Materials Science and Engineering, 42 (1980) 233 - 244
© Elsevier Sequoia S.A., Lausanne -- Printed in the Netherlands
The Intergranular Fragility Index -- a n E n g i n e e r i n g M a t e r i a l s P a r a m e t e r *
C. LEA, M. P. SEAH and E. D. HONDROS
Division of Chemical Standards, National Physical Laboratory, Teddington (Gt. Britain)
SUMMARY
Residual elements affect the performance
o f engineering alloys through their ability to
concentrate at grain boundaries, and this in
turn may lead to certain forms o f intergranular
failure in various metallurgical situations.
In order to identify the m o s t p o t e n t residu-
als occurring in alloys o f commercial purity,
an evaluation exercise was conducted on a
range o f commercial engineering alloys which
had exhibited various forms o f intergranular
failure in service. The results were assessed
according to several behaviour categories:
high temperature (e.g. creep, stress relief
cracking), low temperature (e.g. temper brittle-
ness) and reaction with the environment
(e.g. intergranular stress corrosion cracking).
For each such distinguishable category there
exists a different hierarchy o f effective
elements.
Here we introduce a generalized engineering
parameter, the fragility index, which allows a
rapid assessment o f the quality o f a steel cast
in relation to the above specific behaviour
categories and in terms o f an assessed domi-
nant impurity equivalent. Thus for the above
behaviour categories this index is expressed as
a tin or phosphorus or copper equivalent
depending on the p h e n o m e n o n . A n o t h e r
engineering parameter, the relative fragility,
forms the basis o f a screening test for identify-
ing the most probable embrittling elements.
These parameters may be derived either from
metallurgical test data or from the appropriate
model presented here which requires only a
knowledge o f the bulk composition and
segregation data.
*Presented at the International Chalmers Sympo-
sium on Surface Problems in Materials Science and
Technology, GSteborg, Sweden, June 11 - 13, 1979.
233
1. INTRODUCTION: RESIDUAL ELEMENTS AND
INTERGRANULAR FRACTURE
Common experience demonstrates that
clean grain boundaries in polycrystalline ma-
terials are intrinsically strong. However,
various forms of intergranular weakness occur
in engineering alloys and these are associated
with the presence of residual elements and
their accumulation at interfaces such as grain
boundaries, cavity surfaces or phase boun-
daries. This has been inferred through indirect
metallurgical observations over many years
and the effects have been studied quantita-
tively through interfacial energy measurements
as an indication of this accumulation or
segregation behaviour. In recent years, with
the development of direct surface analytical
techniques, the segregating species have been
unequivocally identified and located at frac-
ture surfaces. The experimental application of
these new surface spectroscopies to materials
problems involving intergranular weakness has
also stimulated theoretical advances and a
fuller understanding of phenomena relating to
segregation.
Among the available surface analysis tech-
niques, Auger electron spectroscopy (AES)
has proved to be the most useful and produc-
tive for the analysis of segregation. For grain
boundary phenomena, measurements have
been made on fracture surfaces formed in situ
by low temperature impact or tensile failure.
This necessity for fracture in ultrahigh vacuum
is a major disadvantage, especially for the
diagnosis of service failures. Where such a
failure is caused by creep embrittlement or
intergranular corrosion there may be insuf-
ficient low temperature brittleness in the
material to propagate an intergranular failure
within the spectrometer; however, a simulated
in situ creep or corrosion test is generally
impracticable.
234
In an alternative approach, and in order to
circumvent the difficulties in obtaining a
fracture surface for analysis, the more readily
accessible experimental measurements of
segregant accumulation at free surfaces have
been made [1]. Such data are directly relevant
not only to segregation at the inner surfaces
of cavities {such as those formed in creep) but
also as a guide to segregation at a grain boun-
dary in materials in which the boundaries
cannot be exposed for direct analysis [2].
At the National Physical Laboratory, fol-
lowing a long interest in segregation phenom-
ena initially pursued through interfacial energy
measurements and the application of Gibbsian
adsorption thermodynamics, AES has been
used in recent years to evaluate the under-
lying laws of segregation in binary and multi-
c o m p o n e n t systems so that predictions can be
made and remedial measures proposed for
segregation-induced metallurgical problems.
Data have been collated from a wide range of
industrial components, commercial materials
and laboratory melts. In this survey the ele-
ments arsenic, boron, copper, chromium,
molybdenum, nitrogen, nickel, phosphorus,
sulphur, antimony, silicon, tin, tellurium and
zinc have all been reported to be segregated in
steels. By using argon ion sputtering to peel
away successive atomic layers from the sur-
face, with simultaneous recording of Auger
electron spectra, it has been found that these
segregants (except nickel) are localized at the
grain boundary within one or two atomic
depths. (In certain low alloy steels nickel
appears to extend up to 20 monolayers into
the grain interior [3] .)
Clearly then, a wide range of impurities
enrich interfaces significantly from commonly
accepted bulk levels and thus contribute to
embrittlement problems. However, since there
exist various forms of intergranular embrittle-
ment which operate for different systems,
service conditions and temperatures and
which owe their property change to different
basic mechanisms, it is obvious that the above
list of segregating elements cannot apply to
the same degree in all circumstances.
In this paper it is our purpose to categorize
the more important expressions of inter-
granular fragility encountered in practice in
terms of the role of segregating elements and
in a hierarchical order of embrittling suscepti-
bility. This is presented in a general format
that suggests an efficient means of material
specification for both steel production and
the proposed end use of the steel.
2. THE CATEGORIES OF I N T E R G R A N U L A R
FRAGILITY
The segregation levels of impurities at
grain boundaries or cavity surfaces depend
upon the heat treatment and mutual inter-
actions between segregants and alloying ele-
ments. For a given steel or class of steels the
level of segregation can be expressed in terms
of the enrichment factor ~, the ratio between
the concentration of the element at an inter-
face and that in the bulk. However, the various
forms of intergranular failure differ mechan-
istically and thus each element has a different
position in the hierarchy of embrittling sensi-
tivities. Here four important categories of
intergranular failure in low alloy steels are
considered in each of which the segregation
phenomenon plays a dominant role.
2.1. Temper brittleness
Here the grain boundary segregation of
residual elements takes place in close associa-
tion with alloying elements during heat treat-
ment or slow cooling through a particular
temperature range. R o o m temperature grain
boundary cohesion is reduced; this is mani-
fested by an increase in the ductile-to-brittle
transition temperature and the onset of an
intergranular fracture mode.
2.2. Stress relief cracking
This occurs in the heat-affected zone of
weldments in creep-resistant materials either
during welding or during the post-weld stress
relief annealing. Impurities segregate to the
internal surfaces of nucleating grain boundary
cavities and increase the rate of cavity genera-
tion. After annealing, the boundaries fail or
are severely weakened by a high density of
small intergranular cavities.
2.3. Creep embrittlement
By impeding grain boundary mass transport
during typical low strain rate creep around
550 °C, the segregation reduces the growth
rate of grain boundary cavities. This again
leads to a high density of small intergranular
cavities and a reduced rupture ductility.

2.4. Intergranular stress corrosion
In an aggressive environment the chemistry
of the grain boundary delineates a preferential
fracture path through changes in the electro-
chemical potential at the crack front. This
increases the rate of crack growth and reduces
the service life.
3. THE RELATIVE FRAGILITY AND THE FRA-
GILITY INDEX
From the point of view of the material's
integrity we require a useful quantitative
engineering parameter that measures the like-
lihood of the material failing through the
presence of naturally occurring concentrations
of p o t e n t impurity elements. Thus we must
distinguish clearly between the intrinsic em-
brittling power of an element and its ability
to embrittle in practice: the former is a funda-
mental property relating to the effect on
atomic cohesion whereas the latter is a func-
tion of the concentration of the element in
the locality of the fracture event and hence
of the concentration of the element in the
bulk. In general we can define a parameter
¢~(a), the relative fragility of the alloy for the
element i:
~ ( a ) ~ Zi/~(a)S~(a ) (1)
where Xi is the bulk concentration of element
i and ~ ( a ) is its enrichment factor, i.e. the
ratio between the molar fractional concentra-
tion at the interface and the bulk concentra-
tion by weight of the element i for the mate-
rial (a) and appropriate to the fracture process
a. S~(a), the embrittling sensitivity of element
i per unit area of interface, can be expressed
most easily as a relative materials parameter.
The relative fragility is n o t expected to be
linear with bulk concentration for long-term
isothermal heat treatments [4] but will
approximate to this for normal commercial
heat treatments over a wide range of concen-
trations [ 5].
It is thus clear that a species to which the
interfacial atomic cohesive force is highly
sensitive will n o t necessarily be responsible
for a high value of the relative fragility if its
bulk concentration is very low; conversely, a
relatively unaggressive element present in large
quantities may constitute the most dangerous
element in the system because of a high value
of ¢~(a).
235
The sum of the relative fragilities for all
active impurities gives the fragility index for
the cast. In this context the fragility index is
an engineering parameter which depends on
the commercial material composition and, for
a fixed material specification and heat treat-
m e n t (a), will define its quality in relation to
the effect of impurities for the fracture process
a. Because the calculation of S~(a) usually
gives only relative effects with accuracy, the
fragility index becomes an absolute parameter
only by normalizing against the effect of one
element in the series. If we choose the most
deleterious element in the sum, the inaccuracy
in the largest term is removed. Thus the
fragility index is defined by
E~(a)
fragility index - (2)
~m(a)S~n(a)
where the element m is the one which has the
highest relative fragility. The fragility index
thus has the dimensions of weight concentra-
tion and, as will be shown later, is an expres-
sion of phosphorus, tin or copper equivalent.
Thus the final representation of the fragility
index is one which is readily understood in
the fields of quality control and materials
specification.
For certain engineering situations, general
overall parameters are available to specify the
suitability or otherwise of a batch of material.
For instance the conventional fracture tough-
ness parameter is used in this manner. The
fragility index would normally be included in
a fracture toughness determination but in an
unspecified form. Here we show how one
important c o m p o n e n t of such parameters,
that due to impurity concentrations, may be
measured separately so that the overall para-
meter may be more effectively optimized.
The introduction of the p a r a m e t e r / ~ ( a )
into eqn. (1} simplifies considerably the pre-
dictive application of this equation because
it allows an estimate of the a m o u n t of segrega-
tion. The extensive studies on grain boundary
and surface segregation have led to a consider-
able understanding of the segregation pheno-
menon and allow predictive correlations to be
made so that, simply from the use of tabulated
bulk parameters and a knowledge of the heat
treatment of the sample, fairly precise esti-
mates may be made of grain boundary and
free surface segregation levels throughout a
wide range of materials. The grain boundary
236
segregation propensity of different elements
in binary metallic systems was first put into a
quantitative form, from which predictions
could be made, by Seah and Hondros [6].
The theory of grain boundary segregation had
until then assumed a fixed number of adsorp-
tion sites up to one monolayer, akin to the
Langmuir isotherm in gas phase adsorption.
Seah and Hondros invoked a solid state ana-
logue of the Brunauer-Emmett-Teller (BET}
isotherm [7] which, in the dilute case, approx-
imates to a very simple proportionality be-
tween the grain boundary enrichment factor
~ ( a ) and the inverse of the solid solubility
Xc0 of the dilute component.
Many values of the grain boundary enrich-
ment factor ~ ( a ) measured by AES and other
techniques are to be found in the literature.
Figure l(a) shows a plot of these results
against the solubility. The results fit the BET
prediction very well and show that
/3~(a) = 5/Xco
(with a standard deviation of x+2.5). Note that
the theoretical basis for this correlation re-
quires ~ ( a ) to be a ratio of atom concentra-
tions, whilst in eqns. (1) and (2) the ratio of
weight concentrations is used in accord with
c o m m o n metallurgical practice.
In binary systems Xc0 is generally available
from the constitutional phase diagram, allow-
ing ~ ( a ) to be estimated directly. The low
solubility solutes such as sulphur in iron or
bismuth in copper have the strongest propen-
sity to segregate, b u t in steels sulphur is usually
killed by manganese while tramp elements
like bismuth in copper are currently at toler-
able bulk levels consistent with a low value of
¢~(a) in eqn. (1).
In a similar way, there are now sufficient
experimental data on surface segregation levels
for a model to be constructed which enables
predictions to be made of the equilibrium
level of segregation to a free surface in binary
metallic systems. This prediction is made in
terms of t h e surface energies of the alloy
constituents, their enthalpy of mixing and the
strain energy released on segregation [8]. The
effectiveness of this prediction is shown in
Fig. l(b) in which the theoretical surface
enrichment ratio is compared directly with
that measured experimentally.
The equilibrium enrichment factors for a
grain boundary or free surface depend on heat
treatment and alloy composition, denoted by
the material function (a), and are n o t simple
constants for an impurity in any ferrous alloy.
AES has been used to study the above depen-
dences, giving a more detailed knowledge of
segregation mechanisms. Seah and Hondros
[6] have measured the effect of isothermal
heat treatment temperature and solute con-
centration on grain boundary segregation,
while Seah and Lea [ 1] have made equivalent
measurements of the effect on the free surface.
During segregation, interactions can occur
between co-segregating species [4, 9, 10];
thus we need data in addition to the binary
correlations of eqn. (3) to analyse multicom-
ponent systems.
In each of the four categories of materials
failure chosen for elaboration, we present
firstly estimates of the relative fragility for a
n u m b e r of impurity elements as deduced
directly from mechanical test data acquired
either as part of this programme or from
(3)
previously published studies at other labora-
tories. These values of¢~(a) are then compared
with values predicted by eqn. (1) by sub-
stituting the quantities Xi, ~ ( a ) and a value
of S~(a) estimated from a theoretical model.
To illustrate the way the relative fragilities
and the fragility index work in practice, typi-
cal impurity contents will be used. These have
been published for U.K. low alloy steels [11]
and such typical values will be used to quantify
the above parameters.
4. THE FAILURE MODES
4.1. Temper brittleness
Temper brittleness is the intergranular
failure problem most conventionally associated
with grain boundary segregation and with
bulk impurity contents. The degree of em-
brittlement is measured with some precision by
monitoring the temperature of the ductile-to-
brittle transition in Charpy impact energies.
Temper brittleness occurs in low alloy steels
because the impurities couple with the alloy-
ing elements and so give rise to high segrega-
tion levels. From earlier work [12, 13] it has
been shown that most of the problems occur
in groups of steels for which 3 ~ N i - C r and
2 ¼ C r - l M o may be taken as archetypal
systems.
 I I , - , I
I I I ,/ ,/

10 ¢ - - 10 4
. * Ni-B/

• Fe -AS
Cu-Sb ~Fe-Co •Fe~P
.4. •6Fe-P
• ~Fe PJI •
/•~Fe pl~~Fe'Sb
• ~eBFe-sn
@.Fe-Sn/~l" @.Fe-As
c 10 2 -- 10 2
-g O.Fe-Cu
~' FeSi • Pt-Au -
• YFe-Cr • / CuSb
• YFe"Mr~Fe S~/ *
E _ /
d
N • - P Ni-Cu
Cu-Au ~_
x _~Fe-SJ • / . -o
LU AueAg CuAu/~ PICu
ul
Au-Ni • •Fe-Cr /
A -Au /Au-Ag
I
I~IV@
/ Pt-Cr
• ~ /•••Pt - Ni

I •Cu-Pt p d / P d _ N i •
t/ •Au

Cu-Ni•
I /;u-N•• Au-Cu•
/ I J J J I i ~ J i
1 10-2 10-4 I 102 104
Atomic solid solubility Xc Predicted 13 (surface)
(a) (b)

Fig. 1. Correlations o f the equilibrium segregation enrichment ratio ~ ( a ) : (a) for grain boundaries after Seah and H o n d r o s [6] ; (b) for free surfaces after
Seah [ 8 ] . The solid lines s h o w the upper and lower quartiles o f the results, and data published since the original papers are included as stars. The ~ ( a ) here, in
line with the theory, are ratios o f a t o m concentrations and should be m u l t i p l i e d by the ratio o f atomic weights for use in eqns. (1) and (2).

t~
CO
238

4.1.1. Temper brittleness in A I S I 3340 importance of tin and antimony in relation to

The U.S. steel AISI 3340 is the only exam-
ple of the 3½Ni-Cr group for which sufficient
data are available on the relative shift ADBTT
in the ductile-to-brittle transition temperature
after step-cooled embrittling heat treatments.
An average for all the sets for AISI 3340
(3.5% Ni, 1.7% Cr) with constant microstruc-
ture gives from direct fracture data
ADBTT
= (0.28P + 0.16Sn + 0.38Sb + 0.048As) K
with other elements making only small con-
tributions. Here the element symbols represent
solute concentrations in parts per million by
weight. For different steels and different hard-
nesses the absolute magnitude of the tempera-
ture shift will differ but the relative coeffi-
cients of the elements should remain unaltered.
For a typical U.K. commercial purity steel
of the composition shown in Table 1 the
relative fragilities from the direct fracture data
are as follows.
Element P Sn Sb
¢~(a) 6 2~1 1~1
They show that phosphorus and secondly tin
are the main cause of temper brittleness in
this low alloy steel. These values are also
approximately correct for 3 ½ N i - C r - M o - V
steel but, as will be shown below, they do not
apply to plain Cr-Mo steels where the relative
phosphorus is much lower than in steels con-
taining nickel [12].
This typical result may be tested against
the model of eqn. (1) very simply. Much
experimental work has been completed and
published in the literature concerning AISI
3340. The material exhibits temper brittleness
readily and, in this state, the grain boundaries
may be easily exposed for the analysis of the
segregation levels by AES. The quantitative
data of these enrichment levels, together with
the grain boundary enrichment ratios appro-
priate to the step-cooled temper embrittling
heat treatment, have been compiled by
Hondros and Seah [ 15]. Table 1 shows these
values and the c o m p u t e d relative fragilities
for comparison with the above experimental
measurements. In obtaining the calculated
relative fragilities the theoretical relative em-
brittling sensitivities S~(a) are required. These
values are taken from the thermodynamic
theory of Hirth and Rice [16] based on the
numerical analysis of Seah [14] using pair
As
bonding theory. The main aspect of this
1
theory concerns the energetic surfaces formed
by bond breaking at the grain boundary,
shown schematically in Fig. 2. The closeness
of the experimental and calculated relative
fragilities is remarkably good, thus giving
strong support to the model which may now
be used predictively. The fragility index

TABLE 1
Temper brittleness of AISI 3340 (3.5Ni-1.7Cr) and 2 1 C r - l M o

Element Typical U.K. Grain boundary Theoretical Relative fragility ¢~(a)

composition enrichment ratio embrittling
(wt.%) (ratio by mass) ~ ( a ) sensitivity S~(a) Theory Experiment

AISI3340 a
P 0.017 1800 8 6 6
Sn 0.012 950 10 3 2~1
Sb 0.003 950 11 1 1•
As 0.016 300 8 1 12
214--Cr-1Mob
P 0.017 2000 4c 14 11
Sn 0.012 200 10 2~1 3
Sb 0.003 300 11 1 1
As 0.016 75 8 1 1

aThe temper brittleness fragility index of this cast is 0.031 wt.% Peq (theoretical value 0.030 wt.% Peq)-
bThe temper brittleness fragility index for this cast is 0.025 wt.% Peq (theoretical value 0.022 wt.% Peq ).
CThe embrittling sensitivity of phosphorus in molybdenum steels is approximately halved because of simultaneous
molybdenum segregation which improves the grain boundary cohesion [ 14 ].

. . . . ~!iii¸ ! iiii~....
i li!(!!!~i!}ill
Fig. 2. Temper brittleness: a schematic model of the
effect of segregants on grain boundary cohesion.
expressed in terms of the d o m i n a n t impurity
phosphorus is 0.031 wt.% Peq -- this is the
phosphorus equivalent of the cast.
4.1.2. Temper brittleness in 2~Cr-lMo
The analysis may be repeated for 2¼Cr-lMo
steel which is a c o m m o n pipe steel susceptible
to temper brittleness. The DBTT fracture data
of Bruscato [17] applied to typical U.K. com-
mercial impurity levels give the following
experimental relative fragilities.
Element P Sn Sb
~(a) 11 3 1
These show once more the dominance of
phosphorus and, to a lesser extent, tin. By an
analysis identical with that for AlSl 3340 the
relative fragilities for 2 ¼ C r - l M o after a step-
cooled embrittling treatment were computed
and are shown in Table 1. The agreement is
again remarkable if the remedial effect of
segregated m o l y b d e n u m is taken into account.
The relative fragilities may be summed to give
a fragility index in terms of a phosphorus
equivalent: for this cast it is 0.025 wt.% Peq.
Thus in both these steels phosphorus is the
d o m i n a n t impurity but for the nickel-bearing
AISI 3340 tin is also important. For these
two archetypal low alloy steels, AlSl 3340
and 2¼Cr-lMo, the experimental and pre-
dicted relative fragility parameters agree very
closely.
4.2. Stress relief cracking
Here we refer to a typical weldable creep-
resistant steel of the C r - M o - V series, ½Cr-
Mo-V, and we consider the effect of impurity
segregation in the heat-affected zone of the
weld. The phenomenon of interest is segrega-
tion to the inner surfaces of the nucleating
cavities formed along grain boundaries under
rapid strain conditions.
Primary metallurgical data of crack length
in a fixed strain bend test are available [18]
239
on commercial stock and a regression analysis
on these by Seah [11] has demonstrated that
impurity effects are as important as micro-
structural effects. The role of impurity content
may be represented by
A (cracking susceptibility) = 0.8P + 4.0Sn +
+ 6.5Sb + 2.4As + 0.37Cu + 0.12Ni
where, as before, the element symbols repre-
sent solute concentrations. Hence for average
impurity contents in U.K. commercial ½Cr-
Mo-V steel the relative fragilities from direct
crack growth data are as follows.
Element Sn Cu As Sb P Ni
~(a) 3 2½ 2 1 <1 <I
In order to test these data against the model
of eqn. (I) we note that the enrichment factor
/~(a) now refers to free surfaces for which in
general there is no simple correlation with
grain boundary enrichment [2]. Accordingly,
As samples of commercial quality ½Cr-Mo-V
were fractured within the high vacuum of the
1
Auger electron spectrometer after the produc-
tion of cracks by stress relaxation tests at
700 °C [11]. Highlycavitated regions offering
surfaces for AES examination of the internal
cavities were found one or two grains ahead
of the crack front. These measurements, to-
gether with a bulk analysis of each sample,
yield the enrichment ratio for each observed
element (Table 2). Furthermore, the segrega-
tion levels measured on the cavitated surfaces
are in agreement with free surface segregation
measured on uncavitated surfaces heated to
700 °C in situ in the AES apparatus. These
measurements, being far more easily obtained
experimentally, may therefore be used as a
good guide to the composition of cavity
surfaces.
In order to assess the embrittling sensitivity
S~(a) we adopt the model depicted schemati-
cally in Fig. 3 of a nucleating cavity and we
consider the competition between the ten-
dency for the cavity to sinter out through
capillarity forces and the opposing tendency
for it to grow under the action of the applied
stress.
Because of adsorption of the impurity ele.
ments on the cavity walls the surface energy
7s is reduced, and since the critical radius rc
above which cavities at the grain boundaries
become stable and start to grow is related to
~'s by
240

TABLE 2
Stress relief cracking in 1M C r - M o - V

Element Typical U.K. Grain boundary Theoretical Relative fragility ~b~(a)

composition enrichment ratio embrittling
(wt.%) (ratio by mass) ~ ( a ) sensitivity S~(a) Theory Experiment

Sn 0.012 3100 1.1 3 3

Cu 0.12 120 1.9 2 2=1
As 0.016 950 1.25 1~1 2
Sb 0.003 4500 1.0 1 1
P 0.017 240 1.9 ! 1
2
T h e stress relief cracking fragility index for this cast is 0.036 wt.% Sneq (theoretical value 0.032 wt.% Sneq).

(5) and are given in Table 2. In stress relief

cracking, surface segregation is important and
acts through the cavity generation rate; for
iii!it!iiiii!i!i!iiii!iiiiiiii!iiiii!i!!!!ii!iiiiiii!i!!iii.iiiiiiiii . ii!iiiiiiiiii
iiiiiiiiiiiiii!iiiii!
iiiiiiiiiiiiiiii!iliiiiiiiiiiiiiiiii!iiiiiiiJi,
iiiii!i!i!i!ii!iiiiii
............
ii!i
iUii!iii
' present impurity levels in U.K. steels tin,
copper and arsenic have the greatest effect.
A comparison between the predicted values
~i~!i~i~:'i~i!~i!~!~!i~i~i~i~i~i~i!~i~i~i~!ii!i!ii!i!i~i!~i~i!ii~i!ii!ii!i!ii!~ of ¢~(a) based on this model and given in
%~ii~!~i!~i!i!~!i!i!i!i~i!~i!i!i!i~!~i!~!i~i!ii~.i.ii.!i.i~.ii~iiiii~ii~ Table 2 and the values quoted earlier from the
(a) (b) regression analysis on the metallurgical data
shows good agreement and confirms the
Fig. 3. (a) Stress relief cracking: surface segregation
dominant effect of tin and then of copper,
on the cavity walls affects the cavity nucleation rate.
(b) Creep embrittlement : grain boundary segregation arsenic and antimony, in that order, on stress
affects diffusion along grain boundaries with a c o n - relief cracking in these steels. The fragility
s e q u e n t effect on the cavity growth rate. index in this case is expressed as a tin equiv-
alent: 0.036 wt.% Sneq for this cast.
rc = 2~,/a
4.3. Creep embrittlement
re is also reduced by surface segregation. Here This phenomenon, as it pertains to ½Cr-
o is the local tensile stress across the grain M o - V , is distinguished from stress relief
boundary. The reduction in 7, as the fraction- cracking by lower strain rates and lower
al surface monolayer coverage X, increases is service temperatures (550 °C). In terms of
given by a combination of the Gibbs' adsorp- mechanisms the rate-determining step is the
tion theorem and the Langmuir isotherm: transport of matter or vacancies along grain
boundaries to feed the growing cavity.
7, = 70 + FORT ln(1 - - X , ) (4)
A regression analysis of the effects of im-
where 7 ° is the grain boundary energy without purities on the rupture ductilities and rupture
segregation and F ° is the monolayer coverage lives during creep at 550 °C on all available
of adsorbate in moles per square metre. tested ½ C r - M o - V samples has shown [11]
The increased cavity nucleation rate N that impurities are more important than
resulting from the impurity-induced reduction microstructural changes in their detrimental
in surface energy reflects the relative em- effect, and both rupture ductility and rupture
brittling sensitivity. This may be quantified in life show approximately the same relative
terms of the rupture life tr and the rupture dependence upon impurities (rupture ductility
strain er referring to the equations derived falling and rupture life increasing): this is
from Skelton's [11, 19] analysis: represented by
tr = Db -215N-3/5 --A (rupture ductility) = 1.5P + 0.36Cu +
er cc D b l / S N ~ l / 5 (5) + 1.6Sn + 1.2S
The embrittling sensitivities of the segregating where the element symbols represent solute
elements can be calculated from eqns. (4) and concentrations. For the typical commercial
 241

purity the relative detrimental importance is
as follows.
Element Cu P Sn
~(a) 2~1 1~1 1 1
In order to compare these values with pre-
dicted performance, we adopt the model of
Fig. 3 and consider the effect of segregation
on grain boundary transport.
The appropriate enrichment factors for
grain boundaries in eqn. (1) may be assessed
from solid solubility data in the manner dis-
cussed earlier; here, however, they were mea-
sured experimentally for improved accuracy.
At 550 °C equilibrium grain boundary seg-
regation is attained after a very small fraction
of creep life. In this alloy, while the grain
boundary segregation is sufficient to exacer-
bate the creep problem, nevertheless it does
n o t provoke temper brittleness and so the
grain boundaries cannot be exposed easily by
low temperature fracture for AES examina-
tion. However, on the few samples where par-
tial failure on uncavitated boundaries occurred,
grain boundary enrichments were measured
and these are presented in Table 3.
Under the applied stress, cavities nucleate
along the boundaries and grow by grain boun-
dary vacancy transport, leading inevitably to
intergranular creep rupture.
The effect of segregation on the grain
boundary diffusivity D b may be measured
through the attendant effect on the grain
boundary energy ~'b; these terms are linked
through the equation due to Borisov et al.
[20] in the form
D b _ d exp/27ba2 ~
| ]
Dv 5 \ kT
where Dv is the lattice diffusivity, d is the
interatomic spacing and 5 the width of the
grain boundary. This equation together with
S
eqns. (4) and (5) allows the relative em-
brittling sensitivities in Table 3 to be calculated
as a change in tr or er concomitant with a
change in segregation level, from which values
of ¢~(a) can be computed.
A comparison of the predicted relative
fragilities with the experimental values shows
a clear agreement that phosphorus, copper
and tin are the dominant elements. The hier-
archies are different however. The measured
effect of sulphur, which was n o t predicted, is
very probably due to sulphide precipitates
and not segregation, while the phosphorus
dependence is somewhat lower than that
predicted by this model and may involve the
contribution of phosphorus to alterations in
microstructure [21]. Nevertheless it is clear
that copper and phosphorus are the most
important elements, followed by tin.
Both stress relief cracking and creep em-
brittlement are thus impurity sensitive, but
the vastly different strain rates cause differ-
ent forms of segregation to be important and
are thus dominated by different elements.
Phosphorus is relatively much more active at
grain boundaries than surfaces and hence, in
this form of creep embrittlement, it is a major
troublesome element along with copper and
tin. Here the fragility index, expressed in
terms of the experimentally observed
dominant element copper, is 0.24 wt.% Cueq.
4.4. Intergranular stress corrosion
The change in chemistry of the grain boun-
daries by impurity segregation, without any
(6)
microstructural changes, can in some service

TABLE 3
Creep embrittlement at 550 °C in ½Cr-Mo-V

Element Typical U.K. Grain boundary Theoretical Relative fragility ~b~(a)

composition enrichment ratio embrittling
(wt.%) (ratio by mass) ~ ( a ) sensitivity S~(a) Theory Experiment

Cu 0.12 70 1.9 2½ 2½
P 0.017 900 1.9 4½ 1½
Sn 0.012 500 1.1 1 1
As 0.016 270 1.25 1 -
Sb 0.003 350 1.0 <½ -

The creep embrittlement fragility index for this cast is 0.24 wt.% Cueq(theoretical value 0.44 wt.% Cueq).
242
conditions affect markedly the propensity for
cracking in the presence of a combination of
stress and an aggressive environment. The
effect of impurities on stress corrosion crack-
ing is illustrated here by mild steel in a nitrate
solution, where failure of commercial quality
material is invariably intergranular.
In extensive recent work at the National
Physical Laboratory [22] the relative harm-
fulness of tramp elements was analysed from
mechanical test data on laboratory melts of
high purity mild steel, each containing a single
impurity at a dilute level comparable with
that found in commercial material. Following
an equilibrium segregation heat treatment,
samples were tested at constant strain rate in
a hot nitrate solution and at the free corroding
potential. The time to failure of samples was
used to derive a ratio R for each melt, this
being the ratio of the time to failure in the
corrosive nitrate solution to that in an inert
paraffin environment at the same temperature.
It was found that after an equilibrium
segregation heat treatment the reduction in R
from its value for the high purity steel could
be expressed by [22]
--AR = 700 S + 1A1 + 0.4As + 27Ca + 1.9Cu +
+ 0.2Ni + 20P + 0.95Sb + 1Sn + 0.3Zn
where the element symbols are the bulk con-
centrations and apply only to very dilute
levels. All these residual elements are detri-
mental, although several of the elements
become beneficial at levels only slightly higher
by acting through microstructural changes. In
commercial steels the sulphur, aluminium and
calcium are stabilized as precipitates and
would not be detected as grain boundary
segregants. Thus at the typical impurity levels
encountered in U.K. steels the relative harm-
fulness of the elements as derived from direct
mechanical test data is as follows.
Element P Cu Ni Sn As Sb
¢~{a) 3 2 0.2 0.1 0.1 <0.1
As in the case of creep embrittlement, it is
normally difficult to expose the grain boun-
daries for direct analysis. However, on stress-
corroded samples where intergranular fracture
had been initiated following impact in the
spectrometer, fresh grain boundaries were
occasionally exposed just ahead of the crack
front. In these instances the chemistry of the
uncorroded grain boundaries could be exam-
ined. The grain boundary enrichments of the
observed elements are given in Table 4.
The importance of a corrosion process in
this environmentally assisted crack propaga-
tion is shown by the fact that it can be con-
trolled electrochemically. This has led to the
association of cracks with pre-existing active
paths, defined by grain boundary segregants
or precipitates, which are anodic to the main
volume of material. Either the active paths
formed by the presence of segregants at grain
boundaries are intrinsically anodic, or the
zones next to the grain boundaries, being
depleted of segregant, are anodic with respect
to the grain boundaries. If the corrosion pro-
ducts are soluble, intergranular corrosion
occurs in the unstressed state, but often a
stress is required to open cracks and to expose
new surfaces to the action of the corrosive
environment. For example, the surface of
mild steel in nitrate solution becomes covered
with a magnetite layer which is protective and
the function of the stress is to fracture this
magnetite layer to allow the reaction to
proceed.
The capacity of segregants at the grain
b o u n d a r y - o x i d e interface to operate as a
local cell, enhancing the localized attack,
depends upon a very large number of factors,
among them the local pH, the potential dif-
ference which exists within the crack, and the
change in solution composition during disso-
lution. Despite this, good theoretical pre-
dictions of stress corrosion crack growth rates
have been made from bulk electrochemical
properties by Doig and Flewitt [23].
The preferential dissolution of the grain
boundary in an aqueous oxidizing environment
is shown schematically in Fig. 4. The em-
brittling role of hydrogen is not considered
here because of the anodic nature of the crack
tip in relation to its oxide-covered walls. To a
first approximation the rate of dissolution of
the grain boundary is directly dependent on
the electrochemical potential set up between
it and the bulk crystallites [24], and here we
assume that this reflects the term S~(a} in
eqn. (1). In Table 4 the difference IAE0$
between these two potentials is given, from
which ¢~(a) is calculated. In this case phos-
phorus and copper are important and to a
lesser extent arsenic, tin and nickel. It should
be noted that there is still uncertainty about
the appropriate dissolution reaction equation
 243

TABLE 4
Stress corrosion cracking of mild steel in nitrate solution

Element Typical U.K. Grain boundary Theoretical Relative fragility @~(a)

composition enrichment ratio embrittling
Theory Experiment
(wt.%) (ratio by mass)/~i (a) sensitivity S~(a)

P 0.017 950 0.5 1.2 3

Cu 0.12 140 0.8 2 2
As 0.016 130 0.6 0.2 0.1
Sn 0.012 270 0.3 0.1 0.1
Ni 0.12 30 0.2 0.1 0.2
Sb 0.003 260 0.6 <0.1 <0.1

The intergranular stress corrosion fragility index for this cast is 0.031 wt.% Peq (theoretical value 0.052 wt.% Peq).

meter, the relative fragility, is defined. This

parameter gives the order of the effect due to
each element and arising from the bulk residu-
tO __ _
al levels in a given cast of steel. In the cate-
gories of intergranular failure treated here,
boundarY ,fM--~-M÷ - - -~ - - - - - --
the parameter has been computed by reference
.

to a model and in each case there is general

Fig. 4. Intergranular stress corrosion: grain boundary
segregation affects the electrochemical dissolution
rate of a grain boundary under stress at a crack tip.
in the case of phosphorus dissolving from a
grain boundary in nitrate solution. This leads
to a large error in S~(a) in Table 4. In view of
the approximate form of this model it is in
surprisingly good quantitative agreement with
the experimental data. This shows that a
reduction in the tolerance levels of phosphorus
and copper would make a substantial step
towards increasing the i m m u n i t y of mild
steel to stress corrosion. Because of the domi-
nance of phosphorus the fragility index is
expressed here in terms of a phosphorus
equivalent, 0.031 wt.% Peq for this cast.
agreement with the quantity as measured by
metallurgical test data. The value of this
approach lies in the ability to predict with fair
accuracy the nature and order of the potent
species, given the bulk composition levels,
w i t h o u t recourse to lengthy metallurgical test
procedures. This allows the steel maker a
more economic control of the condition of
his product to meet a given impurity limit set
by the overall fragility index. The fragility
index sums the effects of all elements, with
appropriate coefficients defined by the rela-
tive fragilities, to give an overall impurity
equivalent for a given cast of steel. Thus the
fragility index of a cast of steel provides the
quality specification in relation to the effect
of impurities on the designed use of the
material.

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In the more important categories of inter-
granular weakness considered here, two or
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important elements and their relative effects
vary markedly from one metallurgical situa-
tion to another. In order to quantify this
hierarchy of potency an engineering para-
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244

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