Materials Letters 57 (2003) 4456 – 4459

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X-ray diffraction study of M7C3 carbide within a high

chromium white iron
S.D. Carpenter a,*, D. Carpenter b
a
Department of Metallurgy of Materials, Birmingham University, UK
b
FURB, Blumenau, Brazil
Received 12 November 2002; accepted 12 December 2002

Keywords: X-ray diffraction; M7C3 carbide; Chromium white iron

High chromium content white irons containing up
to 30% chromium are used commercially for compo-
nents that are designed to endure harsh abrasive con-
ditions. Such conditions are met within the raw
materials processing industry, for example, during
the crushing and grinding of coarse aggregates and
mineral-bearing ores. High chromium irons are essen-
tially based on the iron –chromium – carbon ternary
diagram, and in the as-cast condition, they consist of
hard eutectic (Fe,Cr)7C3 carbides held in an austenitic
matrix. The austenitic matrix of these alloys can be
further hardened by heat treatment. Heat treatment
involves the destabilisation of the matrix by the
precipitation of alloy carbides. The subsequent alloy
depletion increases the martensite start ‘Ms’ tempera-
ture of the austenitic matrix allowing the transforma-
tion to martensite. The matrix hardenability of these
alloys may be improved by the addition of a small
amount of molybdenum.
Eutectic (Fe,Cr)7C3 carbides are reported to be
relatively unaffected by heat treatment [1]. However,
* Corresponding author.
E-mail address: s.d.carpenter@bham.ac.uk
(S.D. Carpenter).
Pearce [2] has reported evidence of a in situ transfor-
mation at the periphery of hexagonal M7C3 to cubic
M23C6 after a hardening treatment. This transforma-
tion has only been observed within very high chro-
mium content irons. Furthermore, no strict crystallo-
graphic relationship has been found between these
two forms of carbide [3,4]. As part of a character-
isation study, this paper may present a small insight
into the mechanism of this particular transformation
within a high chromium white iron [5].
X-ray diffraction (XRD) specimens were prepared
from an as-cast white iron containing 2.72 wt.%
carbon 26.6 % chromium, 0.78 wt.% silicon, 0.17
wt.% nickel, and 0.25 wt.% manganese. Specimens
were also prepared from the same alloy after being
given a commercial heat-treatment cycle. The heat
treatment consisted of three stages: (i) a 1-h anneal at
800 jC and furnace cool to ambient, (ii) a 1-h destabi-
lisation treatment at 1025 jC followed by air cooling,
and (iii) a 1-h temper at 450 jC also followed by air
cooling. XRD specimens were cut from the material
with a precision cutting wheel and measured
10
10
3 mm in thickness so as to accommodate
the Philips X’pert XRD goniometer. Each 10-mm
square face was ground to 800-grit finish using
tungsten carbide paper. This was followed by a

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 S.D. Carpenter, D. Carpenter / Materials Letters 57 (2003) 4456–4459 4457

Fig. 1. Diffractometer trace for the as-cast 26.6% chromium white iron.

mechanical polish to a 1-Am diamond finish and final fractometer was set to scan from an angle of 10 –140j
electropolish in a solution of 10% oxalic acid in water. using a copper K-alpha X-ray source and a nickel filter.
Figs. 1 and 2 are diffractometer traces from the as- The hk(i)l indices for diffraction intensities that are less
cast and heat-treated samples, respectively. The dif- than 2% of the strongest intensity are not shown for

Fig. 2. Diffractometer trace for the heat-treated 26.6% chromium white iron.
4458 S.D. Carpenter, D. Carpenter / Materials Letters 57 (2003) 4456–4459

clarity. Crystallographic data from the diffractometer Table 2

are presented in Tables 1 and 2. These tables show the X-ray diffraction results for the heat-treated 26.6% chromium alloy
sin2h values obtained for phase constituents, where h is d-spacing Intensity sin2h hk(i)l N Phase
(mm) (%)
the Bragg angle. These tables also identify the d-
spacings of phase constituents and show the respective 2.2804 26.3 0.1141 145̄0 28 carbide
2.0316 100.0 0.1438 101 1 martensite
hkil and hkl indices. The actual and calculated values
2.0264 87.2 0.1445 110 2 martensite
for N are shown in some instances, where N is equal to 1.8360 3.4 0.1760 066̄1 36 carbide
h2 + hk + k2 in the case of hexagonal materials and 1.7425 11.2 0.1954 448̄0 48 carbide
h2 + k2 + l2 in the case of cubic materials. 1.7388 7.9 0.1962 448̄0 48 carbide*
The crystallographic data presented in Tables 1 and 1.4400 9.1 0.2861 002 0 martensite
1.4312 11.4 0.2897 088̄1 64 carbide+
2 were used to calculated the lattice parameters of the
(200) mart
eutectic carbide of interest for both the as-cast and 1.4178 3.4 0.2952 112 2 martensite
heat-treated material. The calculations of the other 1.2721 3.9 0.3666 022 8 austenite
phase constituents can be found in reference [5]. The 1.1720 12.5 0.4319 211 5 martensite
lattice parameters a and c for the hexagonal (Fe,Cr)7C3 1.1614 6.9 0.4399 66120 108 carbide
carbide were determined from Eq. (1). Carbide with a slightly smaller lattice parameter a is indicated by *.
N.B. The secondary carbides present within the martensitic matrix

 of the heat-treated iron are less than 1 Am in size and were not
4 h2 þ hk þ k 2 l 2 detected by XRD [5]. Therefore, data for secondary carbide does
þ k ¼ 2sinh ð1Þ not appear in the table.
3 a2 c2

Whereby parameter a is twice the interplanar spac- occurs for (Fe,Cr)7C3 because the crystal is not a close
ing for (112̄0), and c is the interplanar spacing for the packed structure.
(0001). It must be noted that the (0001) reflection The (448̄0) reflection was used to calculate the
lattice parameter a for hexagonal carbide because the
Table 1
X-ray diffraction results for the as-cast 26.6% chromium alloy l2/c2 term in Eq. (1) becomes zero when l (hkil) is equal
d-spacing Intensity sin2h hk(i)l N Ncalc Phase
to zero The d-spacing and sinh for the (448̄0) were
(mm) (%) selected for two reasons, firstly because this peak was
2.280 23.3 0.1141 246̄0 28 28.0 carbide
very close to that in the ASTM index and positive
2.102 8.2 0.1343 022̄2 4 – carbide* identification of this diffractometer peak was made,
2.081 62.3 0.1371 111 3 3.0 austenite and secondly because l is equal to zero. The lattice
2.074 40.6 0.1379 111 3 – austenite# parameter a, d-spacing, and the sinh value for the
2.037 45.8 0.1430 246̄1 28 – carbide (246̄1) reflection were used to calculate c. The (246̄1)
2.012 17.5 0.1465 066̄0 36 36.0 carbide
1.955 2.3 0.1553 156̄1 31 31.0 carbide
planes were used because they gave the strongest
1.837 4.3 0.1758 066̄1 36 36.1 carbide carbide reflection.
1.804 100.0 0.1816 002 4 – austenite The hkil indices for corresponding d-spacings and
1.743 7.1 0.1953 448̄0 48 – carbide sinh values obtained from the diffractometer were
1.432 3.1 0.2893 088̄1 64 63.9 carbide calculated using Eq. (1). The permissible values of
1.275 3.6 0.3651 022 8 8.0 austenite
1.269 2.8 0.3686 022 8 8.1 austenite#
h2 + hk + k2 were found by trial and error by substitut-
1.178 3.5 0.4274 466̄2 76 – carbide* ing different values for l, where l is an integer. The
1.167 6.0 0.4356 0,10,101 100 – carbide** permissible values of h2 + hk + k2 according to Eq. (1)
1.162 5.0 0.4393 66120 108 107.9 carbide are 1, 3, 4, 7, 9, 12, 13, 16, 19, 21, 25, 27, 28, etc. The
1.087 4.7 0.5016 113 11 11.1 austenite sequence can be continued by substituting whole
0.903 3.2 0.7277 004 16 16.0 austenite
0.828 2.3 0.8661 133 19 19.1 austenite
numbers for h and k. Values that do not fall in this
0.826 2.6 0.8678 133 19 19.0 austenite# sequence are referred to as forbidden reflections.
Carbides with a slightly different c/a ratio are indicated with * and The value for a was found to be 1.394 F 0.005 nm,
**. and the value for c was 0.452 F 0.005 nm. A slight
Eutectic austenite is indicated with #. contraction along the c-axis was observed for carbide*.
 S.D. Carpenter, D. Carpenter / Materials Letters 57 (2003) 4456–4459
The precise c/a ratios could not be determined for
carbides * and ** because other corresponding dif-
fraction intensities were not found in the diffractome-
ter trace. The a and c values for (FeCr)7C3 in the heat-
treated 26.6% chromium alloy (Table 2) were found to
be 1.394 F 0.005 and 0.452 F 0.005 nm, respectively.
These are in good agreement with those for the as-cast
alloy and are in good agreement with those reported by
Dyson and Andrews [6].
The unit cell of an M7C3 is described as having a
hexagonal shape and a rhombohedral symmetry. The
atomic structure of (Fe,Cr)7C3 consists of an octahe-
dron of metal atoms. The top and bottom faces of the
octahedral are perpendicular to the c-axis. Triangular
prisms radiate from the other six faces, three inclined
upward and three inclined downwards. The carbon
atoms are located in the centres of the triangular prisms
and complete the rhombohedral structure [7,8].
The triangular prisms are slightly skewed to tes-
sellate with the triangular prisms in the adjacent
structure via a tetrahedra. The lattice parameter a
refers to two neighbouring rhombohedra. The lattice
parameter c is the height of one rhombohedron. The
octahedral centres at the centres of the rhombohedra
act as principal scattering centres and are responsible
for the hexagonal symmetry of the diffraction patterns
[5,9,12].
The lattice parameters ar and ar of a rhombohedral
structure of can determined from the lattice parameters
c and a of a hexagonal unit cell [10], where
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ar ¼ 1=3 3a2 þ c2
and
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
a During Transmission Electron Microscopy of a (Fe,Cr)7C3
sin ¼ 2=2 3 þ ðc=aÞ2
2
Substituting a as 1.394 nm and c as 0.452 nm, ar
equals 0.819 nm and a equals 116.7j. It is interesting
4459
to note that an angle a of 109.47j would result in a
body-centered cubic structure [11]. The difference of
7.2j could account for the in situ transformation of
hexagonal (Fe,Cr)7C3 to cubic (Fe,Cr)23C6 carbide
during hardening heat treatments of very high chro-
mium content white irons [2– 4].
References
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formation mechanisms in Si alloyed high-chromium white cast
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bides in heat-treated 30% chromium cast iron, Journal of Ma-
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