Int. J. Pres. Ves.

& Piping 58 (1994) 231-247

An appraisal of certain factors which

influence toughness restoration
(de-embrittlement) in some temper embrittled
low alloy steels
J. H. Bulloch
Electricity Supply Board, Head Office, Dublin 2, Republic of Ireland

(Received 15 May 1993; accepted 4 June 1993)

This paper describes and assesses the various factors which affect the degree of
de-embrittlement, A F A T T , of a selection of embrittled low alloy steels after a
simple tempering heat treatment. It has been shown that the degree of
de-embrittlement was variable and could be divided into two separate sets of
data depending upon the embrittled fracture mode characteristics. The steels
which failed in a wholly intergranular manner, predominantly the nickel-
containing steels, exhibited large A F A T F values of between 150 and 250°C.
However, the non-nickel-containing steels, viz. the C r - M o and C r - M o - V
steels, fractured in a mixed mode fashion, which comprised intergranular
failure and transgranular cleavage, and exhibited much lower levels of
toughness rejuvenation. When the raw data were corrected for grain size
effects it was clear that the bulk phosphorus content of the steels significantly
influenced the extent of de-embrittlement. Also when the de-embrittlement
data were portrayed in terms of the embrittled condition toughness,
FATI'EMB, and corrected to a constant composition and grain size, it was
observed that the degree of toughness restoration, A F A T F , was insensitive to
FA'ITEMa.

INTRODUCTION isothermally held or slowly cooled through the

Since the time when intergranular fractures of
World War I gun barrels ~ were reported a
significant research effort has been focused on
studying the influence of segregation and
toughness losses on the ductile-brittle transition
temperature, DBTT, and on relating grain
boundary residual element levels to low energy
failure in alloy steels. Indeed the most widely
studied aspect of segregation-induced embrittle-
ment is reverse temper embrittlement, RTE,
which is tantamount to a rather chronic problem
in iron-based engineering alloys.
Reverse temper embrittlement is identified by
a marked decrease in the Charpy V-notch
toughness (see Fig. 1), when alloy steels are
Int. J. Pres. Ves. & Piping 0308-0161/94/$07-00
© 1994 Elsevier Science Limited.
231
temperature range 300-600°C. RTE can seriously
affect the integrity of (i) various engineering
parts that are subjected to temperatures within
this critical range and (ii) heavy-section parts,
such as turbine rotors or large pressure vessels,
which are subsequently slowly cooled through
this range after fabrication and heat treatment.
A significant proportion of RTE research
activities have studied the relation of composition
and heat treatment to the degree of embrittle-
ment or increase in DBTT or fracture ap-
pearance transition temperature, FATT. Indeed,
as early as four decades ago, the research results
indicated that residual or tramp metalloid
elements and alloying elements were both
involved in promoting RTE. Balajiva and
others 2'3 have reported that the presence of
specific metalloid impurities such as tin, phos-
phorus, antimony and arsenic was a necessary
232 J. H. Bulloch
100
TRANSITION
TEMPERATURE
REGION
........
50
BRITTLE
FRACTURE
% FIBROSITY
REGION
/
/
/
/
f
I
....-I
TRANSITION
TEMPERATURE
FATT
TEST TEMPERATURE
Fig. 1. Relationship between temperature and fracture appearance determined by the Charpy V-notch test.
requirement for R T E to occur in N i - C r steels.
Indeed the deleterious influence of phosphorus is
widely accepted; Jolivet and Vidal 4 have reported
that phosphorus levels as low 0-008% increased
the propensity towards RTE.
Opel 5 demonstrated that the degree of
embrittlement in 3½% N C M V steels was greater
at 0.023% P than at 0.007% P, the effects being
greater at slower heat treatment cooling rates. It
has been reported that the degree of R T E
increased in a linear fashion with phosphorus
content, while Viswanathan 6 reported a direct
relationship between the degree of embrittlement
and the grain boundary phosphorus concentra-
tion. Newhouse and Holtz 7 concluded that the
influence of phosphorus in 3½% N C M V steels is
dependent upon some interaction involving the
chromium and nickel levels.
Over two decades ago Low et al. 8 reported the
important role played by purpose alloy additions
inasmuch that they demonstrated that (i) R T E
could be induced in N i - C r steels by impurity
doping but not in plain carbon steels, (ii) the
presence of nickel and chromium increased the
degree of R T E , and (iii) the addition of
molybdenum dramatically reduced the suscep-
tibility of N i - C r steels to RTE. The latter
f l
f
f
/
/
/
/
DUCTILE
/ FRACIURE
REGION
/
j
/'
/
/
findings support the earlier results reported by
Greaves and Jones. 9
The embrittlement of 3½% N C M V steels has
been shown '°''1 to increase with increasing
manganese levels. Indeed the susceptibility to
RTE appeared to be extremely low if the
manganese and silicon levels were maintained
below approximately 0-3% and 0.1% respec-
tively. Powers '2 has reported that vanadium
additions enhanced the beneficial effects of
molybdenum while, almost a decade later,
Comon et al. 13 confirmed the significant benefit
from increasing the vanadium levels in 3½ N C M V
steels.
The reversible characteristics of this particular
embrittlement p h e n o m e n o n can be demonstrated
by heat treating, followed by fast cooling through
the temperature range 600 to 300°C.
The effects of the structural parameter, i.e.
grain size, on R T E were initially reported some
four decades ago when Woodvine '4 showed a
grain size influence on the primary embrittlement
rates, while other workers reported that an
increase in the prior austenite grain size in-
creased the maximum degree of embrittle-
ment. ~5"16 The deleterious influence of enlarged
grain sizes in bainitic microstructures has also
 Toughness restoration in temper embrittled steels
been observed by Tanaka et al. 17 Basically it has
been suggested that the grain size effects on R T E
are due to two separate effects, viz. (i) the effect
of grain size on the yield and fracture stresses in
steels, and (ii) the influence of grain size on the
extent of grain boundary segregation of the
residual impurity elements such as P, Sn, As and
Sb.
About 40 years ago it was demonstrated that
extended tempering could reduce the degree of
embrittlement which subsequently occurred when
steels were isothermally held, and Rosenstein
showed that in a 5% N C M V steel the effects of
R T E were exacerbated by strain and that it was
irrelevant whether the strain was induced by
plastic deformation at ambient temperatures or
through creep processes at elevated service
temperatures. 1 .
The production of electrical power essentially
involved the use of large, sometimes highly
stressed, engineering structures at elevated
service temperatures. One such structure or
component is a steam turbine which contains a
rotor forging and numerous large bolts. The cost
of a new set of turbine bolts is significant and, as
such, any heat treatment which can de-embrittle
or restore their toughness properties after a
specific period of service is important and can
represent an attractive cost saving exercise. Such
heat treatments effectively exploit the reversible
nature of the R T E p h e n o m e n o n in an effort to
I00
80
60
%
F IBROSITY
m
40
20
I I
-200 -I00
Fig. 2. Charpy transition curves for a selection of embrittled low alloy steels from the literature.
233
restore or rejuvenate the toughness properties of
selected engineering components.
The present paper describes a brief review of a
selection of de-embrittlement studies which have
been reported in the literature and specifically
concentrates on the factors that dictate the extent
of toughness rejuvenation in a selection of low
alloy steels.
REPORTED DE-EMBRITI'LEMENT
STUDIES
For about the last two decades a n u m b e r of
studies, dealing with the de-embrittlement of a
range of low alloy steels that have suffered
reverse temper embrittlement, have been re-
ported in the literature. Reverse t e m p e r embrit-
tlement in these particular studies has occurred
either through exposure to elevated temperatures
whilst in service or artificially through step-
cooling or isothermal heat treatment procedures.
A selection of Charpy transition curves, in terms
of fracture appearance, from a range of
embrittled steels is given in Fig. 2. The steels
utilised in this selection included 2"CrlMo,
Ni-Cr, CrMoV and a selection of C r M o V rotor
s t e e l s , m-24 From Fig. 2 it is evident that the
fracture appearance transition temperatures,
FAT-F's, varied from about -100°C in the case of
the very low phosphorus containing steels to
//
/
• REF 2~
I I I
0 +i00 +200 +300 +400
TEST TEMPERATURE (°C)
234
i00
80
60
%
FIBROSIIY 40
20
I I
-200 -100
TEST TEMPERATURE
Fig. 3. Charpy transition curves for a selection of de-embrittled low alloy steels from the literature.
between 0°C and +280°C for the various steels
with normal commercial phosphorus contents of
0.08% to 0-025%. The wide range of embrittled
FATI', FAT-FEMB, data most probably results
from the various (i) grain sizes a n d / o r microstr-
uctures and (ii) alloy compositions, especially
phosphorus content, from the different studies.
The subsequent de-embrittled FAq-T results,
FA'FI'DE.EMB, from the numerous reported
studies are illustrated in Fig. 3. From this figure it
can be seen that the FA'I"FDE_EM B results (i)
exhibited less scatter than the embrittled data
and (ii) showed FAT'I'DE_EMB values that varied
between - 7 0 ° C and +170°C for steels that
contain typical commercial steel phosphorus
levels. The de-embrittlement treatment con-
sidered in the majority of the reported studies
was a simple tempering treatment; however, two
instances of an austenitising and tempering
de-embrittlement treatment were also assessed.
From Figs 2 and 3 it is clear that, on average, the
de-embrittlement treatment reduced the FATI"
level by about 70-100°C. Essentially
FATI'EMB - FATTDE-EMB = AFATT
which defines the extent of de-embrittlement or
toughness restoration imparted by the de-
embrittlement heat treatment.
The extent of de-embrittlement, A F A T I ' , was
plotted as a function of bulk phosphorus content
of the various steels 19-29 and is shown in Fig. 4.
From this figure it is evident that, although the
J. H. BuUoch
I I I
0 +100 +200
(oF)
results show a large amount of scatter, the degree
of de-embrittlement, reflected by the magnitude
of A F A T r , increased with increasing phosphorus
level. Further inspection of the results indicated
the existence of two discrete data sets, viz. (i)
those results at A F A T r values above 100°C
which exhibited little influence of phosphorus
level, and (ii) much lower A F A T T results,
typically below 70°C, which portrayed a sig-
nificant and consistent influence of phosphorus
level on the AFATI" value of the lower data set
which could be adequately expressed by the
following equation:
AFAq-T (°C) = 370x,/P (2)
This is in good agreement with that recently
reported by Bulloch and Hickey. 29
Another manner of showing the effects of
de-embrittlement on the various original or 'raw'
reported data was to exhibit AFAq"-F as a
function of the embrittlement FAq-T values,
FAT-FEMB (see Fig. 5). From this figure it is
apparent that the extent of toughness restoration,
AFATI', was significantly influenced by the level
(1) of embrittlement FATTEMB induced during
service or artificially by heat treatment. Again
two separate data sets are apparent and the lower
set of results can be generally described by the
following expression:
A F A T T (°C) = 0"33(FAq~EMB) + 20 (3)
From Figs 4 and 5 it is evident that the data
 / LEGEND 235
/
• REF 19
/
V / o REF 20
i • • REF 21
/ • A REF 22

= <> / / • REF 23
150 / • REF 24
0 @ REF 25
// • • ~ REF 26

/ II [] REF 27
~ REF 27
/ 0 REF 2B
/
i00 V REF 29
/
/ MAXIMUM EXTENT Q
OF DE-EMBRITTLEMENT
/
&FATT MAX.
AFATT /
(°C)

/ 0
/
/ • [][] [] AFAIT = }70 ~ P

/ i/ • [] [] [][]
l t I i
0 0.01 0.02 0.03 0.04

% BULK PHOSPHORUS

Fig. 4. Relationship between extent of de-embrittlement, A F A T r , and bulk phosphorus levels for a selection of low alloy
steels.

200
LEGEND

AS FIGURE 4
v 4 • /
/,
<>
/
150
/
/
/

v / /
1oo - / /
/ []
AFATT / /
/ /
(°c) • I I
• / A /

so /• • /
/ • /

/• $ / /mm r.
r'm m
/ [] []
o /
/
l l l I I
-I00 0 +100 +200 +)00

FATTEMB (°C)

Fig. 5. Relationship between extent of de-embrittlement, AFATI', and embrittled toughness condition, FAT'FEMB, for a
selection of low alloy steels.
236 J. H. Bulloch

scatter is large and most probably is the result of
differing compositional and microstructural fac-
tors which affect both the intrinsic toughness,
FATT,NT, which is controlled by microstructural
factors such as grain size, grain boundary carbide
thickness and intergranular precipitates, and the
extrinsic toughness, FATTEMT, which is essen-
tially dictated by reverse temper embrittlement
or grain boundary segregation effects. Essentially
the real toughness property, F A T T R E A L , of a
steel is the summation of the intrinsic and
extrinsic toughness components, viz.
F A T T R E A L = F A T T I N T -'f- F A T T E x T
In an effort to identify the true nature of the
AFAT]" component, the separate influences of
microstructure and composition on the intrinsic
toughness and the loss to toughness process, i.e.
RTE effects, need to be considered. Such
considerations, which should reduce the data
scatter, will now be assessed.
FACTORS THAT INFLUENCE
TOUGHNESS PROPERTIES IN LOW
ALLOY STEELS
Composition effects on toughness properties
The influence of phosphorus on the toughness
properties of a selection of various steels, in both
the embrittled and non-embrittled condition, are
illustrated in Fig. 6. From this figure it can be
seen that the data from Viswanathan and Gehl, 3°
Gould '(' and other C r M o V steel s t u d i e s 27'3L32
exhibited good agreement in the embrittled
(4) condition. Indeed the toughness vectors for the
embrittled steels can be described by the
following expressions:
(i) Viswanathan & Gehl: TM
FATTEMB(°C) = I00 + 7550(%P) (5)
(ii) Gould, 3½% N C M V steel: '('
FATTEMB(°C) = 45 + 6000(%P) (6)

+4O0
- .,¢
REF 2 7 , 3 1 , 3 7 ~ - x
REF ~o J scatter BAmD,~.,~--'~x'..~
SCATTER BAND ,~ / / ~ ~ v

+300

+ 201

FATT
(oc)

+I00

REF 33
(NON-EMBRITTLED STEELS)
-I00

I I I I
0.01 0.02 0.03 0.04

,~; BULK PHOSPHORUS

Fig. 6. Relationship between Charpy toughness, FATr, for embrittled and non-embrittled steels, and bulk phosphorus level
for low alloy steels from the literature.
 Toughness restoration in temper embrittled steels 237

+250

+200 LOATA J

+150

FATT
(°C)

+I00

+50

ROTDR STEEL, REF 36

AND BOLl STEEL,
REF. 35

-50 I I I I

0.1 0.2 0.3 0.4

P/FE PEAKHEIGHT RATIO

Fig. 7. Influence of phosphorus grain boundary segregation on the embrittled toughness of a range of Cr-Mo-V rotor and bolt
low alloy steels.

(iii) CrMoV s t e e l : 27"31"32 indicated that the FATI" in a series of N i - C r

FATTEMa(°C) = 8100(%P)
Also shown in Fig. 6 are the non-embrittled data
for a 2¼CrlMo steel reported by Dumoulin et
al. 33 In this case the influence of phosphorus on
the FATI'NoN-EMB was significantly less than is
shown for embrittled steels and could be
described by the following equation:
FATTNoN_EM.(°C) = --75 + 2200(%P)
The embrittling influence of phosphorus is the
result of this particular element diffusing to grain
boundary sites causing localised segregation or
concentration effects. Viswanathan has shown
that the phosphorus is confined to a width of 0.5
to 1.0nm and the extent of phosphorus
segregation is measured in fractions of a
monolayer; a segregation level of 0.1 monolayers
represents a fairly high phosphorus concentration
equivalent to around 5 wt% in the vicinity of the
grain boundaries. This particular study also
steels was directly related to the phosphorus
(7)
concentration at grain boundary phosphorus
segregation measured as a ratio of phosphorus to
iron peaks from auger spectra; see Fig. 7.
In this figure it is evident that both data sets,
i.e., the rotor steel data reported by Kadoya et
at. 34 and the CrMoV bolt steel 35 and C r M o V
rotor steel 36 data, exhibited a linear increase in
(8) the fracture appearance transition temperature,
FATF, with increasing degree of grain boundary
phosphorus segregation. A n o t h e r set of results
recently reported by Hickey and Bulloch 37
illustrated the powerful influence that grain
boundary phosphorus content (in terms of
fractions of a phosphorus monolayer) exerted on
the room temperature Charpy toughness pro-
perties of a range of low alloy rotor and bolt
steels: see Fig. 8. A further recent study
indicated that noticeable embrittlement, i.e.
partial effects, occurred in a 1-3% Cr, 0.8% Mo,
0.3% V bolt steel when the phosphorus level
238
0.4
0.3 mm
FRACTION
PHOSPHORUS
MONOLAYER
• •
0.2 • •
• •
o.1
Fig. 8. Relationship between grain boundary phosphorus segregation and room temperature Charpy energy of a selection of
low alloy steels.
approached 0.05 to 0-07 monolayers. 35 This study
showed good agreement with the trends illustra-
ted in Fig. 8.
As well as phosphorus the metal tramp
element tin and alloying elements chormium and
nickel are known to affect the propensity of a
steel to reverse temper embrittlement. To
account for such composition effects a parameter,
known as the J-Factor, has been proposed and it
has the form 24
J-factor = (P + Sn)(Si + Mn) × 104
The effects of the J-Factor on the degree of
de-embrittlement, AFAqT, from the present
literature survey and other sources are given in
Fig. 9. Two discrete data sets are evident and,
while the high AFATT and low J-Factor agree
well with the trends reported by Viswanathan
and Gehl, 3° the lower AFAT-F data set exhibited
good agreement with those reported by Murak-
ami et al. 3s for commercial steels, and the degree
of de-embrittlement could be described by the
J. H. Bulloch
•
•
• •
• •
• Ii
I I I I
20 40 60 8o
ROOM IEMPERAIUR[ CHARPY ENERGY
(J)
expression
AFATT = 0.143(J-Factor) (9)
Microstructural effects on toughness properties
In general terms the microstructure of the
majority of the low alloy creep resistant steels
dealt with in the present investigation was
tempered upper bainite. This consisted of a
matrix of acicular ferrite containing coarse
intergranular and grain boundary carbides with
the structural parameter being the prior austenite
grain size. The intrinsic toughness, FATTINT, of a
low alloy steel is mainly dependent upon average
grain size and grain boundary carbide size or
thickness, while the intergranular precipitates
will generally be in the overaged condition and
offer little contribution to the strength properties
and hence toughness properties.
The influence of average grain size, d, on the
toughness properties of N i - C r steel has been
 Toughness restoration in temper embrittled steels
150
I00
AFATI
(oc)
50
0
200 400
-J-FACTOR
Fig. 9. Effect of J-Factor on degree of de-embrittlement in low alloy steels. Symbols as in Fig. 4.
reported by Eyre et al. 3 9 The effect of grain size,
in terms of d -la where d is in mm, for this steel
in the (i) embrittled, (ii) non-embrittled and (iii)
pure (low phosphorus) conditions is given in Fig.
10. From this figure it is evident that the trends
were bilinear in nature with FATI" increasing
with increasing average grain size, with the
greater effects of grain size on FATT being
observed at grain sizes above about 5 0 # m .
Indeed the toughness vectors for the embrittled
and non-embrittled steels averaged around 22°C
per d - l a and 9°C per d -u2 in the grain size ranges
greater than 5 0 ~ m and less than 5 0 # m
respectively. In the case of the pure (low
phosphorus) steel the influence of grain size on
FATF values was significantly reduced.
Pickering*~ has reported grain size effects on
toughness for steels exhibiting bainitic microstr-
uctures with tensile strengths within the range
700-850 MPa, which exhibited good agreement
with those reported by Eyre et al., 3 9 viz. 26°C per
d-I/2.
The effect of grain size on the degree of
de-embrittlement imparted by a simple temper-
ing heat treatment, AFAT£, is shown in Fig. 11.
This particular figure portrays the marked
239
/
/
@
3 REF. 38
s*
f
f
I I I
600 800 1000 1200
influence that the average grain size, in terms of
d -la, exerted on the degree of toughness
restoration. Decreasing the grain size caused a
significant increase in the level of AFATT and
the effect could be described by the expression
AFATI" (°C) = 225 - 22-4d - ' a (10)
Interestingly the magnitude of the grain size
effect, i.e. the constant 22-4 in this equation,
exhibited excellent commonality with the tough-
ness observed from the work reported by Eyre et
al. 39
Another parameter which can strongly in-
fluence the toughness properties of low alloy
bainitic steels is the presence of carbide located
at prior austenite grain boundaries. Earlier
Lindley et al. 4~ reported that the presence of
grain boundary carbides could break through
fibre loading and induce microcracks in the
surrounding ferritic matrix; such microcracks
could act as initiators of brittle fracture and
hence seriously reduce the toughness properties.
Mintz 42 later showed that even thin grain
boundary carbide, typically below l # m in
thickness, could be deleterious to the F A T r
values of C - M n steels.
240 +l 2o -

+80

+40

FATT
(°C)
NON-EMBRIITLED
STEEL

-40

-80
PURE STEEL

I i i l I I I
1 2 3 4 5 6 7

GRAIN SIZE, d- ½, (mm) -½

Fig. 1O. Relationship between FATF and grain size for a low alloy steel in various conditions.

m
200
%.
\
\ •
\

• 0 \ .% AFATT = 225-224 d-½

150 --
\
\
•

\\ m\ [] ~ \\\
I00 --

"~. ~ %'%.
z~F ATT

(oc) A~
\ @ • \
50 \
\

LEGEND
AS FIGURE 4.
t I I I
2 4 6 8
GRAIN SIZE, d-½, (mm) -½

Fig. 11. Relationship between degree of embrittlement, AFATT, and grain size for a range of de-embrittled low alloy steels.
 Toughness restoration in temper embrittled steels
Fig. 12. General view of presence of discrete grain
boundary carbides in an embrittled C r - M o - V bolt steel.
Original magnification x8500.
The nature of grain boundary carbides
prevalent in a CrMoV bolt steel is shown in Fig.
12. Recently Bulloch and Hickey 35 have reported
the relationship between the average grain
boundary carbide thickness, t, and the average
grain size, and this is illustrated in Fig. 13. From
this figure it is evident that the average carbide
thickness, t, increased at larger grain sizes.
Indeed at fine grain sizes of d = 10/zm,
t = 0 . 2 / u m , while at d = 6 0 ~ u m , t~-0.5/~m.
Recently Petch 43 demonstrated that the brittle
cleavage fracture stress, of, of low alloy steels
was dependent upon both the carbide thickness
and grain size and reported the influence of
carbide thickness on FATT at various grain sizes.
This study showed that the toughness properties
or FAT-F values were significantly affected by
0.6
0.4
GRAIN
BOUNDARY
CARBIDE
THICKNESS
(pro) 0.2
I I I steel data exhibited AFATI" values that were
0 20 40 60
GRAIN SIZE (pm)
Fig. 13. Relationship between grain size and grain boundary
carbide thickness for a C r - M o - V bolt steel.
241
small changes in t at fine grain sizes. However, at
intermediate to coarse grain sizes, similar small
differences in t exhibited little or no effect on
FATF. Essentially at fine grain sizes of around
10/~m an average change in the carbide thickness
value of - 0 . 2 #m increased FATT by around
40°C. However, in the case of the present low
alloy rotor and bolt steels where the grain size
averaged about 50/um (see Fig. 11), changes in
the average carbide thickness would have to
approach 1 ~m before it affected the FATT level.
In general terms this implies that any changes in
carbide thickness that could be caused by a
tempering de-embrittlement heat treatment
would have no effect on F A T F levels for the
present low alloy steel acicular ferrite + carbide
microstructures. As such any changes in the
intrinsic toughness can be simply related to grain
size.
DISCUSSION A N D CONCLUSIONS
The degree of toughness restoration induced by
subjecting a selection of embrittled low alloy
steels to a simple heat treatment was shown to be
influenced by the bulk phosphorus level; see Fig.
4. This figure illustrates that the data can be split
into two separate sets, viz. (i) a CrMoV and
CrMo steels set which showed that the influences
of phosphorus on AFATT could be expressed by
eqn (2), and (ii) a predominantly 4% Ni-
containing steels set which exhibited little
influence of phosphorus level and high AFATI"
levels of around 150°C. From Fig. 6 the influence
of phosphorus content on the toughness of
embrittled and non-embrittled steel can be
expressed by eqns (5) and (6) respectively. From
these data it is evident that the maxima degree of
de-embrittlement would be
AFATI~MAX = F A T T E M B -- FATTNoN_EM a (11)
and from eqns (7) and (8),
AFATTMAx -- 5900(%P) + 75 (12)
This relationship is shown in Fig. 4 and it can be
seen that essentially (a) the CrMoV and CrMo
dramatically smaller than those levels which
could practically be realised, and (b) the
predominantly 4% Ni-containing steel results
exhibited AFAT-F levels that showed good
242 J. H. Bulloch

/
/

- /
200 MAXIMUM EXTENT
/ ~ DE-EMBRITTLEMENT
/ AFATT MAX.
/

150

FATT
(%)
~ I~ O / • •

i00 , . /. /
/ " / / / / / /
• "/ / /
& / // o
/ a / /"
/ ~/ /

/ ml I I I
0.01 0.02 0.03 0.04

% BULK PHOSPHORUS

Fig. 14. Relationship between extent of de-embrittlement, FATT, and bulk phosphorus level for a series of low alloy steels.
Data corrected to a constant grain size of 50 #m. Symbols as in Fig. 4.

agreement with the maximum levels predicted by
eqn (12).
The data portrayed in Fig. 4 were 'raw'
inasmuch that composition and microstructure
variations were implicit and could be the cause of
some scatter in the results. In an effort to
ascertain the real influence that phosphorus
exerted on A F A T F the data in Fig. 6 were
corrected to a constant grain size of 50 ~m, i.e.
d -1/2 = 4.5 mm 1/2, utilising the vector given by eqn
(10) from Fig. 11, and the corrected data are
exhibited in Fig. 14. From this figure it can be
seen that the influence of phosphorus on the
extent of de-embrittlement, AFATF, was de-
pendent upon the particular low alloy steel type.
Indeed the real effects of bulk phosphorus level
on the degree of de-embrittlement can be
described as follows:
for non-Ni-containing CrMoV and CrMo steels:
AFATI'(°C) = 3570(%P)
and for Ni-containing steels (4% Ni):
AFATT = AFAT-FMAX= 5900(%P) (14)
as given approximately by eqn (12).
The Ni-containing steel data group in Fig. 14
comprised one result from a CrMoV steel and
further clarification of the differing influences of
phosphorus on the level of AFAT-F can be
obtained if the fractrographic details of the two
Ni-containing steel types in the embrittled
condition are examined. The fractographic
details of one study concerning an embrittled
CrMoV bolt steel 44 are given in Fig. 15. In this
instance the fracture mode was mixed and
contained approximately transgranular cleavage
(70%) and intergranular failure facets (30%).
Also from a detailed view of an intergranular
facet (see Fig. 16), on examination of the
majority of the studies reported in the literature,
it was established that the non-Ni-containing
steels ( C r - M o and CrMoV) exhibited similar
(13) details of the grain boundary fracture surface;
 Toughness restoration in temper embrittled steels
Fig. 15. Fractographic details of an embrittled Cr-Mo-V
bolt steel. Note that the fracture mode is mixed and consists
of intergranular failure (mainly lower half of figure) and
transgranular cleavage (mainly upper half of figure).
Original magnification x700.
thus mixed m o d e fracture and rough grain
b o u n d a r y surfaces were c o m m o n fractographic
featues observed in the lower data set of Fig. 14.
Fig. 16. Detailed view of an intergranular failure facet in an
embrittled Cr-Mo-V steel bolt. Note roughness on
intergranular fracture surface which exhibited some measure
of ductility. Original magnification x2000.
243
Fig. 17. Fractographic details of an embrittled Cr-Mo-V
steel bolt that exhibited the maximum extent of
de-embrittlement. Note that fracture mode is almost 100%
intergranular failure. Original magnification x800.
In the case of the Ni-containing steels data set it
was evident, upon inspection of the r e p o r t e d
literature, that the embrittled failure features
consisted of smooth intergranular failure which
essentially covered the whole fracture surface
(Fig. 17). Indeed the only C r M o V steel data
point, which resided in the high A F A T T data set
from Fig. 14, exhibited similar fractographic
features within which the individual grain
surfaces were smooth in nature.
From the foregoing fractographic observations
it is suggested that the differing response
regarding the influence of bulk phosphorus on
AFATI" largely results from the fracture
response of a reverse t e m p e r embrittled low alloy
steel. Essentially the maximum degree of
de-embrittlement is o b s e r v e d in embrittled low
alloy steels which exhibit 100% smooth inter-
granular failure, while much lower values of
AFATI" which exhibit 100% smooth intergranu-
lar failure, while much lower values of A F A T T
are evidenced in low alloy steels which yielded
mixed rough intergranular and transgranular
244 J. H. Bulloch
cleavage type failure. From a simple fracture
viewpoint such fractographic influences on the
extent of de-embrittlement are consistent inas-
much that, when the de-embrittlement treatment
caused a change from a 100% intergranular
failure to a 100% transgranular failure, the
effects should be greater than those observed
when changing from a 30% intergranular, 70%
transgranular failure to a 100% transgranular
failure, as was the case for the non-Ni-containing
low alloy steels.
Both Viswanathan and Joshi 45 and Yu and
McMahon 46 have observed certain effects in
embrittled CrMoV and C r - M o respectively
which were absent in embrittled steels which
contain significant amounts of nickel. In a similar
way to the observations of the present review,
these studies indicated that the fracture surface
contained mixed amounts of intergranular failure
facets and transgranular cleavage. Also the
extent of intergranular failure was temperature
dependent and attained a maximum at a specific
temperature. Knott and Cottrel147 have dem-
onstrated that the fracture stress, OF, in notched
specimens almost coincides with the stress
required for initial notch tip yielding at low
temperatures. However, as the temperature rises
and the yield strength drops, OF increases until it
exceeds the general yield stress orgy; such effects
are shown schematically in Fig. 18 for the
embrittled and non-embrittled conditions for
Ni-containing CrMo steels. The non-Ni-
containing steels differ from the Ni-containing
steels in a significant manner, i.e. because they
lack the cryogenic properties that Ni imparts to
steels their inherent toughness or resistance to
brittle cleavage fracture is much reduced and as
such the non-embrittled condition is raised to a
higher temperature range. This will have the
effect of narrowing the temperature difference
range between the embrittled and non-embrittled
conditions which can change the type of
failure-mode transition caused by reverse temper
embrittlement. From Fig. 18 it is evident that the
fracture stress curves for cleavage and for
intergranular fracture in an embrittled Ni-
containing steel are wide apart and, as such,
RTE produces a failure transition from rupture
(microvoid coalescence) to total intergranular
fracture at most test temperatures: see Fig. 18(a).
In the case of the non-Ni-containing steels, as
shown in Fig. 18(b), however, the transition is
from cleavage to intergranular failure over a wide
(a) Nz-CrSTEELS
o.
"~- "---'--"-"""- EMBRITTLED
NOMINAL
APPLIED
SfRESS \ (b) Non N t STEELS
\
~ °GY
CL
~ GB
~F
NON- / ~
EMBRITTLED/ J
~ _ / / e~rIttuEO
-.,,,..
~ ~ ~ ~ ~ ~ I Y
TEST TEMPERATURE
Fig. 18. Schematic illustration of fracture stress versus
temperature for Ni-containing and non-Ni-containing steels
in the non-embrittled and embrittled conditions. For
explanation see text.
temperature range, and within the transition
temperature range the energetics of these two
static failure modes are similar and both compete
on an equal basis; hence the occurrence of mixed
failure modes in C r - M o and C r - M o - V steels.
Another manner in which the degree of
de-embrittlement, A F A I T , was portrayed (see
Fig. 5) was to plot A F A T T as a function of the
embrittled toughness, FATTEMB. This figure,
showing the raw or uncorrected data, illustrates
that again two separate data sets, which could be
labelled Ni-containing and non-Ni-containing
steels, were evident. The latter exhibited
significant effects of FAqTEMB o n the degree of
de-embrittlement, while a trend in the former
data set was difficult to assess because of the
small span in the FATFEMB data. When the data
are shown as AFAT-F v e r s u s FAq'TEMB the real
influence of starting embrittled toughness on
A F A T T can be readily assessed because both the
intrinsic toughness (grain size) and extrinsic
toughness (phosphorus content a n d / o r J-Factor)
factors can be corrected to constant values. The
raw or uncorrected data shown in Fig. 5 were
 Toughness restoration in temper embrittled steels 245

250

U
V

lii
200 --

0
[]
vo
150 --

AFATT
(oC)

I0~

/%"

• • 0 ~ A
• • QOI

50- • OI
nl

rl

I I I I
-i00 0 +i00 +200

FATT (°C)
EMB

Fig. 19. Relationship between degree of de-embrittlement, AFATF, and FATTEMBfor low alloy steels corrected to a grain size
of 50/~rn and a composition of 0-02% P and J-Factor = 400. Symbols as in Fig. 4.

corrected to a constant composition, 0.02% P,
and a J-Factor of 400 (using AFATI" = 0.17 J and
FATF~MB = 8100(%P)) and a grain size of 50 ~ m
(using A F A T T = 5°C per d -1~2 and FAT-FEMB =
24°C per d-1/2); and the corrected data,
illustrating the real influence that FATTEMB
exerted on the degree of de-embrittlement, are
shown in Fig. 19. From this figure it is evident
that again two separate data sets existed which
can be distinguished as the higher A F A T T
Ni-containing steel data and the much lower
AFATI" non-Ni-containing steel data. However,
unlike the trends apparent in Fig. 5, the extent of
de-embrittlement, A F A T T , for the C r - M o and
C r - M o - V steels data was insensitive to the
original embrittled toughness, FAT-FEMB, and the
magnitude of AFATI" varied between about 30°C
and 80°C. The mainly Ni-containing steel
AFATI" data, however, exhibited much higher
degrees of de-embrittlement and A F A T T values
varied between 150°C and 250°C.
In terms of fracture surface features it was
established that again the C r - M o and C r - M o - V
steels exhibited mixed intergranular and trans-
granular cleavage failure, while the higher
A F A T T data set exhibited wholly intergranular
failure along prior austenite grain boundaries in
the initial embrittled condition. These data,
however, were with one exception for Ni-
containing steels whose tough intragranular
properties p r o m o t e d failure along weakened
grain boundary locations. The exception was data
246 J. H. Bulloch
for a C r - M o - V steel 2s w h i c h u n l i k e t h e o t h e r
n o n - N i - c o n t a i n i n g steels failed in a c o m p l e t e l y
intergranular manner. The only noticeable
d i f f e r e n c e s b e t w e e n this p a r t i c u l a r steel a n d
o t h e r C r - M o a n d C r - M o - V steels w a s t h a t it did
n o t c o n t a i n a n y silicon o r a l u m i n i u m . A l s o t h e
N i - c o n t a i n i n g steels did n o t c o n t a i n a p p r e c i a b l e
a m o u n t s o f t h e s e p a r t i c u l a r d e - o x i d a t i o n ele-
m e n t s . Silicon h a s b e e n r e p o r t e d to p r o m o t e
phosphorus segregation and hence reverse
t e m p e r e m b r i t t l e m e n t effects. A s such, d u r i n g
the d e - e m b r i t t m e n t h e a t t r e a t m e n t , it is p o s s i b l e
t h a t p h o s p h o r u s diffusion a w a y f r o m g r a i n
b o u n d a r y sites was n o t i n h i b i t e d to t h e s a m e
e x t e n t in low silicon steels t h a n in silicon-killed
steels a n d t h u s m o r e d e - e m b r i t t l e m e n t w a s
realised. A l s o silicon is a fairly g o o d s u b s t i t u -
tional h a r d e n e r w h i c h s h o u l d r e n d e r t h e steel o r
i n t r a g r a n u l a r m a t r i x less t o u g h , t h u s p r o m o t i n g a
m i x e d f r a c t u r e m o d e in t h e e m b r i t t l e d c o n d i t i o n .
A l u m i n i u m a d d i t i o n s a r e k n o w n to i n c r e a s e a
s t e e l ' s r e s i s t a n c e to r e v e r s e t e m p e r e m b r i t t l e m e n t
a n d , as such, a l u m i n i u m - k i l l e d l o w alloy steels
s h o u l d u n d e r g o less e m b r i t t l e m e n t a n d h e n c e
subsequent de-embrittlement after heat treat-
ment.
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