,n
-! 300
u,
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
Figure B-14 Stress strain curve of a BOS high N+B steel tested at 130°C after a delay of 600 seconds after prestrain.
294
700
600
500
-
3!_ 400
-
:ii:
in
-
in
! 300
en
200
100
0
0 0.5 1 1.5 2 2.5 3
Strain
295
700 --r----------------- -------------------- ,
600
500
':: 400
-
=5
I I)
II)
~ 300
tn
200
100
0 -1-------.....-------......------. .....------......------"T""------ -1
0 0.5 1 1.5 2 2.5 3
Strain
296
Appendix C
APPENDIXC
COMPUTATION OF WORK HARDENING
EXPONENTS
297
Appendix C
The following figures numbered C-1 to C-33 are plots of log stress versus log strain.
Figures C-1 to C-16 are plots of log stress-log strain for values computed from the
initial prestrain part of the stress-strain curve. While figures C-16 to C-33 represent log
stress-log strain plots for the strain to failure region. The method of calculating the
exponents is described in section 8.3.1.1.
- - - - - - - - - - - - - - - - - - - - - - - - - - - - 2.65
Log stress = 0.3033*1og strain + 2. 754 2.6
2.55
2.5
2.45
2.4
2.35
2.3
- - - . . - - - - . . . . . . - - - - , - - - -........- -........- - - . - - - - - - - - - - - 2.25

-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
Figure C-1 Work hardening exponent in the prestrain region of the stress strain
curve of BOS low N tested at 130°C and 30 seconds delay time after prestrain.
298
Appendix C
2.6
log stress= 0.28421og strain+ 2.7176
2.55
2.5
2.45
/.
2.4
• 2.35
2.3
2.25
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS high N steel tested at 130°C after 30 seconds delay after prestrain.
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2.65
y = 0.2441x + 2.7258 2.6
2.55
Ill
2.5
-
Ill
I!!
Cl)
CJ)
0
...J
2.45
2.4
2.35
- - - . . . . . - - -.........- -.......- - - - . - - - - - , . - - - - , . - - - . - - - - . . - - - - 2.3

-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
Figure C-3 Work hardening exp(ment in the prestrain region of strain curve of
EAF low B tested at 130°C and 30 seconds delay time after prestrain.
299
Appendix C
-----------------------------,3
...... , ...
log stress= 0.2283109 strain+ 2.6293
........ ,1111111111 I
1
2.5
Ill
-!
I I)
Cl
0
1.5
..I
0.5
~ - -.......- - - . - - - - - - , - - - - - - , - - - - - - - . - - - , - - - - - , - - - - - , - - - ~ 0
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS high N+ B tested at 130°C and 30 seconds delay time after prestrain .
. - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - , 2.6
log stress = 0.2686109 strain + 2.6951
2.55
2.5
,,,
2.45
-
e!
u,
Cl
0 2.4
...J
2.35
2.3
- - - - . - - - -........- - - - - - . - - - - - - - - - - - - - - - - - - - - - - 2.25
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS low N tested at 130°C and 600 seconds delay time after prestrain.
300
Appendix C
. . . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - , 2.65

2.6
2.55
2.5
2.45
2.4
2.35
2.3
- - - - - - - . - - - - . - - - - - , - - - - - - , - - - . . . . . , . . . - -........- -.......- - - . - - - 2.25

-2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS high N tested at 130°C and a time delay of 600 seconds after
prestrain.
. . . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . 2.65
log stress= 0.2502109 strain+ 2.7182 2.6
2.55
Ill
Ill 2.5
...
I!?
U)
g> 2.45
.J
2.4
2.35
1----...,....---,-----,.---...----...,....----,-----,,---....----1 2.3
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of EAF low B tested at 130°C after a time delay of 600 seconds after
prestrain.
301
AppendixC
.------------------------------3
log stress= 0.1728Iog strain+ 2.5941
2.5
0
1.5
0.5
1----...-----,------,----.....--------,------,----.....-------! 0
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS high N+B tested at 130°C and a time delay of 600 seconds after
prestrain.
. - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2.7
2.65
2.6
2.55
2.5
2.45
2.4
2.35
1----------.------------------------
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
2.3
Log Strain
curve of BOS low N tested at 200°C after a 30 seconds delay after prestrain.
302
Appendix C
. - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - , 2.7
2.65
2.6
2.55
2.5
2.45
2.4
2.35
2.3
- - - - - - - - - - - - - - - - . - - -........- - - - . - - - - - - - , - - - - - - 2.25
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS high N tested at 200°C after 30 seconds delay after prestrain.
2.75
log stress = 0.3539109 strain + 2.8783 2.7
2.65
2.6
2.55
2.5
2.45
2.4
2.35
2.3
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of EAF low B tested at 200°C after 30 seconds delay after prestrain.
303
AppendixC
...-------------------------------.3
.. 0 ,. co ...
' I tllfil S2 it11 I 1 2.5
jCl)
1.5
0
...J
0.5
----,------,---.....,.----,---,-----,------,------,---- 0
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS high N+B tested at 200°C after 30 seconds delay after prestrain.
. - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . 2.7
log stress = 0.3221og strain + 2.8366
2.65
2.6
2.55
2.5
2.45
2.4
2.35
2.3
2.25
1------,-----,.----.---........- -.......--....-----,,-----.-----,----'1 2.2

-2 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS low B tested at 200°C after 600 seconds delay after prestrain.
304
Appendix C
- - - - - - - - - - - - - - - - - - - - - - - - - - - - . 2.7
2.65
2.6
2.55
2.5
2.45
2.4
2.35
2.3
- - - . . . - - - . . . . . - - - - , - - - - - , - - - - . . . . . . . - - -.......- - . . . - - -.......- -.... 2.25

-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
FigureC-14 Work hardening exponent in the prestrain region of the stress strain
curve of BOS high N tested at 200°C after 600 seconds delay after prestrain
.------------------------------,3
• 0 Ct T
' ...
log stress= 0.2947Iog strain+ 2.7318 ,
t U uet II $11 1111
11111
'1 2.5
1.5
0.5
- - - - , - - - - . . . . - - - - - , - - - - - , - - - - - , . - - - . - - - - . . . - - -.......- - - ! 0
-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of EAF low B tested at 200°C after 600 seconds delay after prestrain.
305
Appendix C
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - , 2.75
2.7
log stress = 0.34641og strain + 2.8589
2.65
2.6
2.55
2.5
2.45
2.4
2.35
2.3
- - - - - - - . - - - - - - , . - - - . - - - -.......- -.......- - - - - - - - - 2.25

-1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0
Log Strain
curve of BOS high N+B tested at 200°C after 600 seconds delay after prestrain.
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2.77
log stress= 0.14481og strain+ 2.7506 2.76
2.75
2.74
2.73
2.72
2.71
2.7
---.. . . --.. . . --.. . . .-----.---..--------------1-------1 2.69

-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
log strain
Figure C-17 Work hardening exponent in a portion of 'strain to failure' region of

the stress-strain curve of BOS low N tested at 130°C and 30 seconds delay after
prestrain.
306
Appendix C
. . . . - - - - - - - - - - - - - - - - - - - - - - - - - , - - - - - - - . 2.7
log stress = 0.0679Iog strain + 2.6924 2.695
2.69
Ill
2.685
ICl)
0 2.68
...J
2.675
2.67
1------,----.------,----,-----,------,,-----+------I 2.665
-0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain

the stress-strain curve of BOS high N tested at 130°C and 30 seconds delay after
prestrain.
. . . . - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . 2.77
2.76
2.75
2.74
2.73
2.72
2.71
2.7
- - - . . . . - - - - . - - - - , - - - - - - - - - - - - - - - - - - - " " " ' 2.69

-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain

the stress-strain curve of EAF low B tested at 130°C and 30 seconds delay after
prestrain.
307
AppendixC
- - - - - - - - - - - - - - - - - - - - - - - - , - - - - - , 2.7
log stress = 0.06791og strain + 2.6924 2.695
2.69
-i
2.685
Ill
C>
.3 2.68
2.675
2.67
1-----,-----.---...-----,----....---- -,----1-----1 2.665

-0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain

the stress-strain curve of BOS high N+B tested at 130°C and 30 seconds delay after
prestrain
. - - - - - - - - - - - - - - - - - - - - - - - - - - . . . . - - - - - . 2.73
2.72
2.71
2.7
2.69
2.68
2.67
2.66
2.65
- - - - - - - - - - - - - - - . - - - - - - - - - - - - - - - - - 2.64
-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain
FigureC-22 Work hardening exponent in a portion of 'strain to failure' region of

the stress-strain curve of BOS low N tested at 130°C and 600 seconds delay after
prestrain.
308
AppendixC
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - . - - - - , 2.78
2.77
2.76
2.75
2.74
2.73
2.72
2.71
- - - - - - - . - - - - - - , . - - - . . . - - - . . . . - - - . . . . - - - . . . , . . . - - - - - - 2.7
-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain

the stress-strain curve of BOS high N tested at 130°C and 600 seconds delay after
prestrain.
- - - - - - - - - - - - - - - - - - - - - - - - - - . . . - - - - 2.78
2.77
2.76
2.75
2.74
log stress = 0.05991og strain + 2. 7043
2.73
2.72
2.71
....
-- 2.7
.... .
2.69
-0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain

the stress-strain curve of EAF low B tested at 130°C and 600 seconds delay after
prestrain.
309
Appendix C
. - - - - - - - - - - - - - - - - - - - - - - - - - - , - - - - - - , 2.77
2.76
2.75
2.74
2.73
2.72
2.71
2.7
2.69
1----..---..---..----..----..-----,----- ,-----1------1 2.68

-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log Strain

the stress-strain curve of BOS high N+B tested at 130°C and 600 seconds delay
after prestrain.
2.78
2.77
2.76
2.75
2.74
2.73
2.72
2.71
2.7
2.69
-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05 0.1
LOG STRAIN
Figure C-26 Work hardening exponent in 'strain to failure region of the stress-
strain curve of BOS low N tested at 200°C and 30 seconds delay after prestrain.
310
Appendix C
- - - - - - - - - - - - - - - - - - - - - - - - - - - . - - - - . 2.75
2.74
2.73
2.72
2.71
2.7
2.69
1-----,-----,-----.-----,,----,---..----........---+------'I 2.68
-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log Strain
Figure C-27 Work hardening exponent in the 'strain to failure'region of the stress-
strain curve of BOS high N tested at 200°C and 30 seconds delay after prestrain.
. . - - - - - - - - - - - - - - - - - - - - - - - - - - . - - - - . 2.79
2.78
log stress= 0.11631og strain+ 2. 7661
2.77
ICII
0
..J
2.76
2.75
2.74
2.73
1----..----..----..-----,----...,....---,-----,----+----'I 2.72
-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain
strain curve of EAF low B tested at 200°C and 30 seconds delay after prestrain.
311
AppendixC
. - - - - - - - - - - - - - - - - - - - - - - - - - - . , . . . . . . - - - - , 2.722
2.72
2.718
2.716
2.714
2.712
2.71
2.708
2.706
.,__----,-----,------,.---......----,,----...,...---+-----'I 2.704
-0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain
strain curve of BOS high N+B tested at 200°C and 30 seconds delay after prestrain.
. - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - , 2.79
2.78
log stress= 0.13211og strain+ 2.7737 2.77
2.76
2.75
2.74
2.73
2.72
2.71
2.7
- - - - , - - - - - , . - - - . . - - - -.......- - - - . - - -.......- -......- - - 2.69

-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0
Log Strain
strain curve of BOS low N tested at 200°C and 600 seconds delay after prestrain.
312
Appendix C
- - - - - - - - - - - - - - - - - - - - - - - - -........- - - . 2.74
2.73
2.72
2.71
2.7
2.69
2.68
1----....---........ ---.-----.----------.....----+-----I 2.67

-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain
strain curve of BOS high N tested at 200°C and 600 seconds delay after prestrain.
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - 2.79
2.78

2.77
2.76
2.75
2.74
2.73
2.72
1 - - - -........----,-----,,---.-----,----,-----,,----+-------! 2.71
-0.4 -0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain
strain curve of EAF low B tested at 200°C and 600 seconds delay after prestrain.
313
Appendix C
- - - - - - - - - - - - - - - - - - - - - - - - - - - -.... 2.78
2.77
2.76
2.75
II)
-
II)
2.74
I!!
I I)
CD
0 2.73
...J
2.72
2.71
2.7
- - - . . . . . . - - - - - - - - - - - . - - - - . . . . - - - - - - - - - - - - - - . . . , , 2.69
-0.35 -0.3 -0.25 -0.2 -0.15 -0.1 -0.05 0 0.05
Log strain
strain curve of BOS high N+ B tested at 200°C and 600 seconds delay after
prestrain.
314

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The University of New South Wales

Strain Ageing Of Low Carbon Steel

Submitted in Partial Fulfilment

knowledge it contains no materials previously published or written by another

award of any degree or diploma at UNSW or any other educational institution,

to the research by others, with whom I have worked at UNSW or elsewhere, is

acknowledged in the thesis.

conception or in style, presentation and linguistic expression is acknowledged.

I wish to express my deepest sense of gratitude and appreciation to my supervisor Dr.

supply of test material and use of hot torsion testing facilities.

Dr. Alan Brownrigg, formerly Manager, BHP Laboratories, Melbourne, currently at

guidance during transmission electron microscopy work.

A major problem encountered during metal forming operations, in particular wire

drawing is strain ageing. This phenomenon manifests itself as an increase in strength

dislocations. These interstitials form atmospheres around dislocations, effectively

impeding further movement. At lower temperatures, nitrogen typically plays a greater

conditions typical of industrial wire drawing. However, the absence of precipitate

steels was due to atmosphere formation around dislocations.

It is concluded that boron additions of 0.0012wt% and 0.0038wt% to steels of 0.006-

temperature at a cooling rate of 2°C/s.

TABLE OF CONTENTS Vlll

LIST OF TABLES XXll

CHAPTER 2 PHYSICAL METALLURGY OF LOW CARBON

CHAPTER 3 PRECIPITATION KINETICS 23

CHAPTER 4 STRAIN AGEING OF LOW CARBON STEELS 53

CHAPTER 5 RESEARCH OBJECTIVES 127

CHAPTER 6 EXPERIMENTAL METHODS 131

CHAPTER 7 RESULTS 139

CHAPTER 8 DISCUSSION 180

CHAPTER 9 CONCLUSIONS 256

9.2.3 Influence of material composition 260

Figure 3.1 Free energy and chemical potential changes during

Figure 7.10 Stress-strain curves of BOS low N steel as a function of test

Figure 7.28 Stress-strain curves of the four material compositions

Figure 8.7 Stress-strain behaviour as a function of temperature of

Figure 8.27 Comparison of maximum stress values in the strain to

Figure C-1 Work hardening exponent in the prestrain region of the

Figure C-16 Work hardening exponent in the prestrain region of the

Figure C-31 Work hardening exponent in the 'strain to failure 'region of

simple structural load-bearing ones to the more sophisticated aerospace applications.

agemg. Suppose a steel specimen is strained to a point A and then unloaded. If it is

characteristics of strain ageing are described more fully in Chapter 4.

both beneficial and detrimental effects.

A Y = chan1• in yield stress due to strain a1ln1

be incorporated into thermomechanical treatment to improve room-temperature tensile

markings during forming.

and Bar Division, Newcastle and the Australian Research Council.

will concentrate particularly on the physical and mechanical metallurgical principles

experimental details are described in Chapter 6. Initially, the laboratory work

commenced with hot tension experiments. However, subsequently it became evident

PHYSICAL METALLURGY OF LOW CARBON

STEELS USED FOR WIRE/ROD PRODUCTS

have been included at the beginning of this Chapter.

like drawability/formability, strength, toughness, corrosion resistance and weldability

2.2 WIRE DRAWING - A GENERAL DESCRIPTION

The reduction in the diameter of a solid bar/rod by a successive drawing operations is

process somewhere in the range of 40-70°C. In extreme conditions it may exceed

carbon and alloy steels.

drawing, the rod is cleaned by pickling in a sulphochrome bath (sulphuric acid -

subsequent controlled cooling or transforming in a lead bath held at a temperature

2.3 PHYSICAL METALLURGY OF LOW CARBON GRADES USED FOR WIRE/ROD

Nitrogen levels vary from a minimum of 0.008 to 0.012 %.

nitrogen content than the BOS grade.

2.3.1 Fe - Fe3C phase diagram