The Effect of Phosphorus Segregation on

the Intermediate-Temperature Embrittlement

of Ferritic, Spheroidal Graphite Cast Iron
S.F. CHEN, T.S. LUI, and L.H. CHEN

The objective of this article is to study the effect of phosphorus segregation on the fracture
modes of the intermediate-temperature intergranular embrittlement which occur in ferritic, sphe-
roidal graphite cast iron. The specimens were quenched from 820 ~ and 500 ~ during the
furnace-cooling period of ferritization annealing in order to vary the degree of phosphorus seg-
regation, then deformed in tension at various temperatures between 20 ~ and 520 ~ with a
constant crosshead speed of 0.01 mm/s. These two kinds of specimens were also fractured by
impact at about - 5 0 ~ in the vacuum chamber of a scanning Auger microscope in order to
analyze the phosphorus segregation and compare the fracture modes. The results show that the
fracture mode of the intermediate-temperature embrittlement is influenced by the history of heat
treatment prior to tension. When the specimens were held at 500 ~ and quenched from this
temperature, the fracture was intergranular. However, the specimens quenched from 820 ~
revealed cleavage fracture with cracks propagating radially from a central region with
magnesium-rich particles. Identified by transmission electron microscopy (TEM), the particles
were MgO. Grain-boundary segregation of phosphorus in the specimen held at 500 ~ was
confirmed by Auger analysis of the impact fracture surface. Segregation of phosphorus must
play an important role in the fracture mode of the intermediate-temperature intergranular
embrittlement.

I. INTRODUCTION Systematic investigation of the effect of phosphorus

BECAUSE of its good mechanical properties and
phase stability, the use of ferritic, spheroidal graphite
cast iron has been well established. However, the reli-
ability of application in the temperature range of about
300 ~ to 500 ~ is reduced owing to the so-called
"intermediate-temperature embrittlement" that often oc-
curs with intergranular fracture, rl-6] Correlated to the
intergranular fracture is the loss in ductility. In order to
increase the reliability of ferritic, spheroidal graphite
cast iron in this temperature range, the factors affecting
intermediate-temperature intergranular embrittlement
should be understood. It has been demonstrated that the
occurrence of intergranular embrittlement is associated
with a triaxial stress field induced by spheroidal graphite
voids or artificial notch, fl,2,4,SJ Along with mechanical
factors, the embrittlement is also affected by silicon con-
tent 16~ and the size of the graphite nodule or ferrite
grain.~s~
Intergranular fracture usually occurs with grain-
boundary segregation of impurities. The fact that phos-
phorus segregation results in temper embrittlement of
steel is a well-known example. Ferritic nodule iron also
suffers from temper embrittlement. ~7,s,91 As in the case
of steel, the sensitivity of embrittlement is raised with
higher phosphorus content. The most sensitive temper-
ing temperature is between about 450 ~ to 600 ~
When a specimen is cooled slowly through this temper-
ature range, its impact strength is severely reduced and
intergranular fracture is obtained.
S.F. CHEN, Graduate Student, and T.S. LUI and L.H. CHEN,
Professors, are with the Department of Materials Science and
Engineering, National Cheng Kung University, Tainan, Taiwan
70101, Republic of China.
Manuscript submitted May 28, 1993.
segregation on the intermediate-temperature intergranu-
lar fracture has not yet been reported. Therefore, the
purpose of this investigation is to study whether phos-
phorus segregation plays the same role in intermediate-
temperature intergranular embrittlement as it does in
temper embrittlement.
II. EXPERIMENTAL PROCEDURE
The chemical composition of the ferritic, spheroidal
graphite cast iron used in the current investigation, as
determined by emission spectrometry, is 3.44 wt pct C,
3.90 wt pct Si, 0.065 wt pct Mn, 0.041 wt pct P, 0.024
wt pet S, and 0.055 wt pct Mg. The material was melted
in a high-frequency induction furnace, spheroidized, in-
oculated, and poured into Y-shaped sand molds of di-
mensions 30 • 100 • 150 mm. The ingots were then
cut into 14 • 14 • 100 mm bars to prepare for ferriti-
zation heat treatment.
The ferritization began with isothermal holding at
930 ~ for 3 hours and then furnace cooling to 820 ~
After being maintained at 820 ~ for 5 hours, some of
these bars were directly quenched to room temperature.
The others were furnace cooled to 500 ~ and held iso-
thermally for 20 hours prior to water quench. The re-
sultant microstructure, as illustrated in Figure 1, consists
of fully ferritic matrices and spheroidal graphite nodules.
After heat treatment, these bars were machined to round-
type tensile pieces with a 6-mm diameter and 30-mm
length in the gage-length section.
A computerized testing machine was used to perform
tensile tests with a constant crosshead speed of 0.01
mm/s (i.e., an initial strain rate of 3.33 • 10-4 s-~).

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 25A, MARCH 1994--557

The test temperatures were selected in the range of 20 ~
to 520 ~ For the high-temperature tests, each specimen
was heated in an attached furnace to a desired temper-
ature and held isothermally for 20 minutes prior to its
test. During tensile deformation, the temperature fluc-
tuation was within -+ 1 ~
The fracture surfaces of the tensile pieces were put in
a scanning electron microscope (SEM) for secondary
electron imaging and energy dispersive spectroscopy
(EDS). Slices cut from the deformed gage-length section
were ground and thinned by an ion mill for transmission
electron microscope observation.
The analysis of impurity segregation on grain bound-
ary was performed in a scanning Auger microscope
(SAM). Prior to the analysis, some bars quenched from
820 ~ and 500 ~ were machined into notched round
rods and fractured by impact at about - 5 0 ~ in the
SAM chamber with a 10 -~~ torr vacuum. The acceler-
ation voltage for this analysis was set at 3 kV.
tensile tests were performed in the intermediate-
temperature range of about 300 ~ to 500 ~ The frac-
ture mode of the specimens quenched from 500 ~ and
tested in the intermediate-temperature range is inter-
granular, as can be seen in Figure 3(a). The figure also
indicates that the intergranular facets around graphite
nodules are flat. However, those in the middle of the
graphite nodules are scattered with microvoids. Pre-
sented in Figure (b) is the micrograph of higher mag-
nification, which shows that some microvoids contain
particles inside. The EDS analysis of these particles, as
illustrated in Figure 4 indicates that these particles are
magnesium rich. The fracture mode of the specimens
quenched from 820 ~ and tested in the intermediate-
temperature range is illustrated in Figure 5. Instead of

III. RESULTS
Figure 2 gives the elongation data of the specimens
quenched from 820 ~ and 500 ~ As revealed in this
figure, the elongation deteriorates seriously when the

Fig. 1 --Optical metallography of the ferritic, spheroidal graphite cast Fig. 3 - - ( a ) Illustration of intergranular fracture of the specimens
iron. quenched from 500 ~ the micrograph was taken from the fracture
surface of the specimen tested at 400 ~ (b) The same specimen at
a higher magnification showing microvoids on the intergranular
facets.
20
0
Fe
-- 0
0
9 9
9 0

o 820Q o o
H9
ds 9 500Q "
9 O

l l l i l l
0
0 100 200 300 400 500 ........ ...... JI/ .........
I1 r2 13 ~4 15 16 17 '8 19
TEMPERATURE('C) %.48o Range = lO.23okeV 10.230 -)

Fig. 2--Elongation data of the specimens quenched from 820 ~ and Fig, 4 - - T h e EDS spectrum obtained from a particle of the 500 ~
500 ~ during the period of ferritization annealing. quenched specimen after fracturing at 400 ~

558--VOLUME 25A, MARCH 1994 METALLURGICAL AND MATERIALS TRANSACTIONS A

intergranular fracture, cleavage occurs with cracks prop- IV. DISCUSSION
agating radially from a central region which contains
second-phase particles. The EDS spectrum of these Besides the function of spheroidization, magnesium
particles (not shown here) reveals that they are also mag- also serves as a deoxidizer. 1~~ The MgO particles, a re-
action product during spheroidization treatment, can act
nesium rich. In addition, microvoids with magnesium-
rich particles are also found on the surface of shrinkage, as the nuclei of graphite nodules) t~J However, they can
as shown in Figure 6. A particle with a similar size as also become inclusions gathered in the final solidified
those shown in Figure 3 was examined by transmission
electron microscopy (TEM). The diffraction pattern con-
firms that it is a MgO particle. The bright-field and dark-
field images of this particle are shown in Figure 7. The
selected-area diffraction pattern with zone axis [001] is
also illustrated in this figure.
The fractography of the specimen quenched from
500 ~ and impacted at about - 5 0 ~ for SAM analysis
is given in Figure 8(a). It reveals intergranular fracture
with second-phase particles. The SAM spectra of the
flat-grain facet and the particle surface are shown in
Figures 8(b) and (c), respectively. Evidently, phospho-
rus segregation has occurred on the grain boundary and
particle surface, and the particles are MgO as in the
aforementioned cases. The fracture mode of the speci-
men quenched from 820 ~ and impacted at about
- 5 0 ~ is cleavage. As shown in Figure 9(a), the type
of cleavage is not the same as the radial type shown in
Figure 5 and no magnesium-rich particles are found.
Also, SAM analysis of the cleavage surface, as depicted
in Figure 9(b), does not reveal any phosphorus
segregation.

Fig. 5--Illustration of radial cleavage of the specimens quenched

from 820 ~ the micrograph was taken from the fracture surface of
the specimen tested at 400 ~
m

220 200 0

020 0 0

Fig. 6 - - Microvoids with magnesium-rich particles scatter on the sur-
face of shrinkage.
(d)
Fig. 7 - - T h e micrographs of an MgO particle identified by TEM:
(a) bright-field image, (b) dark-field image by (200), (c) selected-area
diffraction pattern with zone axis [001], and (di corresponding anal-
ysis of diffraction pattern.

METALLURGICALAND MATERIALSTRANSACTIONS A VOLUME 25A, MARCH 1994--559

 r ~ ! '' i i ~ i i '"

dN(E) dN(E)_
dE dE Fe
Fe Fe

Fe

(b) (b)
I I I t I I I I

100 200 300 400 500 600 700 800 O0 200 300 400 500 600 700 800
Kinetic Energy(eV) Kinetic Energy(eV)
Fig. 9--(a) The fracture surface of the specimen quenched from
820 ~ and fracturedby impact at about -50 ~ and (b) SAM spec-
trum on the cleavage surface.

or transgranularly depending on the history of heat treat-

ment prior to tension. It leads to the suggestion that seg-
regation of impurity plays an important role in the
dNE
(_____d
)E resultant fracture mode. The SAM spectra and micro-
graphs shown in Figures 8 and 9 suggest strongly that
the extent of phosphorus segregation decides the fracture
mode of the intermediate-temperature embrittlement.
P According to the literature, t]z,]3} the level of phosphorus
segregation in ferrite increases with decreasing temper-
(c)
ature from 800 ~ to 400 ~ When a specimen is held
I I I I I I
200 400 600 800 1000 1200 isothermally at 500 ~ phosphorus segregation on grain
boundary is enriched and it becomes easier for cracks to
Kinetic Energy(eV) propagate intergranularly. If the specimen is quenched
Fig. 8--(a) The fracture surface of the specimen quenched from from 820 ~ grain-boundary segregation of phosphorus
500 ~ and fractured by impact at about -50 ~ (b) SAM spectrum should be reduced, leading to subsequent fracture in
on the flat-grain boundary, and (c) SAM spectrum on the surface of cleavage. The lower degree of segregation may simul-
a magnesium-richparticle. taneously reduce the ease of crack initiation on MgO
particle clumps, since the ductility is somewhat im-
proved, as shown in Figure 2.
region. The distribution of magnesium-rich particles The fracture modes of the intermediate-temperature
shown in Figures 3(a) and 6 suggests that these particles embrittlement reported in the literature I2-6] are all inter-
are MgO. The TEM observation (Figure 7) and SAM granular. In other words, the radial cleavage described
analysis (Figure 8(c)) of selected magnesium-rich par- in the current investigation has never been found. Com-
ticles support this implication. pared to the 820 ~ quenching process in this investi-
The two different fracture modes of the intermediate- gation, the cooling period of conventional ferritization
temperature embrittlement shown in Figures 3 and 5 can annealing is furnace cooling from about 750 ~ to room
be rationalized as follows. When a specimen is de- temperature, tA-ri During this slow cooling period, seg-
formed, MgO particles serve as the crack initiation sites. regation of phosphorus on grain boundary should be en-
After initiation, the cracks may propagate intergranularly hanced, giving rise to intergranular fracture as reported.

560--VOLUME 25A, MARCH 1994 METALLURGICAL AND MATERIALS TRANSACTIONS A

 That the fracture mode of the impact specimens, as
shown in Figures 8(a) and 9(a), varies with the history
of heat treatment is a typical characteristic of temper em-
brittlement. Although the fracture mode of intermediate-
temperature embrittlement has the same heat-treatment
dependence as that of temper embrittlement, the mech-
anisms of these brittle fractures are different. The oc-
currence of intermediate-temperature embrittlement does
not depend on the extent of phosphorus segregation,
which can be confirmed by the SAM spectra given in
Figures 8 and 9.
V. CONCLUSIONS
According to this study, the following conclusions are
drawn:
1. Intergranular fracture is not the only fracture mode
of the intermediate-temperature embrittlement of fer-
ritic, spheroidal graphite cast iron. When the speci-
mens are held at 500 ~ the fracture is intergranular.
If the specimens are quenched from 820 ~ radial
cleavage with cracks propagating from a central re-
gion with magnesium-rich particles is obtained.
2. Identified by SEM, TEM, and SAM, it is suggested
that the magnesium-rich particles are MgO.
3. Both the fact that the fracture mode changes from
cleavage to intergranular fracture when the quench-
ing temperature changes from 820 ~ to 500 ~ and
the results of SAM analysis suggest strongly that
grain-boundary segregation of phosphorus plays an
METALLURGICAL AND MATERIALS TRANSACTIONS A
important role in the fracture mode of the
intermediate-temperature embrittlement.
ACKNOWLEDGMENTS
This project was supported by the Chinese National
Science Council (Contract No. NSC 82-0405-E-006-
107) to whom we are grateful.
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