Mechanism of Work Hardening in

Hadfield Manganese Steel

Y. N. D A S T U R A N D W. C. LESLIE

When Hadfield manganese steel in the single-phase austenitic condition was strained in
tension, in the temperature range - 2 5 to 300 ~ it exhibited jerky (serrated) flow, a
negative (inverse) strain-rate dependence of flow stress and high work hardening, charac-
teristic of dynamic strain aging. The strain rate-temperature regime of jerky flow was
determined and the apparent activation energies for the appearance and disappearance of
serrations were found to be 104 k J / m o l and 146 kJ/mol, respectively. The high work
hardening cannot be a result of mechanical twinning because at - 5 0 ~ numerous twins were
produced, but the work hardening was low and no twins were formed above 225 ~ even
though work hardening was high. The work hardening decreased above 300 ~ because of
the cessation of dynamic strain aging and increased again above 400 ~ because of
precipitation of carbides. An apparent activation energy of 138 k J / m o l was measured for
static strain aging between 300 and 400 ~ corresponding closely to the activation energies
for the disapperance of serrations and for the volume diffusion of carbon in Hadfield steel.
Evidence from the present study, together with the known effect of manganese on the
activity of carbon in austenite and previous internal friction studies of high-manganese
steels, lead to the conclusion that dynamic strain aging, brought about by the reorientation
of carbon members of C-Mn couples in the cores of dislocations, is the principal cause of
rapid work hardening in Hadfield steel.

A U S T E N I T I C manganese steel, called Hadfield man- Although this steel has been used for nearly a century
ganese steel after its inventor, Robert Hadfield, t is a since its development in 1882, the mechanism of rapid
tough, nonmagnetic, Fe-C-Mn alloy, useful for severe work hardening remains unclear. The purpose of this
service combining abrasion and heavy impact. The study was to determine the mechanism of rapid work
ASTM Standard A-128-642 covering this steel allows hardening in Hadfield steel with the intent of solving
composition ranges from 1.0 to 1.4 pct C and from 10 to one of the classical mysteries of physical metallurgy.
14 pet Mn. However, commercial alloys with manga-
nese contents greater than 12 to 13 pct are seldom used PREVIOUS S T U D I E S A N D
because of cost. Moreover, work hardening in a 1.15 P R O P O S E D M E C H A N I S M S OF W O R K
pct C alloy reaches a maximum at 13 pct Mn. 3 Hadfield H A R D E N I N G IN H A D F I E L D STEEL
steel is usually austenitized to dissolve carbides and to
It is commonly taught that the rapid work hardening
produce homogeneous austenite, which is preserved by
in Hadfield steel arises from strain-induced transfor-
water quenching from above 1000 ~ Typical me-
mation of y to ~ or c martensites: but it has been shown
chanical properties are: 3 a) yield strength (0.2 pct
that the austenite of Hadfield's composition is stable
offset), 379 MPa; b) ultimate tensile strength, 965
during plastic strain, 6-8 even below - 1 9 6 ~176 Strain-
MPa; c) elongation in 50 mm, 50 pet; d) reduction of
induced transformation occurs only because of decar-
area, 40 pct; e) hardness, as quenched, 190 HB;
burization or local segregation of manganese that leads
f) hardness, at fracture, 500 HB; g) Charpy V-notch
to unstable austenite compositions. Some workers l~'12
impact, 169 J at 22 ~ 7 J at - 196 ~ The unique
attributed the rapid work hardening to fine mechanical
feature of this tough, high-strength steel is the rapid
twinning. However, their studies did not include meas-
work hardening, from a yield strength of 379 MPa to an
urements of rates of work hardening nor description of
ultimate tensile strength of 965 MPa. In gouging
microstructures obtained at a variety of strain rates and
abrasion tests, the Hadfield steel performs better than
temperatures. Lambakakhar and Paska113 observed no
wrought alloy steels, cast alloy steels, stainless steels,
correlation between frequency of twins and hardness.
tool steels or high-chromium white irons. 4 These com-
Instead, they concluded that the hardness of Hadfield
binations of properties make it useful in such diverse
steel is more likely a function of the general dislocation
applications as crawler treads for tractors, railroad
structure than of the specific microstructure. Drobnjak
frogs, grinding mill liners, crusher jaws and cones,
and Parr 14suggested that stacking fault-dislocation
impact hammers, dipper bucket teeth and nonmagnetic
interactions were responsible for increasing the strain-
plates for electromagnets.
hardening rate. However, according to Roberts, 7 stack-
ing faults were present only in hammered specimens,
Y. N. DASTUR and W. C. LESLIE are at the Department of not in tensile or explosive shocked specimens which
Materials & Metallurgical Engineering,Universityof Michigan, Ann
Arbor, MI 48109. deformed by twinning. The stacking fault energy of
Manuscript submitted August 11, 1980. 1.1 C, 12 pct Mn steel was determined to be 50 m J / m 2
ISSN 0360-2133/81/0511-0749500.75/0
METALLURGICALTRANSACTIONSA 9 1981 AMERICAN SOCIETY FOR METALS AND VOLUME 12A, MAY 1981--749
THE METALLURGICAL SOCIETY OF AIME
at room temperature, decreasing with decreasing tem-
perature and decreasing carbon content. 15This value is
higher than those of fcc metals such as Ag (16 m j/m2), ]6
Au (32 m j/m2) ~7 and austenitic stainless steels (---20
m J/m2) ~8whose work-hardening rates are lower than
that of Hadfield steel. Serrated flow in this alloy has
been observed 9,19but its limits have not been deter-
mined. Several authors 7a~ have proposed that the
rapid work hardening is due to the interaction of
dislocations with carbon atoms in solid solution in
austenite. No one has observed carbide precipitation in
this alloy at ambient temperature nor seriously pro-
posed that the exceptional work hardening is due to
carbide precipitates. From a comparison of the defect
structures and hardening in shock-hardened Fe-32 Ni,
Fe-23 Ni-0.6 C and Hadfield steel, Leslie 2~concluded
that the most likely cause of the rapid work hardening
in Hadfield steel is interactions between dislocations
and Mn-C couples in solution in austenite. Sastri's TM
studies of MOssbauer spectroscopy of Hadfield steel
indicated a clustering of carbon atoms in austenite
during cold working with the process being enhanced
by aging.
MATERIALS AND PROCEDURE
Tension specimens 6.25 mm in diameter with a gage
length of 25 mm were machined from commercial
hot-rolled bars of Hadfield manganese steel having the
composition 1.13 pct C, 11.4 pct Mn, 0.2 pct Si, 0.17 pct
Ni, 0.16 pct Cr and 0.08 pct Mo. These specimens were
sealed in stainless steel envelopes, annealed at 1100 ~
xvl vx*~-xxo, zl ll~t,~l, ux~,xL ~-ll.,~lx~.,LL~.,~
produce a single-phase austenite with grain size ASTM
3-4, without decarburization.
Strain aging
In tests of dynamic strain aging, several heat-treated
specimens were strained in tension at rates between
10-Ss - ] and 10-2s -l and at temperatures ranging from
- 50 to 600 ~ in a 250 kN Instron machine equipped
with a radiant-heating chamber and a low-temperature
bath. Static strain aging experiments were performed on
other specimens as follows: specimens were prestrained
4 pct in tension at - 2 5 to 400 ~ (_+ I~ in con-
trolled-temperature liquid baths for short aging periods
(less than 30 mins) and in an air-circulating furnace for
longer periods. At aging temperatures below 300 ~ the
stress increment, Ao, was measured as shown in Fig. 1.
At higher aging temperatures Ao was defined as the 0.2
pct offset yield stress after aging less the flow stress
before aging. Straining before and after aging was done
at - 25 ~ to eliminate the possibility of dynamic strain
aging during the test; therefore, no aging tests were
performed for periods of less than two minutes.
Metallography
Sections parallel and perpendicular to the tensile axis
were cut from dynamically strain-aged specimens, elec-
tropolished in a sodium chromate-acetic acid solution
and examined by light microscopy. Thin foils for
7 5 0 - - V O L U M E 12A, M A Y 1981
~o"
T
O3
5O
LO
cr
I--
C/)
I /lUnlood, AcJe, Relood
Prestroin
STRAIN
Fig. l--Stress-strain curve illustrating static strain aging.
transmission electron microscopy were prepared by
cutting sections about 300/~m thick with a diamond
saw, grinding them carefully to about 100/~m thickness
and then electrothinning in a dual-jet electropolisher/
thinner in a mixture of 80 g anhydrous sodium chro-
LLL ll,,~.,~..t t)lLIX~., tV IIIK~.I.~ K~.ll~t "I'K/K/ 1111 ~I~II.~,IKI.I ( , t ~ l . , ~ , l ,l v ~ O . ~ l ~ l ~L ,./KS (.I.IIK.I~ 1 J,J K S ltt,/~
for 6 to 8 min. Foils were examined in a JEOL 100CX
STEM at 100 kV.
MOssbauer Spectroscopy
A Ranger M6ssbauer spectrometer was used in
conjunction with a Tracor Northern NS-600 multi-
channel analyzer. 25/~m thick samples were prepared
from specimens strained 20 pct in tension, within and
outside the dynamic strain-aging region. All spectra
were taken at room temperature, in the transmission
mode, using 57Co/Rh as source of y-rays and a-Fe foil,
enriched in 57Fe, as a reference absorber. The data were
computer curve fitted by the flexible least-square rou-
tine for general MOssbauer effect spectra fitting of
Wilson and Swartzendruber. 22
RESULTS
In the temperature range between - 2 5 and 300 ~
Hadfield manganese steel, strained in tension, exhibited
serrated flow (jerky stress-strain curves), negative
strain-rate dependence of flow stress (decrease in flow
stress with increase in strain rate) and high work-
hardening rates. Stress-strain curves, at room temper-
ature, showing these characteristics are presented in
Fig. 2. Figure 3 illustrates serrations at various temper-
atures and a nominal strain rate of 3 • 10-% -1. Three
different types of serrations, A, B and C, were observed,
depending on strain rate and temperature. Types A and
M E T A L L U R G I C A L TRANSACTIONS A
 t.-;., 2800

|OOC E = 3 x IO -4 s-1

W~t~"600
rr
at
,...f
/T I KN on
600m~
I-- |ff Mogmhed
Or) 4 0 0 61- ~ STle 1200

2OO 4 I 800
aW~.(TypeB
2 [ Serrohons) I 2% I 400
I I I I I I I I I I I I ~ I
0 4 8 12 16 20 24 28 32 36 4 0 44 48 65
STRAIN, % g -
o
Fig. 2--Engineering stress-strain curves o f Hadfield manganese steel ELONGATION P
at 24 ~ Fig. 4 - - A p o r t i o n o f the load-elongation curve o f H a d f i e l d man-
ganese steel at 24 ~ showing the effect of strain rate on serrated
flow.

-10~ 24~ 125~ 190oc

YPE A TYPE C.
TYP7 El

EG=45%
05
INN ~Ec=09%
E==6.2% = , %
~t ~164secl /
/
I 5 0 sec 4 0 sec 24 sec
I
/,
Fig. 3--Serrated flow in Hadfield steel as affected by temperature.
Nominal strain rate 3 x 10-4 s - l , ec = "critical s t r a i n " .

B serrations were observed at lower temperatures and

type C at higher temperatures. The serrations increased Fig. 5--Variation of strain-rate dependence of flow stress with tem-
perature in Hadfleld steel.
in magnitude and frequency as the temperature was
raised, then vanished at temperatures above 190 ~
The strain at which serrations first appeared, e~, the
so-called critical strain, first decreased then increased
with increasing temperature. The effect of strain rate on
serrations is shown in Fig. 4. On increasing the strain TEMPERATURE,~
rate type B serrations disappeared, with a drop in 300 200 t00 25 0 -25
average level of flow stress, that is, the flow stress had a
negative strain-rate dependence. The temperature range
of this phenomenon is shown in Fig. 5.
_
I I I
/ I L

i Termination *
Figure 6 shows the strain rate-temperature regime of t46 Kd/mole
serrations. Outside this region the flow was smooth. The
apparent activation energies for the appearance and ,S
disappearance of serrations were 104 k J / m o l and 146 L~ KJ/mole
kJ/mol respectively. The estimated error in these values ~ t6 3
is _ 15 pet. Figure 7 is a comparison of stress-strain z oO
curves at -25, 24 and 500 ~ to illustrate rates of work No
hardening within and outside the dynamic strain aging r~ ;erra-
I-- Serrotions
'ions
region. The correlation of serrated flow, negative r . o-.
strain-rate dependence and work hardening is shown in tions
Fig. 8. The measure of work hardening used in this 1(~4 -- o o
figure is the difference in flow stress at plastic strains of
r J 1
0.04 and 0.002 (0oo4 - 0o.oo2).It is obvious that work 1.5 2.0 3.0 4.0
hardening is high within the negative strain-rate depen- tO00/T, K -I
dence range and drops off sharply at both ends of this Fig. 6 - - S t r a i n rate-temperature regime of serrations in Hadfield
range. At temperatures above 400 ~ the work harden- steel.

METALLURGICAL TRANSACTIONS A V O L U M E 12A, M A Y 1981--751

 ing rises again. Similar results (not shown here) were
= 3 x 10"4s-I obtained when the measure of work hardening was (%.08
500 -
- 00.002)or (002 - 00.002).
Figure 9 shows the tensile properties of the Hadfield
o 400 steel. A peak in ultimate tensile strength and a slow,
(3-
continuous decline in yield stress were observed in the
~o~300 dynamic strain-aging region. Ductility, measured as pct
I.l.l elongation in 25 ram, is high and also reaches a
IX
I-- 200
maximum within the dynamic strain-aging region. In
O9
the temperaure region from - 2 5 to 300 ~ in which
the uniform elongation equaled the total elongation,
t00 specimens failed predominantly by intergranular frac-
ture with void formation at grain boundaries, as ob-
I I I I I I I I served by scanning electron microscopy. At 500 ~ the
0 2 4 0 4 8 12 16 20
fracture was accompanied by a large reduction of area.
STRAIN,%
The fracture surface contained dimples.
Fig. 7--Comparison o f engineering stress-strain curves of Hadfield
manganese steel illustrating different rates of work hardening within
Figures 10 to 18 show the microstructure of Hadfietd
and outside the dynamic strain aging region. steel after 20 pct strain in tension at several temper-
atures. Mechanical twins are present in profusion at the
lowest temperature studied ( - 50 ~ Comparisons of
t601f Rangeof 9 microstructures at several temperatures within the dy-
JSerrated Flow namic strain aging region (Figs. 10 to 12) indicate that
r i - the twin density decreases with increasing temperature,
i / i approaching zero at 225 ~ At this temperature, the

',, loo ,,
/ /i - i5 ~,

bq 80 =tO'"sec-'~, /\\ / ~2" -10

6C V \q1oZsec'
40 I I I I i i I
-500 100 200 300 400 .500 600
T EMPERATURE,~
Fig. 8--Temperatu~,dependence of work hardening in Hadfield
steel. (*Negative strain-rate dependence)

1100
e ~' 10"4sec"I 150
~000
900

"~
800
(u)
70o I00

o 600
(I" RE~,O~
~A 4,1
Ksl
~E.5OO

400
50
30C
20C
Ioc 0 2 % Offset

c
I" E,~. -: E~r "I g
~ s e c - ' <z
~m
Z
~ 6o
~ `5o
B4
I.iJ
N 0T I i J t [ f
-100 0 100 200 300 400 500 (b)
TEMPERATURE, *C Fig. 10--Deformation twins in Hadfield steel after 20 pct strain in
Fig. 9---~'Temperature dependence o f tensile properties of Hadfield tension at (a) - 5 0 ~ and (b) 24 ~ Sodium chromate, acetic acid
steel (El u = uniform elongation, E l T = total elongation). electrolytic etch.

7 5 2 - - V O L U M E 12A, MAY 1981 M E T A L L U R G I C A L TRANSACTIONS A

 Ca)

Fig. 13--Carbide precipitation on austenite grain boundaries in

Hadfield steel after 20 pct strain in tension at 400 ~ Sodium
chromate, acetic acid electrolytic etch.

(b)
Fig. 1 1 - - D e f o r m a t i o n twins in Hadfield steel after 20 pct strain in
tension at 190 ~ (a) ~ -- 10-4 s - l , (b) e = 10-2 s- l . Note the
reduced twin density compared to Fig. i0. Sodium chromate, acetic
acid electrolytic etch.

(b)
Fig. 12--Microstructure of Hadfield steel after 20 pct strain in ten- Fig. 14--Carbides in Hadfield steel after 20 pct strain in tension at
sion at 225 ~ Austenite matrix with few mechanical twins. Sodium (a) 500 ~ a n d (b) 600 ~ Sodium chromate, acetic acid electro-
chromate, acetic acid electrolytic etch. lytic etch. Magnification 185 times.

METALLURGICAL TRANSACTIONS A V O L U M E 12A, M A Y 1981--753

 r
(b)
Fig. 15--Transmission electron micrographs of deformation twins
in Hadfield steel strained 20 pct in tension at 24 ~ (a) Bright field
image. (b) Dark field image from (131) reflection.
work hardening is the same as at temperatures where
twinning was profuse (Fig. 8). A comparison of Figs. 8
and 10 to 12 reveals no correlation between twinning
and work hardening. Figures 13 and 14 show carbide
(M3C) precipitates, which correlates well with increased
work hardening above 400 ~ as shown in Fig. 8.
Comparison of Figs. 1 l(a) and (b) shows that strain rate
has little effect on twin density, within the range of
strain rates studied (10 -5 to 10-2s-~).
Figures 15 to 18 are transmission electron micrographs
and electron diffraction patterns of Hadfield steel
after 20 pct strain in tension at 24 and 500 ~ These
corroborate~d observations by light microscopy and
confirmed the presence o f twins at low temperatures
and precipitation of (Fe, Mn)3C at higher temperatures.
Results of static strain aging at temperatures below
300 ~ are shown in Fig. 19. The increase in flow stress,
Ao, shown in Fig. 1, rapidly increased to a constant
value of about 18 M P a at all temperatures studied
except for - 2 5 ~ No further rise in zao was observed
even after long periods at these temperatures. Samples
taken from this group of specimens showed a single-
phase austenitic structure by light microscopy. Results
of static strain aging at temperatures of 300 ~ and
754--VOLUME 12A, MAY 1981
(a)
rb)
Fig. 16--(a) Electron diffraction pattern from twinned austenite for
the area in Fig. 15. [111] matrix and [114] twin normal to the foil.
(b) Indexed pattern. 9 matrix reflections, O twin reflections.
higher are shown in Fig. 20 with data from Fig. 19
included for comparison. In contrast to low-tempera-
ture aging, At, increased sharply after relatively long
aging, then approached a plateau. Samples from this
group of specimens showed carbide precipitates under
light microscopy. These specimens had very limited
total elongation. The activation energy for the aging
process, between 300 and 400 ~ was 138 kJ/mol, as
shown in Fig. 21. The kinetics of aging were determined
from plots of (Ao -- Aoo) vs time at various tempera-
tures, as shown in Fig. 22. The slopes of the lines are
close to one, i.e., (Aa - Aoo) is proportional to aging
time, which is not in accord with Cottrell's t 2/3 law, 23
perhaps because of the very high carbon concentration
and precipitation of carbides.
Figure 23(a) is a MOssbauer spectrum of Hadfield
steel in the as-quenched condition. Figures 23(b)
through (d) show spectra of specimens strained 20 pct at
24, 190 and 350 ~ respectively. Each spectrum can be
resolved into a central peak, with a negQ.tive isomer
METALLURGICAL TRANSACTIONSA
 (a)

(a)

(b)
Fig. 17--Transmission electron micrographs of a carbide plate in
Hadfield steel strained 20 pct in tension at 500 ~ (a) Bright field
image. (b) Dark field image from (021) carbide reflection.
(b)
shift, and a quadrupole-split pair with values indicated Fig. 18--(a) Electron diffraction pattern from carbide plate in
austenite for the area in Fig. 17. (b) Indexed pattern. 9 Austenite
on the figure. These peaks agreee with those published spots, O carbide spots.
for iron-carbon austenite 24-27and iron-carbon-manganese
austenite. 21 The central peak can be attributed to iron
atoms free of carbon neighbors and the quadrupole pair
to iron atoms in a noncubic environment because of
carbon neighbors. N o strain-induced martensite was
observed, in agreement with the results of Sastri and
Ray 21 and Katz, Mathias and Nadiv. 28 There was no 2m lh Id 7d
I I I I
difference, within experimental error, between the rel-
ative areas under the central and the quadrupole peaks
for different spectra, therefore, no effects of strain aging
could be detected.
2s
[] o g 4~ n

DISCUSSION
b
<3
A. S u m m a r y of Observations
10
The results of tension tests of Hadfield steel at ( 0 o 0~-25 C
various temperatures and strain rates, supplemented by
5
data from static strain aging experiments, show that a
strain-aging mechanism operates between - 25 and
0 I I I
300 ~ and within this temperature range the alloy 101 10 2 10 3 10 4 t0 5
TIME, see
work hardens rapidly. As in other alloys undergoing
dynamic strain aging (DSA), such as low-carbon steel, 29 Fig. 19--Static strain aging of Hadfield steel at low temperatures.

METALLURGICAL TRANSACTIONS A VOLUME 12A, MAY 1981--755

 150 5tmin. 1hour
j 24Lhrs 7d~ 15
2O
days
t00~ SLOPE : 118
125
1oo 4oo*cf/ /~ - ]5 ~50F
~~rlOj~_L~ / / 5 7 ~ ~ /SLOPE=098/
':' r~
o / / // / / 35~176 r
oo c/- I0
so I 7 //
,/ j
E
/2z~c 5
....

25 . a
200 ~C
t]"IOs
106 0
I "
102 103 104 ]05 t04 tO5 t06
TIME,sec TIME, sec
Fig. 22--Stress increment after aging, corrected for initial time-
Fig. 20--Static strain aging of Hadfield steel at high temperatures. independent stress (Ao - A a o ) , plotted v s time, from data in Fig. 20.

400 350 500,0C
tVal I I I [
Q=t38Kd/mole
1(9"*
t 0 MPa
MPo
--~ MPo
t.25 1.50 1.75 2.00
IO00/T, K-I
Fig. 2t--Activation energy for static strain aging of Hadfield steel
between 300 and 400 ~ (data taken from Fig. 20).
austenitic stainless steel3 ~ a T i , 31 V - N b , 32 Inconel 60033
and maraging steel, 34 such pronounced work hardening
is associated with serrated load-elongation curves and a
negative (inverse) strain-rate dependence of the flow
stress. Serrated flow curves during DSA have been
explained in terms of the initiation, propagation and
pinning of Luders bands. 3s,36,37N u m e r o u s studies 3s-45
have shown that the increased work hardening accom-
panying serrations can be attributed to an increased
rate of dislocation multiplication, which increases the
dislocation density for a given strain.
The activation energy for the onset of serrations, 104
_+ an estimated 15 k J/tool, (Fig. 6) is considerably less
than the activation energy for bulk diffusion of carbon
in austenitic Hadfield steel - 1 4 0 to 150 k J / m o l (Fig.
24) 46.47
The static strain aging experiments showed that an
increase in the lower yield stress was produced in aging
periods of less than two minutes at 22, 100 or 200 ~
and that the magnitude of the increase was independent
of temperature and aging time, up to one week (Fig. 19).
The much smaller increase in yield stress noted after
aging at - 25 ~ m a y be attributable to a Haasen-
Kelley effect 48 but this cannot be stated with certainty.
The much larger increases in the yield stress observed
after lengthy aging at 300 to 400 ~ (Fig. 20) can be
attributed to formation of Cottrell atmospheres and to
precipitation of (Fe, Mn)3C. The activation energy for
these static strain aging effects is in excellent agreement
with the activation energy for bulk diffusion of carbon
in Hadfield steel (Fig. 21).
Work hardening was high and remained nearly
constant throughout the dynamic strain aging range
and decreased at temperatures above and below this
range (Fig. 8). At temperatures above 400 ~ the initial
rate of work hardening was high (Fig. 7) because of the
presence of carbides.
In the present study, no strain-induced transforma-
tion of austenite of Hadfield composition to a or c
martensite was observed by light or electron microscopy
or by MOssbauer spectroscopy, in agreement with
results obtained by a n u m b e r of previous workers. 6-;~
B. Mechanism of Work Hardening
As a result of the rapid pinning of dislocations in
Hadfield steel during plastic deformation within the
temperature range of normal usage, work hardening is
high. This pinning is a diffusion-controlled process with
an activation energy m u c h below that for bulk diffusion
of carbon in this steel. The only process that would
appear to satisfy these requirements is short-range
diffusion of carbon within the cores of dislocations. In
his review of core diffusion in fcc metals, Balluffi 49
concluded that the activation energy for diffusion
within the core was 0.4 to 0.7 of the activation energy
for bulk diffusion. The activation energy for the onset
of serrations is about 0.6 to 0.7 of the activation energy
for bulk diffusion of carbon in Hadfield steel. Esti-
mations of the relative mobilities of substitutional
solutes in dislocation cores and in the undisturbed
lattice of bcc iron have shown that serrations appeared
at temperatures where the solute was mobile in the core
but immobile in the lattice. 36 Similar calculations from
our data indicate that a few j u m p s of carbon atoms can
occur in a dislocation core in the time between serra-
tions, even at - 10 ~

7 5 6 - - V O L U M E 12A, MAY 1981 M E T A L L U R G I C A L TRANSACTIONS A

 1.2-- ' ~-

1 . C - - 1.0 _

Z
s 0.8- 0.8
Co P.
03
0.G 0.6
Z
<
0.4 0.4
IS=-0. 064 mm/s

0.2 0.2 OS= O. 6 3 m m / s

Fig. 23--(a) Room temperature M0ssbauer
spectra of Hadfield steel. (a) as quenched; 0O I 0.0 I I I I
after 20 pct strain at 24 ~ (b), 190 ~ (c), 9 -IO -5 0 5 I0 -tO -5 0 5 10
and 350 ~ (d). 9 Data, --fit. IS = isomer VELOCITY, m m / s VELOCITY, mm/s
shift of central peak with respect to t~-iron. (a) (b)
QS = quadrupole splitting. Estimated error
in IS = • m m / s . Estimated error In 1.2 1.2
QS = _+0.021 m m / s .
1.0 1.0 _~

0.8 0.
If)
If)
M
E
0.6- 0.6
(13
Z
<
IE 0.4 0.4
I-- I S = - O . 06 Omm/s I S = - 0 . 068 mm/s

0.2 OS= O. 65 mm/s 0.2 QS= 0 . 6 4 m i n i s

O. I I I I
-t0 -5 0 5 IO O. _110 -5 0 5 tO
VELOCITY, mm/s VELOCITY, mm/s
(c) (d)

- ~ On the unrealistic assumption of a uniform dispersion

of manganese and carbon atoms in a steel containing 12
1200 6 0 0 5 0 0 100 0-25
-5 1 [ 1 1 II at. pct manganese and 5 at pct carbon, the mean
mocrodiffusion) distance between manganese atoms on a volume basis
would be 0.46 n m and between carbon atoms 0.62 nm.
Thus, within one Burgers vector of the center of a
dislocation there is an ample supply of solutes to serve
as pinning agents.
In fcc alloys, internal friction peaks are attributed to
Ke end point defect pairs. Ke and W a n g 46 and K a n d a r p a and
-15
Wong. internel friction
Spretnak 5~ concluded that the internal friction peak in
\ a2 austenitic manganese steel arose from stress-induced
\ Temp, T = 12D ordering of carbon atoms arising from the distortion of
o \ 200"C I sec. octahedral sites by neighboring manganese atoms. Such
50"C 68 see. ordering can occur more readily within dislocation
\ 100eC 7.6 hrs.
cores than in the elastically strained lattice.
\ 24~ 109 yrs.
Thermodynamic data 5~ for Fe-Mn-C alloys show that
"25
\ manganese decreases moderately the activity of carbon
\ in austenite, indicating an attractive force between
\ manganese and carbon which is necessary to produce
\ the point defect pairs which pin dislocations. The
manganese-carbon combination is unique in that their
interaction energy is appreciable but not so high that
-35 I I I I I carbides are quickly precipitated. Thus, large concen-
0 I 2 5 4 5
trations of both can be held in supersaturated solid
I O 0 0 / T , K"1 solution in austenite. These large concentrations have
Fig. 24--Temperature dependence of the diffusivity of carbon in an important practical effect. It is generally noted that
Hadfield steel (r is the time for one j u m p of a carbon atom). DSA reduces ductility, as measured by uniform elon-

M E T A L L U R G I C A L TRANSACTIONS A VOLUME 12A, MAY 1981--757

gation. 52 Baird and Jamieson 53 proposed that the early
onset of necking during extension in the DSA range is
caused by local exhaustion of interstitial solutes so that
the supply becomes insufficient to lock mobile dislo-
cations, thus providing a site for localized plastic flow
and necking. Because of the high concentrations of
carbon and manganese in Hadfield steel, this exhaus-
tion cannot occur and the result is a high work-
hardening rate, high uniform elongation and a tough
alloy.
Work hardening of Hadfield steel decreases at tem-
peratures above and below the DSA range. At low
temperature, ~ - 25~ or at high strain rates at higher
temperatures, the carbon atoms are immobile both in
the dislocation cores and in the lattice so pinning does
not occur. It is tempting to speculate that at temper-
atures and strain rates at which serrations disappear the
carbon atoms can diffuse with the gliding dislocations,
as might be indicated by the similarity of the activation
energies for bulk diffusion of carbon and for the
termination of serrations, Fig. 6. Unfortunately, this
encounters the same difficulty noted previously36--an
unreasonably high density of mobile dislocations is
required. The mechanism of the termination of serra-
tions remains obscure.
Both twinning and DSA were observed in the tem-
perature range -25 ~ to 225 ~ in which work harden-
ing was high and constant, but the density of twins
decreased monotonically as the temperature was raised.
High work hardening persisted at temperatures above
225 ~ in the absence of twinning, but in the presence
of DSA. Work hardening decreased when flow became
smooth at temperatures below - 25 ~ even though
twinning was profuse. We conclude that twinning
cannot be the principal cause of rapid work hardening
in this alloy.
C. Recommendation for Increasing the Wear
Resistance of Hadfield Steel
Hadfield steel performs best under conditions of
gouging or battering wear, the conditions existing in jaw
or cone crushers. Diesburg and Borik 4 showed that the
gouging wear ratio of Hadfield steel--the weight loss of
the test specimen divided by the weight loss of a
reference specimen of "T-l Type A" steel, 260 HB
--decreased with increasing carbon content. Although
it is known that the gouging wear resistance of Hadfield
steel can be improved by increasing the carbon content,
there is a practical upper limit to the carbon content, set
by the need to minimize carbide precipitation during
quenching from the austenitizing temperature. Such
precipitation decreases the toughness of the alloy. To
increase the concentration of carbon in solution in
Fe-Mn austenite, it may be necessary to reduce the
activity of carbon by the addition of another substitu-
tional solute.
CONCLUSIONS
1) Dynamic strain aging is the principal cause of
work hardening in Hadfield steel. The carbon members
of C-Mn couples reorient in the cores of dislocations,
758--VOLUME 12A, MAY 1981
thereby locking the dislocations. This then leads to a
high dislocation density for a given strain.
2) Twinning is not a major factor contributing to
rapid work hardening of Hadfield steel.
3) No strain-induced transformations were observed
in Fe-Mn-C alloys of Hadfield composition.
4) The service performance of Hadfield manganese
steel may be improved by increasing the carbon content
in solution in austenite, which may be accomplished by
adding a second substitutional solute that further de-
creases the activity of carbon in austenite.
ACKNOWLEDGMENT
We are grateful to Professor J. Datsko for advice and
assistance in machining Hadfield steel, to Professor
D. Vincent for his continued interest and valuable
advice in Mossbauer spectroscopy, to Mr. Y. Hong for
assistance in light microscopy, to Mr. L. F. Allard for
assistance in electron microscopy, to Mr. R. J. Sober of
the U.S. Steel Research Laboratory for his advice on
high-temperature strain measurements and to
Mr. R. Schoone, also of the U. S. Steel Research
Laboratory, for his advice on preparation of thin foils
for electron microscopy. The support of the National
Science Foundation, under Grant No. DMR 77-02000,
is greatly appreciated.
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