Characterization and Corrosion Behavior of High-Chromium

White Cast Irons

A. NEVILLE, F. REZA, S. CHIOVELLI, and T. REVEGA

Erosion-resistant high-chromium white cast irons (CWIs) are widely used in hydrotransport com-
ponents, particularly in oil-sand operations. Due to the acceptance that corrosion processes can
accentuate material degradation by erosion processes and vice versa, it is important to understand
the corrosion resistance of these materials in the environments in which they are used. Three CWI
alloys with different chemical compositions—chromium (26 to 40 wt pct) and carbon (2.5 to 4.3 wt
pct)—were investigated in this study. Electrochemical DC potentiodynamic polarization and poten-
tiostatic tests were carried out in a solution of 1000 ppm Cl" at a pH of 8.5 (obtained by adding
NaOH) that simulates a recycle cooling water. A detailed characterization of the microstructures was
also performed. There are significant effects of microstructural features and alloy composition on the
corrosion behavior of CWIs. Two key factors have been shown to determine the corrosion behavior:
the primary carbide area fraction and the amount of chromium as well as other elements in the matrix.
The corrosion resistance of the CWI alloys strongly depends on the ratio of chromium content in the
M7C3 carbide to that in the matrix (CrM7C3/Crmatrix).

I. INTRODUCTION Na2SO4 solution (pH 6.8). This was due to the microgal-
vanic coupling between the carbides and the matrix. It was
HIGH-CHROMIUM white cast irons (CWIs) can be found that the matrix acted as a sacrificial anode, since the
divided into three main alloy types according to their key
corrosion potential of the carbides was believed to be more
elements (e.g., Fe, Cr, C), which determine whether they
noble than that of the matrix.[1,7] The depleted zone around
are hypoeutectic, eutectic, or hypereutectic alloys.[1–4] As
the carbide was thought to be responsible for the main
the genuine Fe3C carbide in the Fe-C system can accept
corrosion attack on the CWI alloy.
partial substitution of Fe by Cr in the Fe-Cr-C system,
Zumelzu et al.[8] studied the role of chromium and nickel
hypoeutectic alloys are formed in the Fe-Cr-C system at
on the corrosion behavior of CWI alloys in sugar media and
Cr/C ratios ranging from 15 to higher ratios with low chro-
reported that the combination of high Cr/C ratio (larger
mium and carbon contents, while hypereutectic alloys are
than 27) and Ni/C ratio (1.8 to 6.2) gave the best corrosion
formed at Cr/C ratios lower than 15. Hypoeutectic alloys resistance for CWI alloys. Adding other beneficial elements
indicate that solidification of CWI is initiated by the for-
such as nickel in CWI alloys acts to stabilize austenite in
mation of austenite (g) as a primary phase, and the eutectic
the matrix. Due to minimal alloying of carbides, nickel can
phase is formed later. In hypereutectic alloys, M7C3 acts as
reduce the precipitation of carbide-forming elements.[7,9]
a main phase since it is the phase formed primarily and is
Furthermore, it is quite common that the corrosion resist-
followed by the solidification of the eutectic phase with a
ance is proportional to the chromium to carbon (Cr/C)
eutectic structure (M7C3 1 g).
ratio,[10] since the Cr/C ratio can indicate the amount of
Erosion-resistant CWIs have been used in the mining
chromium in the matrix. Decreasing the Cr/C ratio will
industry because of their ultrahigh hardness.[5,6] Manage-
reduce the matrix area and thereby the volume fraction of
ment of corrosion to an acceptable level is a major issue
carbides (i.e., the amount of M7C3 becomes larger). It is
in materials selection and in aggressive environments (i.e., well known that carbon has a strong affinity to chromium
in slurry pipes/pumps), it is often necessary for materials
during the casting process. Therefore, once most of the
to resist both corrosion and erosion. For CWIs, it is docu-
chromium is tied up with carbon to form carbides, the
mented that it is necessary to have at least 12 wt pct Cr in regions adjacent to the carbides become depleted in Cr
the matrix for ambient temperature service from a corrosion
and passivation protection is locally removed.
point of view.[1] This amount of chromium will form a
The purpose of this paper is to study the corrosion behav-
sufficiently protective chromium oxide (Cr2O3) on the sur- ior of three CWIs (with 25 to 40 wt pct Cr) using electro-
face to protect the materials from its environment.[2] chemical techniques in a solution simulating a recycle
Watson et al.[7] reported that the binderless-carbide mate- cooling water. The deionized water was fully aerated and
rials offered the best corrosion resistance, while a commer- had approximately 1000 ppm of Cl", and a pH of 8.5
cial CWI sample suffered the highest corrosion rate in a 1 N
adjusted by adding NaOH. Electrochemical tests included
anodic polarization scans and potentiostatic tests.
A. NEVILLE, Professor of Tribology and Surface Engineering, and
F. REZA, Materials Engineer, are with the Corrosion and Surface Engi-
neering Research Group, School of Mechanical Engineering, University II. EXPERIMENTAL TECHNIQUES
of Leeds, Leeds, U.K., LS2 9JT. Contact e-mail: a.neville@leeds.ac.uk
S. CHIOVELLI, Director of Research, and T. REVEGA, Senior Materials A. Materials
Technologist, are with Syncrude Canada Ltd., 9421-17 Avenue, Edmonton,
Alberta, Canada, T6N 1H4. Three different grades of as-cast materials are studied in
Manuscript submitted August 5, 2005. this work, with the chemical compositions listed in Table I.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 37A, AUGUST 2006—2339

 Table I. Specified Chemical Composition (Wt Pct) of High-Chromium Cast Iron Alloys

Alloy C Mn P S Si Ni Cu Cr Mo V Ti Co Mg Cr/C
CWI28 2.5 0.98 0.032 0.035 0.57 0.62 0.04 25.9 0.43 0.055 0.023 0.048 0.04 10.4
CWI32 3.0 0.92 0.028 0.031 0.56 0.45 0.44 27.5 1.82 0.065 0.023 0.044 0.045 9.2
CWI38 4.3 1.72 0.041 0.017 0.40 0.45 0.01 40.6 0.37 0.33 0.088 0.060 0.046 9.44

The designations CWI28, CWI32, and CWI38 are used

throughout this paper for these alloys. The alloys chosen
were supplied by Georgia Iron Works (GIW) Industries.
The sand casting process was used for production of the
CWI-alloy bars. The cast bars were 51 mm thick, 102 mm
wide, and 610 mm long.

B. Apparatus
The microstructural characterization of the CWIs was
performed using a scanning electron microscope equipped
with an energy dispersive X-ray analyzer (SEM-EDAX).
Care was taken to ensure that the kV setting during EDX
point analysis maintained an interaction volume between
the electron beam and the phase under analysis of ;1 mm
in diameter. A field emission scanning electron microscope
(FEGSEM) was also used in this work to investigate the
presence of martensite in the eutectic matrix and Fig. 1—Schematic representation of the three-electrode cell for electro-
chemical tests.
precipitated carbides around primary M7C3 carbides of
the CWI alloys. The crystalline phases were characterized
using a Siemens D500 X-ray diffractometer with copper
electrode. The corrosion cell consisted of the CWI speci-
radiation Ka1 1 Ka2 and a scintillation counter (point
men as the working electrode, a platinum wire/mesh coun-
detector), which produces a u vs 2u scan (Bragg-Brentano
ter electrode, and an Ag/AgCl reference electrode.
geometry).
DC anodic polarization tests in static conditions were
The carbide area fraction was automatically measured
conducted at 18 °C, 40 °C, and 60 °C. According to the
using commercial image-analysis software (ImageJ). For
following protocol, the sample potential was polarized
this purpose, the specimens were ground with a diamond
away from Ecorr in a positive direction at a scan rate of
disc and SiC papers (320, 400, and 600 grit), polished with
15 mV/min. Once the current density reached 500 mA/cm2,
6-mm and 1-mm diamond paste, respectively, and rinsed
the potential scan was reversed and the potential was moved
first with distilled water and then with acetone, and finally
at the same scan rate back to Ecorr.[11] The maximum current
air dried. To reveal the matrix microstructure, the CWIs
(imax) represents the value reached in the polarization test
were chemically etched with Villela’s etching reagent.[4]
once the potential scan is reversed. The extent to which imax
exceeds 500 mA/cm2 is a measure of the propagation of
corrosion after the potential is reversed.
C. Static Corrosion Tests
The specimens were connected to an electrical wire via a
Electrochemical corrosion tests were used to investigate soldering process and embedded in a nonconducting resin.
the corrosion behavior of CWI alloys in waters mimicking The test surfaces had an area of #0.5 cm2 and were ground
a recycle cooling water. The simulated recycle water was with diamond disc and SiC papers (320, 400, and 600 grit),
fully aerated and had approximately 1000 ppm of NaCl, polished with 6-mm diamond paste, and rinsed first with
and a pH of 8.5 adjusted by adding NaOH. Electrochemical distilled water and then with acetone, and finally air dried.
tests included anodic polarization scans and potentiostatic To standardize the crevice region, the exposed interface
tests. Figure 1 depicts a typical three-electrode cell for between the resin and the sample edges was sealed with
electrochemical corrosion tests. Electrical current from a lacomit varnish.
potentiostat shifts a working electrode from its free corro- In potentiostatic tests, the potential of the working elec-
sion potential or Ecorr to a potential value determined by the trode was fixed after scanning to 0 V (Ag/AgCl). Potentio-
magnitude of the current. Changing an electrode potential static tests were conducted with the primary aim of
from its Ecorr is referred to as polarization. To maintain determining the ‘‘critical’’ corrosion-initiation temperature
electrode electrical neutrality, electrical current has to be for each alloy. The current density as a function of temper-
concurrently drawn from a test electrode when current is ature was then recorded as the temperature was increased
supplied by potentiostat to a counter-electrode (and vice from ambient temperature (18 °C) up to 90 °C at a rate of
versa). The working electrode polarization is measured as 2 °C/min. Each test was repeated at least three times and a
a potential difference between the reference and working mean value was obtained.

2340—VOLUME 37A, AUGUST 2006 METALLURGICAL AND MATERIALS TRANSACTIONS A

 III. RESULTS AND DISCUSSION
This section will detail several points relating to the
corrosion behavior of CWIs in the recycled cooling water.
First, the microstructural characterization of CWIs will be
presented, with emphasis on how the microstructural fea-
tures can affect the corrosion resistance of the materials.
Further discussion on the corrosion results as a function of
temperature is then presented.
A. Microstructural Characterization
Back-scattered electron (BSE) SEM images showing the
microstructure of the CWI alloys are shown in Figure 2.
Fig. 2—Back-scattered electron images of high-chromium white cast iron
for (a) the CWI28 alloy, (b) CWI32 alloy, and (c) CWI38 alloy.
METALLURGICAL AND MATERIALS TRANSACTIONS A
The CWI28 alloy contains large primary M7C3 carbides
with a rosette morphology and eutectic cells composed of
finer M7C3 carbides and austenite (Figure 2(a)). The micro-
structures of the CWI32 and CWI38 alloy are composed
of primary M7C3, with eutectic cells (M7C3 1 g) filling the
space between them. The carbides in the CWI32 alloy are
principally a combination of blade-like and rod-like struc-
tures (Figure 2(b)). However, the blade-like types of car-
bide are completely observed in the CWI38 alloy, and the
size of primary M7C3 carbides (Figure 2(c)) is greater than
those in the CWI32 alloy. In addition, there are some pre-
cipitated carbides aligned around the primary carbides in
both the CWI32 and CWI38 alloys. The carbide precipita-
tion in the CWI32 and CWI38 alloys can be clearly seen
on the SEM images in Figures 3(a) and (b), respectively. The
carbide area fractions for the CWI28 alloy, CWI32 alloy, and
CWI38 alloy are 30 pct, 39 pct, and 51 pct, respectively.
The chromium-depleted region can be clearly seen in
Figure 2 as a brighter color at the periphery of the large
M7C3 carbides. This region occurs when solidification takes
place during casting. It is well known that the periphery of
the primary carbides solidifies later relative to the central
part, and the temperature at the periphery would also be
higher than in the center.[3,4] Consequently, mass transfer
occurs faster in this region. This phenomenon occurs
together with the formation of fine carbides around the
primary carbides, as the depleted elements coming from
the primary carbides will react with the elements (e.g.,
Fig. 3—Precipitated carbides around primary M7C3 carbide for (a) the
CWI32 alloy and (b) the CWI38 alloy.
VOLUME 37A, AUGUST 2006—2341
carbon) in the remaining liquid in front of the solidified
carbides.
The element depletion is less prominent and the carbide
precipitation is generally absent in CWI28 because it has
the lowest carbon concentration and the cooling rate of
solidification may be lower than for CWI32 and CWI38.
Therefore, the rosette-like M7C3 carbides are formed
because of the wide range of temperature between solid
and liquid during solidification. The primary carbides in
CWI28 take longer to grow, and the element supply
becomes lower as the temperature falls. Consequently, in
the latter stages of solidification, the primary carbides sol-
idify with relatively lower element concentrations than in
the early solidification stages. The latter primary carbides
are believed to be the M3C type, which have a lower ratio
of Cr to C. This observation is supported by the EDX
mapping analysis for Cr shown in Figures 4(a) and (b). It
can be seen that Cr element analysis shows less contrast in
the M3C region compared to the M7C3 region (Figure 4(b)).
The phase analyses were done using XRD (Figure 5). It
can be seen that all CWIs have a predominant primary M7C3
phase, in addition to austenite iron (g) and finer M7C3 car-
bides. However, there are some shifts in d-spacing of partic-
ular phases. This observation may be due to the different
parameters during casting, such as pouring superheat and
solidification cooling rate. These parameters can affect the
crystal lattice of the phase due to differences in stress level
applied during the process. It can also be seen that there is
one secondary phase appearing in all alloys, which is mar-
tensite at 2u of 64.343, and a phase of M3C type of carbide at Fig. 4—The SEM-EDX mapping analysis for CWI28 CWI alloy (a)
a 2u of 48.431 in CWI28 alloy only.[12,13] There is also an microstructure and (b) Cr analysis.
indication of possible phases (weak peaks), which are the
M2C or the M23C6 types of carbide at 2u of 52.05.[3,14]
The high-resolution SEM images in Figure 6 show that
the austenite surrounding some carbide grains is trans-
formed to martensite platelets, which exhibit a spear-like
morphology. Choi and Chang reported that molybdenum
in the g-solid solution can raise the martensite transforma-
tion temperature (Ms).[14,15] They also found that the Ms
increases as the ratio of Cr/C increases because it reduces
the carbon content in the austenite. Therefore, it is expected
that the amount of martensite phase in alloys CWI32 and
CWI28 should be higher than in the CWI38 alloy, since
the molybdenum content in the CWI32 alloy is highest
and CWI28 has the highest Cr/C ratio value. In the case
of CWI32 and CWI38 alloys, the formation of martensite
surrounding carbide grains can be explained as follows. Fig. 5—XRD spectrum for the three CWI alloys.
As mentioned previously, a Cr-depleted region forms at the
periphery of the M7C3 carbides, and the fine carbide precip-
B. Potentiodynamic and Potentiostatic Behaviors
itation occurs in the vicinity of the M7C3 carbides. Therefore,
the carbon content in the austenite surrounding the carbides The anodic polarization characteristics of CWIs at test
will be reduced and can favor the formation of martensite. temperatures of 18 °C, 40 °C, and 60 °C are illustrated in
As the solubility of Mo into the austenite fcc of Fe is very Figures 7(a), (b), and (c), respectively. Figure 7 shows that
limited (about 3 wt pct) and metastable,[16] some Mo may even though the materials show active corrosion behavior,
be rejected from the austenite matrix in the CWI32 alloy. there are very low currents in the region near Ecorr, indicat-
Therefore, the CWI32 alloy, which has the highest Mo ing the presence of a very limited passivity on the g-eutec-
content, is expected to have more martensite phase than tic matrix of the Cr-white irons. As the temperature is
the two other alloys. The excess of molybdenum in the increased (40 °C and 60 °C), the maximum current (imax),
austenite matrix is tied up with carbon, and it may form which represents the value reached in the polarization test
Mo2C as fine carbides scattered in the matrix in addition to once the potential scan is reversed, exceeds 500 mA/cm2.
fine M7C3 eutectic carbides, and as the amount of carbon in This observation indicates that there is pit propagation or
the matrix is also reduced, then martensite is formed.[14] some form of localized corrosion after the potential is

2342—VOLUME 37A, AUGUST 2006 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 6—FEGSEM images show the presence of martensite phase in
(a) the CWI28 alloy, (b) CWI32 alloy, and (c) CWI38 alloy.
reversed,[11] as confirmed from the optical micrographs in
Figures 8, 9, and 10 for the CWI28 alloy, CWI32 alloy, and
CWI38 alloy, respectively. The positive hysteresis observed
in all conditions in the reverse scan indicates that once the
corrosion attack at matrix/carbide interfaces is introduced,
it propagates into the matrix. It also can be seen that Ecorr
shifts to negative values with increasing temperature, which
indicates that the CWIs become more active as the temper-
ature increases. The corrosion mechanisms will be dis-
cussed in detail in the next section.
Figure 11 presents the corrosion current density (icorr) of
the three CWI alloys as a function of temperature. It can be
generally concluded that the CWI38 alloy shows the best
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 7—Anodic polarization curves for the three different Cr/C chromium
white irons in recycle cooling water (pH 8.5, 1000 ppm of NaCl) at
(a) 18 °C, (b) 40 °C, and (c) 60 °C.
corrosion resistance under static conditions, followed by
the CWI28 alloy; the CWI32 alloy in all conditions con-
sistently shows the lowest resistance. The reasons for this
observation are as follows:
1. Figure 2 clearly shows that CWI28, with the highest Cr/C
value, has the largest area fraction of matrix, and the area
fractions for the CWI32 and CWI38 alloys look similar.
2. Even though the CWI32 alloy has more chromium than
CWI28, the CWI28 alloy shows better corrosion resist-
ance than the CWI32 alloy. This is because the CWI32
alloy contains much more carbon and has the lowest
Cr/C value; more carbon is therefore tied up with chro-
mium to form M7C3 carbides (Table I).
3. The amount of chromium in solid solution in the aus-
tenite as a main contributor for corrosion resistance is
VOLUME 37A, AUGUST 2006—2343
Fig. 8—Corrosion mechanisms on CWI28 alloy (Cr/C 5 10.44) after
anodic polarization at (a) 18 °C, (b) 40 °C, and (c) 60 °C in recycle cooling
water (pH 8.5, 1000 ppm of NaCl).
[1,7–9]
then reduced. The measurement of chromium com-
position in carbides and in the matrix is discussed in the
next section.
In addition to obtaining information regarding the corro-
sion behavior of each CWI from the anodic polarization as
discussed in the previous section, it is possible to analyze
current transients as the temperature is increased in poten-
tiostatic tests. Here, the potential of the working electrode
was fixed after scanning to a potential of 0 V. The current
density as a function of temperature was then recorded as
the temperature was increased from ambient temperature
(18 °C) up to 90 °C at a rate of 2 °C/min. Figure 12 shows
2344—VOLUME 37A, AUGUST 2006
Fig. 9—Corrosion mechanisms on CWI32 alloy (Cr/C 5 9.2) after anodic
polarization at (a) 18 °C, (b) 40 °C, and (c) 60 °C in recycle cooling water
(pH 8.5, 1000 ppm of NaCl).
clearly that the current measured on the CWI32 alloy is
much greater than on other two alloys over the whole range
of temperature. This confirms the superior resistance of the
CWI38 alloy and the poor resistance of the CWI32 alloy as
presented from potentiodynamic tests. There is an immedi-
ate increase in current density even at low temperature for
CWI32 alloy. A critical value akin to the CPT or CCT
measured on stainless steels,[17] where a sharp increase in
the current occurs, is not really observed, but a small
change in the i/T slope appears to exist at 45 °C.
METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 10—Corrosion mechanisms on CWI38 alloy (Cr/C 5 9.44) after
anodic polarization at (a) 18 °C, (b) 40 °C, and (c) 60 °C in recycle cooling
water (pH 8.5, 1000 ppm of NaCl).
The small current registered on the CWI28 and CWI38
alloys in the first stage of tests indicates that some very
limited passivity is offered by the austenite matrix, as dis-
cussed earlier. These alloys have a small ratio of Cr in the
M7C3 carbides to Cr in the matrix compared to the CWI32
alloy. Therefore, there is enough chromium to generate
limited passivity in the matrix. This observation is absent
in the CWI32 alloy. Figure 13(a) confirms that corrosion
attack occurs around the precipitated and fine eutectic car-
bides. However, all alloys show similar behavior during
potentiostatic tests from 45 °C until the peak temperature
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 11—Corrosion current density (icorr) for the three different Cr/C of
high-chromium white cast iron as a function of temperature in recycle
cooling water (pH 8.5, 1000 ppm of NaCl).
Fig. 12—Potentiostatic curves (0 V) with temperature variation from 18 to
90 °C on high-chromium white cast irons in recycle cooling water (pH 8.5,
1000 ppm of NaCl).
reached. At 45 °C and beyond, the principal corrosion
mechanism is to pit propagation.[17]
Beyond the temperature of 70 °C for CWI28 and CWI32
and 78 °C for CWI38, the current density then decreases. The
main reason for this decrease is the reduction of dissolved
oxygen content with the increased temperature.[11] Figure
13(b) shows that there is pitting in the matrix and at the
matrix/carbide interface. The primary carbides appear to be
the only phase that remains unaffected and offers passivity.
C. Corrosion Mechanisms
Figures 8 to 10 show that corrosion attack (dark color)
and the pits in the eutectic matrix are generally more prev-
alent as the temperature increases. However, the primary
carbides seem untouched by the attack. Optical micro-
graphs at higher magnification showing corrosion mecha-
nisms after anodic tests at 40 °C are presented in Figure 14.
It is quite clear that corrosion attack is initiated around the
M7C3 primary carbides, as confirmed by optical micro-
graphs after anodic polarization tests at 18 °C in Figures
8(a), 9(a), and 10(a), where black lines are observed sur-
rounding the carbides. The black lines occur in the element-
depleted region (e.g., Cr) that envelopes chromium-rich
zones in the bulk carbide. Therefore, the corrosion attack at
this site can be caused by three factors: microgalvanic inter-
action between two regions, simply chromium depletion lead-
ing over corrosion resistance, and microcrevice attack due to
a restricted oxygen supply inside the microcrevice areas at
VOLUME 37A, AUGUST 2006—2345
Fig. 13—Corrosion mechanisms on CWI32 alloy after potentiostatic test
(a) at 40 °C and (b) at 70 °C in recycle cooling water (pH 8.5, 1000 ppm of
NaCl).

the carbide/depleted region interface. The composition differ-

ences of elements (Cr, Fe, and C as the main constituents) are
confirmed by EDX analysis on three regions: in the M7C3
carbides, at their periphery, and in the matrix. The results are
presented in Table II. In general, it can be concluded from
Table II that there is a significant reduction of the chromium
in the depleted region compared to the carbide regions. The
biggest reduction occurs in the matrix.
Table II confirms that the ratio of chromium content
in the M7C3 carbide and in the matrix (CrM7C3/Crmatrix)
follows the ranking of the corrosion rate (Figure 11). The
CWI32 alloy shows the highest value of CrM7C3/Crmatrix.
This indicates that in fact chromium in the CWI32 alloy is
used largely to form carbides rather than to form solid
solution in the eutectic austenite. Even though the CWI38
has a much smaller value of Cr/C than the CWI28 alloy, the
CWI38 alloy shows the opposite value of CrM7C3/Crmatrix.
This is because the CWI38 alloy has a very high chromium
content (40.6 wt pct). Even though there is a relatively high
C content (4.3 wt pct), there is still excess Cr in the CWI38
alloy to ensure a very high concentration in the matrix.
Another reason why the CWI28 and CWI32 alloys show
less corrosion resistance than the CWI38 alloy is the effect
of martensite phase and small M2C types of carbides in
the eutectic matrix. As already discussed, the CWI28 and
CWI32 alloys have a higher martensite amount in the
Fig. 14—Corrosion mechanisms on (a) CWI28 alloy, (b) CWI32 alloy,
and (c) CWI38 alloy after anodic polarization at 40 °C in recycle cooling
water (pH 8.5, 1000 ppm of NaCl).
matrix than the CWI38 alloy. It is then suggested that the
presence of martensite can deteriorate corrosion resistance
of the alloy, since the morphology of martensite phase is
thin flakes, which have many interfaces with retained aus-
tenite matrix. These interfaces provide potential sites for
pitting attack.[18,19] The presence of the M2C type of carbide
(believed to be Mo2C) may also exaggerate the interface
effects on the corrosion mechanisms of this alloy. The EDX
measurements for Cr, C, and Fe in the matrix region may
include the fine eutectic carbides (M7C3), austenite, and
the other variants of fine carbides (i.e., M2C and M23C6).
Therefore, the EDX analysis in this region indicates the

2346—VOLUME 37A, AUGUST 2006 METALLURGICAL AND MATERIALS TRANSACTIONS A

Table II. Chemical Point Analysis of SEM-EDX (Wt Pct) for 2. The decrease in Cr/C ratio promotes the primary car-
the High-Chromium Cast Iron Alloys bides’ morphology to a blade-like shape. A combination
of small Cr/C ratio and high Cr content leads to the
Alloy-(Cr/C)
largest carbide area fraction.
Wt pct element CWI32 CWI38 CWI28 3. The corrosion mechanisms are linked to specific features
(the M7C3 carbide) (9.2) (9.44) (10.4) of the microstructure. The corrosion behavior/properties
C 8.97 9.65 9.04 of the CWI alloys are dominated by their matrix alloys,
Cr 62.65 65.41 64.14 since the hard phases (i.e., M7C3 carbides) show inert
Fe 27.83 24.03 26.88 behavior during anodic polarization.
Wt pct element CWI32 CWI38 CWI28 4. There is not a simple relationship between Cr/C ratio
(depleted region (9.2) (9.44) (10.4) and corrosion resistance; other factors are likely to be
around the important. The corrosion resistance of the CWI alloys
M7C3 carbide) strongly depends on the ratio of chromium content in the
C 6.35 4.18 6.33 M7C3 carbide to that in the matrix (CrM7C3/Crmatrix).
Cr 36.10 27.89 50.40
Fe 54.95 65.87 42.55
5. The addition of nickel in the matrix can also enhance
the corrosion resistance of CWI alloys, but not so
Wt pct element CWI32 CWI38 CWI28 significantly.
(the matrix) (9.2) (9.44) (10.4)
C 2.42 4.72 3.66
Cr 13.33 18.77 15.1 ACKNOWLEDGMENTS
Fe 82.44 73.83 76.96
The authors are grateful for the financial support for
CrM7C3/Crmatrix 4.70 3.48 4.24 F.R. from Syncrude, Canada, and Heriot-Watt University,
Edinburgh.
maximum values; consequently, the alloys that act as a solid
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additions on corrosion resistance in high-chromium ferritic 2. P. Dupin, J. Savema, and J.M. Schissler: AFS Trans., 1983, vol. 90,
iron.[8,9] Since all the white iron alloys used in this work have pp. 711-18.
3. Ö.N. Doan: Scripta Mater., 1996, vol. 35, pp. 163-68.
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ance of the chromium white irons. Table I shows that the 7. S.W. Watson, B.W. Madsen, and S.D. Cramer: Wear, 1995, vol. 181–
CWI28 alloy contains a slightly higher nickel composition 183, pp. 469-75.
compared with two other alloys. This can also explain why 8. E. Zumelzu, C. Cabezas, O. Opitz, E. Quiroz, L. Goyos, and A.
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ance of CWIs depends not only on the chromium content; it 10. J.T.H. Per: AFS Trans., 1984, vol. 92, pp. 599-622.
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IV. CONCLUSIONS 13. S.D. Carpenter, D. Carpenter, and J.T.H. Pear: Mater. Chem. Phys.,
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morphology. 20. J. Tomiska: J. Alloys Compd., 2004, vol. 379, pp. 176-87.

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