Materials Characterization 99 (2015) 52–60

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Effects of W on microstructure of as-cast 28 wt.%Cr–2.6 wt.%C–(0–10)

wt.%W irons
S. Imurai a, C. Thanachayanont b, J.T.H. Pearce b, K. Tsuda c, T. Chairuangsri d,⁎
a
Department of Physics and Materials Science, Chiang Mai University, Chiang Mai 50200, Thailand
b
National Metal and Materials Technology Center, Pathumthani 12120, Thailand
c
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan
d
Department of Industrial Chemistry, Chiang Mai University, Chiang Mai 50200, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: Microstructures of as-cast 28 wt.%Cr–2.6 wt.%C irons containing (0–10)wt.%W with the Cr/C ratio about 10 were
Received 24 August 2014 studied and related to their hardness. The experimental irons were cast into dry sand molds. Microstructural in-
Received in revised form 6 November 2014 vestigation was performed by light microscopy, X-ray diffractometry, scanning electron microscopy, transmis-
Accepted 10 November 2014
sion electron microscopy and energy-dispersive X-ray spectrometry. It was found that the irons with 1 to 10
Available online 13 November 2014
wt.%W addition was hypereutectic containing large primary M7C3, whereas the reference iron without W addi-
Keywords:
tion was hypoeutectic. The matrix in all irons was austenite, partly transformed to martensite during cooling. The
Microstructure volume fractions of primary M7C3 and the total carbides increased, but that of eutectic carbides decreased with
Electron microscopy increasing the W content of the irons. W addition promoted the formation of W-rich M7C3, M6C and M23C6. At
High chromium cast irons about 4 wt.%W, two eutectic carbides including M7C3 and M6C were observed together with primary M7C3. At
Effects of tungsten 10 wt.%W, multiple carbides including primary M7C3, fish-bone M23C6, and M6C were observed. MxC where
Carbides x = 3 or less has not been found due possibly to the high M/C ratio in the studied irons. W distribution to all car-
bides has been determined increasing from ca. 0.3 to 0.8 in mass fraction as the W content in the irons was in-
creased. W addition led to an increase in Vickers macro-hardness of the irons up to 671 kgf/(mm)2 (HV30/15)
obtained from the iron with 10 wt.%W. The formation of primary M7C3 and aggregates of M6C and M23C6 were
the main reasons for hardness increase, indicating potentially improved wear performance of the as-cast irons
with W addition.
© 2014 Elsevier Inc. All rights reserved.

1. Introduction
High chromium white cast irons containing 12–30 wt.%Cr are widely
used as cast wear parts in mining, minerals and cement industries due
to their superior wear resistance and relatively low production cost [1,
2]. Most of these irons are hypo-eutectic and solidify as primary austen-
ite dendrites followed by a eutectic mixture of austenite and M7C3 car-
bides. Hyper-eutectic irons containing primary M7C3 are used for
certain applications.
Some additional carbide-forming elements, particularly Mo and V,
have been added into high chromium cast irons for improving their
properties (e.g. [3]). Recently, the influence of Mo addition on micro-
structure of as-cast 28 wt.%Cr white cast irons has been reported by
the present authors [4]. However, less information can be found for
the case of tungsten addition. Dupin and Schissler [3] studied as-cast
20 wt.%Cr–2.6 wt.%C white cast iron (Cr:C ratio about 7.7) with 1.2
wt.%W addition. They found only W-containing M7C3 and reported no
difference in the microstructure of the W-containing iron as compared
⁎ Corresponding author.
E-mail addresses: tchairuangsri@gmail.com, torranin.c@cmu.ac.th (T. Chairuangsri).
to the basic iron. On the other hand, at the W content higher than 10
wt.%, Sawamoto et al. [5] reported the formation of M6C as fine eutectic
structure in the final stage of solidification of high chromium white cast
irons. Yu and Matsubara [6] studied several multicomponent white cast
irons containing carbide forming elements including Cr, V, Mo and W.
They reported rod-like M7C3 and fish bone-like M6C in as-cast 5
wt.%Cr–3 wt.%C–2.5 wt.%Mo–12.5 wt.%W iron (Cr:C ratio about 1.7). It
was also noted that the M2C precipitates preferably in the iron with a
low W/Mo ratio (e.g. W/Mo ratio about 1.0), the M6C in the iron with
a high W/Mo ratio (e.g. W/Mo ratio about 5.0) and the MC in the iron
with V addition. Mousavi Anijdan et al. [7] investigated as-cast 28
wt.%Cr–3 wt.%C–(0 to 2.5)wt.%W irons (Cr:C ratio about 9). The forma-
tion of WC carbides in the matrix domain and large hexagonal (often
hollow) M7C3 carbides apart from eutectic carbides was found in the
W-containing irons. The total amount of eutectic carbides
was increased with increasing W content. Recently, Lv et al. [8] report-
ed, based on scanning electron microscopy (SEM), that tungsten
addition at relatively lower content of 0 to 3 wt.% led to a formation
of WC1 − x, W6C2.54 and W3C in 24 wt.%Cr–3 wt.%C white cast irons
(Cr:C ratio about 8) and W2C appears after heat treatment, but WC as
reported previously by Mousavi Anijdan et al. [7] was not observed

http://dx.doi.org/10.1016/j.matchar.2014.11.012
1044-5803/© 2014 Elsevier Inc. All rights reserved.
 S. Imurai et al. / Materials Characterization 99 (2015) 52–60 53

due possibly to the higher content of W. It was also noted that tungsten
distributed uniformly in the matrix and carbides, indicating an equal ef-
fect on the hardness and strength of both matrix and carbides. There-
fore, the bulk hardness and the matrix microhardness both increased
gradually as the tungsten content increased reaching the peak at
about 67HRC and 913HV, respectively. Heydari et al. [9] studied the ef-
fect of carbon content on carbides in several (21 to 22.8)wt.%Cr–(3.2 to
2.34)wt.%C white cast irons (Cr:C ratio about 6.6 to 10) with 12.8 to 10
wt.%W addition. In the irons with the carbon content more than about
3.0 wt.% (i.e. Cr:C ratio about 6.6–7.3) with 12.8 wt.%W addition, pre-
eutectic carbide (also called “hyper chromium carbide”) and fish-bone
tungsten carbide (denoted as M6C) were found. Their X-ray diffraction
(XRD) results indicated the presence of only M7C3 and M6C in the as-
cast condition, whereas W2C or WC formed after heat treatment.
In the present study, the influence of W additions in the range of 0 to
10 wt.% on the microstructure of as-cast 28 wt.%Cr–2.6 wt.%C irons (the
Cr:C ratio about 10) was investigated by light microscopy (LM), scan-
ning electron microscopy (SEM) and transmission electron microscopy
(TEM). Phase identification was performed by X-ray diffraction (XRD),
selected-area electron diffraction (SAED), and energy-dispersive X-ray
spectroscopy (EDS) in SEM and TEM. Distinctive characteristics of
carbides in these irons were determined. Partitioning of W, carbide for-
mation, solidification sequence, and the microstructure–hardness rela-
tionship of the W-containing irons are discussed. The results from this
work are beneficial for an improvement in wear performance of high
chromium white cast irons with W addition, especially under severe
erosion–corrosion conditions.
fraction of constituents was determined by measuring area fractions
from LM or SEM micrographs as appropriate using Image J® software
and the mean value was based on 3–10 different areas. Distribution of
elements into constituents in the microstructure was determined
based on energy-dispersive X-ray spectrometry (EDS) in SEM by an
Oxford® Inca EDS detector, and the average values were based on mea-
surement from 3 to 5 different areas.
2.3. Transmission electron microscopy (TEM)
Twin-jet electropolishing was applied for preparing TEM thin foils
using a Fishione Instruments® twin-jet electropolisher operated
at 20 V and 30–50 mA. The electrolyte used was a solution containing
10 vol.% perchloric acid and 30 vol.% of 2-butoxyethanol in absolute eth-
anol maintained at −10 °C. A JEOL® JEM2010 transmission electron mi-
croscope equipped with an Oxford® Inca EDS detector was utilized and
operated at 200 kV. The average TEM-EDS values were based on mea-
surement from 3 to 5 different areas. Carbide phases were also identi-
fied by electron diffraction and interpretation was facilitated by the
MBFIT software version 3.7 developed by Tsuda and Tanaka [10].
2.4. X-ray diffraction (XRD) analysis
A Philips® X'pert diffractometer was used with a Cu Kα X-ray source
set for covering a 2θ range of 20–130° and recording data at 0.04° steps
with a speed of 0.004° min−1.

2. Materials and methods

2.1. Materials preparation
The chemical composition of the experimental alloys, obtained from
spark emission spectroscopy, is given in Table 1. Casting was performed
into dry sand molds for obtaining cylindrical bars, 25 mm in diameter
× 300 mm in length. The alloys were studied in the as-cast condition.
The composition of the alloys in terms of Cr and C contents as compared
to that in previous studies is plotted on the Fe–C–Cr liquidus surface in
Fig. 1. The density of the irons was calculated from the difference of their
weight in air and in water.
2.5. Macro- and micro-hardness measurement
A Brooks® MAT24 hardness tester was utilized for measuring
Vickers macro-hardness on unetched specimens at 30 kgf load and
15-seconds indentation time (HV30/15). A Galileo® Microscan OD
V.98 hardness tester was used for measuring Vickers micro-hardness
on certain phases or structures in etched specimens at 100 gf load and
15-seconds indentation time (HV0.1/15). The average values were
based on ten different areas.
3. Results and discussion

2.2. Light microscopy (LM) and scanning electron microscopy (SEM) 3.1. Microstructure

Standard grinding by water-lubricated silicon carbide papers and
polishing by diamond pastes down to 1 μm finish were applied. Three
etchants used for etching are including: (i) 4 g of potassium permanga-
nate and 4 g of sodium hydroxide in 100 ml distilled water (Groesbeck's
reagent), (ii) 1.5 g copper (II) chloride in a solution of 33 ml concentrat-
ed HCl, 33 ml absolute ethanol and 33 ml distilled water (Kalling's re-
agent), and (iii) 10 g of potassium ferricyanide and 10 g of sodium
hydroxide in 100 ml distilled water (Murakami's reagent). An
Olympus® BX60M light microscope was used for light microscopy. A
JEOL® 5910LV scanning electron microscope was used for scanning
electron microscopy and operated at 15 kV and a working distance
(WD) of 10 mm for backscattered electron imaging (BEI). Volume
3.1.1. The reference alloy
The reference alloy was hypoeutectic with austenite/martensite ma-
trix. Figs. 2(a) and 3(a) show the typical microstructure of the reference
iron (R) consisting of primary dendritic austenite (partly transformed to
martensite during cooling) and eutectic (austenite + M7C3). The pres-
ence of austenite, martensite and M7C3 in the R alloy was confirmed
by the XRD in Fig. 4 and TEM study in Fig. 5. Regarding EDS results
given in Table 2, two highest peaks in the order of CrKα and FeKα
peaks with the Fe/Cr atm% ratio about 0.3 to 0.5 were characteristics
of typical eutectic M7C3, whereas the two highest peaks in order of
FeKα and CrKα with relatively high Fe/Cr atm% ratio about 3.4 to 5
were those of EDS spectra from the austenite/martensite matrices.

Table 1
Chemical composition of the cast irons in this experiment.

Alloy Element (wt.%) Cr/C Casting temperature Density (g/cm3)

Fe C Cr Mo Mn Ni W Si P S

R Bal. 2.36 27.86 0.03 0.11 0.20 0.01 0.20 0.02 0.01 11.8 1538 7.62
W1 Bal. 2.87 26.67 0.03 0.15 0.22 0.99 0.44 0.03 0.01 9.3 1500 7.62
W4 Bal. 2.79 28.10 0.03 0.17 0.22 3.88 0.21 0.03 0.01 10.1 1522 7.66
W10 Bal. 2.56 27.84 0.04 0.11 0.22 9.91 0.17 0.03 0.01 10.9 1580 7.74
54 S. Imurai et al. / Materials Characterization 99 (2015) 52–60

Fig. 1. Chemical composition and the Cr/C ratio of W-containing, high chromium cast irons investigated in previous studies [3,6–9] as compared to those in the present study.

3.1.2. The W1 alloy as reported in previous studies (e.g. [11]). This is different from the case
With tungsten addition, the irons containing 1 to 10 wt.%W became of molybdenum addition reported previously [4], in which the irons
hypereutectic with relatively large, primary M7C3. This primary M7C3 is containing 1 to 10 wt.%Mo are hypoeutectic or eutectic/peritectic. At
typically hexagonal in cross-section and often hollow filling by austenite 1 wt.% W addition, the W1 alloy consisted mainly of primary M7C3

Fig. 2. Light micrographs show the microstructure of the irons: (a) the reference iron (R), (b) 1 wt.%W addition (W1), (c) 4 wt.%W addition (W4) and (d) 10 wt.%W addition (W10)
(etching: Groesbeck's reagent).
 S. Imurai et al. / Materials Characterization 99 (2015) 52–60 55

Fig. 3. SEM-BEIs show the microstructure of the irons: (a) the reference iron (R), (b) 1 wt.%W addition (W1), (c) 4 wt.%W addition (W4) and (d) 10 wt.%W addition (W10) (etching:
Kalling's reagent).

and eutectic (austenite + M7C3) (see Figs. 2(b) and 3(b) with XRD re-
sults in Fig. 4). As widely reported (e.g. [3,12–15]), some parts of the
austenite was also transformed to martensite in the vicinity depleted
in Cr and C close to carbides, so the matrices in the W1 alloy are a mix-
ture of austenite and martensite. No additional carbide was found apart
from typical M7C3 containing W. Results from EDS in Table 2 revealed
comparable contents of W in all constituents of the W1 alloy, both
matrices and M7C3. Si revealed in M7C3 in Table 2 is believed to be
from the adjacent matrices, and Si was therefore disregarded in deter-
mining the stoichiometric formula in Table 2.
3.1.3. The W4 alloy
At 4 wt.%W addition in the W4 alloy, the microstructure was hyper-
eutectic (Figs. 2(c) and 3(c)). XRD results in Fig. 4 indicated the

Fig. 4. XRD results: (a) the reference iron (R), (b) 1 wt.%W addition (W1), (c) 4 wt.%W addition (W4) and (d) 10 wt.%W addition (W10).
56 S. Imurai et al. / Materials Characterization 99 (2015) 52–60
Fig. 5. (a) BF-TEM micrograph shows austenite and eutectic M7C3 in the R iron. (b–c) Cor-
h i h i
responding SAED patterns from the 112 austenite zone axis and the 102 M7C3 zone
axis, respectively. (d–e) TEM-EDS spectra from austenite and M7C3, respectively.
presence of M7C3 and M6C, together with the austenite/martensite ma-
trices. M6C can be distinguished by LM on etching by the Groesbeck's re-
agent from its dark-brown color (Fig. 2(c)) or by the brightest contrast
in SEM-BEI (Fig. 3(c)). Fig. 6(a) is SEM-BEI showing the microstructure
of the W4 alloy at a higher magnification. Two chemical compositions of
eutectic M7C3 carbides were observed and hence denoted as “W-rich
eutectic M7C3” (brighter contrast in Fig. 6(a)) and “W-lean eutectic
M7C3” (darker contrast in Fig. 6(a)). This inhomogeneity of W content
is generally observed in eutectic M7C3 in the W4 alloy and indicates
that W can dissolve in M7C3 structure with a wide range of chemical
composition.
TEM observation of the W-rich, eutectic M7C3 and M6C in the W4
alloy is given in Fig. 7(a) together with the austenite matrix. SAED pat-
terns corresponding to each phases are given in Fig. 7(b)–(d), which are
in agreement to the XRD results. TEM-EDS results in Fig. 7(e)–(f) and
Table 2 reveal the two highest peaks in order of CrKα and FeKα with
the Fe/Cr atm% ratio of about 0.3 to 0.4 for both W-rich and W-lean eu-
tectic M7C3 carbides. However, the W/Cr atm% ratio of the W-rich eutec-
tic M7C3 is about twice that of the W-lean one. W may replace Cr
positions in the M7C3 structure. Regarding M6C, its characteristics
from TEM-EDS are the three highest peaks in order of FeKα, WLα and
CrKα with the Fe/Cr and W/Cr atm% ratios of about 1.7 and 0.7, respec-
tively. Despite a higher A:B ratio than 4:2 in stoichiometric formula as
shown in Table 2, the M6C in the present study corresponds to η1 =
A4B2C or A3B3C described by Goldschmidt [16], where A atoms can be
from the first long period (e.g. Fe, Cr) and B atoms from the second or
third long periods (e.g. W) in the periodic table. Comparing to high
chromium cast irons with Mo addition in a previous study [4], these
characteristic of W-containing M6C are comparable to those of Mo-
containing M6C.
3.1.4. The W10 alloy
At 10 wt.%W addition (Figs. 2(d) and 3(d)), the microstructure
of the W10 alloy consists of large primary M7C3, M23C6 aggregates
as a majority, and M6C aggregates as a minority. The brightness
level in SEM-BEI shown in Fig. 3(d) is in an order of
M7C3(M2.3C) b M23C6(M3.8C) b M6C according to the increasing M:C
ratio, which help on the recognition of these carbides. The morphology
of the M23C6 aggregates is radiating colonies with fish-bone M23C6
structure found in some areas. The M6C aggregates situate between
those M23C6 colonies. SEM investigation at a higher magnification in
Fig. 6(b) revealed two chemical compositions of M23C6: one is W-rich
M23C6 as relatively thick layers adjoining to primary M7C3 and M6C, an-
other is W-lean M23C6 associated with fine cellular/lamellar austenite in
the fish-bone structure.
Fig. 8(a–b) is BF-TEM images showing the microstructure of the
W10 alloy. Corresponding SAED patterns in Fig. 8(c)–(f) can be
interpreted as M7C3, M23C6 and M6C, which agree to the results from
XRD in Fig. 4(d). TEM-EDS spectra in Fig. 8(g)–(i) from M7C3 and
M23C6 are qualitatively comparable, so that they can be misinterpreted
easily. However, with careful inspection, comparison of the Fe/Cr and
W/Cr atm% ratios from TEM-EDS as given in Table 2 indicates that
M23C6 has higher Fe/Cr and W/Cr ratios (about 0.6 and 0.1–0.2, respec-
tively) as compared to those of M7C3 (about 0.3–0.5 and 0.01–0.04, re-
spectively). Regarding M6C in the W10 alloy, its characteristics are the
three highest peaks in order of WLα, FeKα and CrKα with the highest
Fe/Cr and W/Cr atm% ratios among all carbides (i.e. about 1.85 and
1.79, respectively) and the presence of Si with the Si/Cr atm% ratio
about 0.01. In Table 2, Si was assumed as a substitutional element in
M6C for determining its stoichiometric formula, but it is also possible
to enter into M6C as interstitial element [16].
The volume fraction (Vf) of microstructural constituents in the ex-
perimental irons is summarized in Table 3. The volume fraction of
M7C3 and M23C6 can be measured in the W10 iron because M23C6 was
etched out deeper by the Murakami's reagent [17] as can be seen in
Fig. 6(b). With increasing the W content from 1 to 10 wt.%, the volume
fractions of primary M7C3 and the total carbides increased (4.2 vol.% up
to 19.6 vol.% and 37 vol.% up to 59 vol.%, respectively), but that of eutec-
tic carbides decreased (37 vol.% down to 21 vol.% in the W4 iron). This is
quite different from the previous results [7], in which an increase of eu-
tectic carbides with increasing W content was reported. W addition pro-
motes formation of M23C6 and M6C, which is similar to the influence of
Mo reported previously [4]. The volume fraction of M6C in the W4 and
W10 irons is comparable, but the volume fraction of total carbides is
about twice and the M23C6 dominates in the W10 iron.
3.2. Solidification sequence and the formation of multiple carbides
Solidification sequence of the reference (R) iron (28 wt.%Cr–2.6
wt.%C iron) has been well-documented as: L0 → primary γ + L1, L1 →
eutectic (γ + M7C3) (e.g. [13,18]). From the results given above, W ad-
dition induced the chemical composition of the irons towards hypereu-
tectic, even at a relatively low content of 1 wt.%W. The finding of
primary M7C3 carbide agrees to the previous investigations by Mousavi
Anijdan et al. [7] and Heydari et al. [9]. Solidification sequence of
the W1 iron can be written as: L0 → primary M7C3 + L1, L1 → eutectic
(γ + M7C3). Only W-containing M7C3 was found in the W1 iron,
which is in agreement to the study by Dupin and Schissler [3] on the
iron with 20 wt.%Cr and 1.2 wt.%W.
Table 2
SEM-EDS and TEM-EDS analyses of microstructural constituents in the irons by a standardless method.

Alloy EDS techniques Peak height ratios Chemical analysis⁎ atm% ratios wt.% ratios Stoichiometric formula
FeKa WLa SiKa atm% (wt.%) Fe W Si Fe W Si
CrKa CrKa CrKa Cr Cr Cr Cr Cr Cr

C Si Cr Fe W

R Austenite TEM 3.85 – 0.04 30.69 ± 7.31 0.67 ± 0.2 15.55 ± 2.1 53.09 ± 5.4 – 3.41 – 0.04 3.67 – 0.02
(9.08 ± 3.0) (0.46 ± 0.1) (19.35 ± 1.3) (71.11 ± 2.1) –
Eutectic M7C3 TEM 0.42 – 0.01 35.41 ± 5.3 0.77 ± 0.2 46.68 ± 4.5 17.15 ± 0.9 – 0.37 – 0.02 0.40 – 0.01 (Cr5.1Fe1.9)C3
(11.22 ± 2.2) (0.56 ± 0.2) (63.21 ± 2.5) (25.00 ± 0.6) –

S. Imurai et al. / Materials Characterization 99 (2015) 52–60

W1 Austenite/martensite SEM 4.53 0.01 0.02 16.89 ± 2.5 0.90 ± 0.2 13.66 ± 0.8 68.26 ± 2.9 0.29 ± 0.1 5.00 0.02 0.07 5.36 0.08 0.04
(4.23 ± 0.7) (0.53 ± 0.1) (14.79 ± 1.0) (79.32 ± 1.8) (1.13 ± 0.3)
Primary M7C3 SEM 0.37 0.01 – 40.71 ± 1.9 – 40.74 ± 1.0 18.27 ± 1.0 0.27 ± 0.1 0.45 0.01 – 0.48 0.02 – (Cr4.81Fe2.16W0.03)C3
(13.31 ± 0.9) – (57.56 ± 0.3) (27.72 ± 1.1) (1.42 ± 0.2)
Eutectic M7C3 SEM 0.43 0.01 – 39.24 ± 2.3 0.03 ± 0.05 40.62 ± 0.8 19.87 ± 0.9 0.25 ± 0.1 0.49 0.01 – 0.52 0.02 – (Cr4.68Fe2.29W0.03)C3
(12.63 ± 1.1) (0.02 ± 0.04) (56.50 ± 1.0) (29.61 ± 2.9) (1.25 ± 0.2)
W4 Austenite/martensite TEM 3.16 0.10 0.05 22.19 ± 13 0.30 ± 0.3 15.47 ± 4.9 60.79 ± 8.8 1.25 ± 0.7 3.93 0.08 0.02 4.26 0.28 0.01
(6.00 ± 4) (0.18 ± 0.2) (16.92 ± 4.4) (72.08 ± 1.4) (4.82 ± 2.3)
Primary M7C3 SEM 0.34 0.01 – 39.77 ± 1.5 – 44.84 ± 1.3 14.95 ± 0.7 0.44 ± 0.1 0.33 0.01 – 0.36 0.03 – (Cr5.21Fe1.74W0.05)C3
(12.38 ± 0.7) – (62.58 ± 1.1) (22.41 ± 0.8) (2.18 ± 0.3)
W-lean eutectic M7C3 TEM 0.34 0.01 – 13.51 ± 2.4 0.02 ± 0.02 63.73 ± 1.6 21.77 ± 0.9 0.97 ± 0.1 0.34 0.02 – 0.37 0.05 – (Cr5.16Fe1.76W0.08)C3
(3.35 ± 0.7) (0.01 ± 0.01) (68.04 ± 0.6) (24.96 ± 0.4) (3.65 ± 0.5)
W-rich eutectic M7C3 TEM 0.39 0.03 – 26.12 ± 9.3 0.02 ± 0.03 52.74 ± 6.3 19.28 ± 2.8 1.85 ± 0.3 0.37 0.04 – 0.39 0.12 – (Cr5Fe1.83W0.17)C3
(7.31 ± 3.2) (0.01 ± 0.02) (61.16 ± 1.7) (23.96 ± 1.3) (7.56 ± 1.1)
M6C TEM 1.58 0.50 – 45.65 ± 18 – 16.02 ± 5.4 27.02 ± 8.8 11.32 ± 3.9 1.69 0.71 – 1.82 2.49 – (Cr1.77Fe2.98W1.25)C
(12.62 ± 8.4) – (16.47 ± 1.5) (29.90 ± 2.4) (41.02 ± 4.6)
W10 Austenite/martensite TEM 5.16 0.37 0.20 54.07 ± 8.8 0.98 ± 0.2 7.22 ± 2.2 36.94 ± 6.4 0.80 ± 0.02 5.12 0.11 0.14 5.55 0.40 0.074
(20.31 ± 5.2) (0.84 ± 0.1) (11.35 ± 2.0) (62.98 ± 3.6) (4.52 ± 0.4)
Primary M7C3 SEM 0.38 0.03 – 35.96 ± 1.1 – 48.64 ± 1.0 14.38 ± 0.2 1.01 ± 0.1 0.30 0.02 – 0.32 0.07 – (Cr5.32Fe1.57W0.11)C3
(10.94 ± 0.5) – (64.03 ± 7.4) (20.33 ± 0.4) (4.7 ± 0.5)
W-lean M23C6 TEM 0.59 0.08 0.07 16.26 ± 10.2 0.05 ± 0.05 49.55 ± 6.1 29.85 ± 3.4 4.29 ± 0.9 0.60 0.09 0.001 0.65 0.30 0.001 (Cr13.62Fe8.2W1.18)C6
(3.99 ± 3.0) (0.03 ± 0.03) (49.17 ± 5.6) (31.84 ± 0.8) (14.98 ± 1.8)
W-rich M23C6 TEM 0.60 0.10 – 28.52 ± 3.6 – 40.50 ± 2.5 25.06 ± 1.2 6.37 ± 0.1 0.62 0.16 – 0.67 0.56 – (Cr12.95Fe8.01W2.04)C6
(6.87 ± 1.1) – (41.66 ± 6.5) (28.00 ± 0.6) (23.47 ± 0.9)
M6C TEM 1.80 1.31 1.20 9.62 ± 19.7 0.21 ± 0.2 19.29 ± 0.2 35.67 ± 0.6 34.56 ± 0.4 1.85 1.79 0.01 1.99 6.34 0.006 (Cr1.28Si0.01Fe2.38W2.31)C
(1.21 ± 19.8) (0.06 ± 0.08) (10.52 ± 0.1) (20.90 ± 0.2) (66.65 ± 0.6)
⁎ The average values were based on measurement from 3 to 5 different areas.

57
58 S. Imurai et al. / Materials Characterization 99 (2015) 52–60

Fig. 6. SEM-BEIs at a higher magnification show the microstructure of the irons: (a) 4 wt.%W addition (W4) and (b) 10 wt.%W addition (W10) (etching: Murakami's reagent).

At content higher than 4 wt.%, W addition promotes a formation of
W-rich M7C3, M6C and M23C6. The M6C as observed in the W4 iron
(Figs. 3(c) and 6(a)) is often restrained in eutectic M7C3. Accordingly,
solidification sequence of the W4 iron can be proposed as: L0 → primary
M7C3 + L1, L1 → eutectic (γ + M7C3/M6C). The area of M7C3/M23C6/M6C
transition as found previously in the as-cast Mo-containing irons with
comparable chemical compositions [4] has not been observed in the
as-cast W-containing irons in the present study, but two types of eutec-
tic M7C3 carbides (W-rich and W-lean) were found instead. Seemingly,

Fig. 7. (a) BF-TEM micrograph shows austenite and W-rich eutectic M7C3 in the W4 iron.
h i h i Fig. 8. (a–b) BF-TEM micrographs show the microstructure of the W10 iron. (c–f) Corre-
(b–d) Corresponding SAED patterns from 112 austenite, 102 W-rich eutectic M7C3 and h i
h i sponding SAED patterns from [100] primary M7C3, 112 W-lean M23C6, [111] W-rich
112 M6C, respectively. (e–g) TEM-EDS spectra from austenite, W-rich eutectic M7C3 and M23C6, and [111] M6C, respectively. (g–j) TEM-EDS spectra from primary M7C3, W-lean
M6C, respectively. M23C6, W-rich M23C6 and M6C, respectively.
 S. Imurai et al. / Materials Characterization 99 (2015) 52–60 59

Table 3 3.3. Distribution of Cr and W in microstructural constituents

Volume fraction and distribution of W and Cr in microstructural constituents of the irons.

Alloys Phases Volume fraction Mass fraction Because the irons in the present study contain multiple carbides, dis-
(Vf)
W Cr
tribution of Cr and W can be described by mass fraction of each element
distributed in each constituent in the irons. Calculation of mass fraction
R Austenite/martensite 62.8% NA 0.32
can be done by performing mass balance using data in Tables 1 to 3. De-
Eutectic M7C3 37.2% NA 0.68
W1 Austenite/martensite 67.0% 0.58 0.36 tails of the mass-balance equation have been given elsewhere [4]. Be-
o o o cause the density of M6C is not known, mass fraction of Cr and W in
Primary M7C3 4.2% 0.05 0.08
33.0% 0.42 0.64
Eutectic M7C3 28.8% 0.37 0.56 M6C was obtained by subtracting their mass fraction in other constitu-
W4 Austenite/martensite 70.4% 0.47 0.32 ents from 1. The results from calculation are given in Table 3.

g g g
Primary M7C3 8.3% 0.04 0.16
W-lean eutectic M7C3 19.5% 0.14 0.41
For the irons with 0–4 wt.%W addition, distribution of Cr to all car-
29.6% 0.53 0.68 bides was somewhat constant as about 0.6–0.7 in mass fraction. An ex-
W-rich eutectic M7C3 1.4% 0.02 0.03
M6C 0.4% 0.33 0.08 ception is in the case of the W10 iron where the distribution of Cr to all
W10 Austenite/martensite 41.0% 0.18 0.14 carbides was raised to about 0.86 in mass fraction. The results in Table 3

g g g
Primary M7C3 19.6% 0.07 0.34
also revealed an increase in W distribution to all carbides from about 0.4
W-lean M23C6 23.6% 0.30 0.35
59.0% 0.82 0.86 to 0.8 in mass fraction. As given in Table 2, the W content in M7C3 in the
W-rich M23C6 15.5% 0.34 0.17
M6C 0.4% 0.11 0.0001 irons was up to about 7.6 wt.%W, whereas that in M23C6 and M6C was up
to about 23.5 wt.%W and 66.6 wt.%W, respectively.

the influence of Mo on a formation of M23C6 in high chromium cast irons
is stronger than that of W, because M23C6 was observed in the irons con-
taining from 1 wt.%Mo up to 10 wt.%Mo [4] but it was found only in the
iron with 10 wt.%W in the present study. In Figs. 3(d) and 6(b), it can be
seen that the primary M7C3 was partly consumed by the M23C6 reaction
resulting in curly M7C3/M23C6 boundaries, so the M23C6 in the W10 iron
should occur by a peritectic reaction leading to the fish-bone structure
of M23C6. Hence, solidification sequence of the W10 iron can be pro-
posed as: L0 → primary M7C3 + L1, L1 + primary M7C3 → peritectic
(γ + fish-bone M23C6) + L2, L2 → eutectic (γ + M6C). The observation
of eutectic M6C structure at the final stage of solidification in this W10
iron agrees to that reported by Sawamoto et al. [5] in the iron with
higher than 10 wt.%W. The formation of primary M7C3 would require
high amount of Cr and led to segregation of W into the adjacent liquid,
which then enable a formation of W-rich M23C6 as observed in Fig. 6(b).
Because M7C3 (M2.3C) contains more carbon than M23C6 (M3.8C), the
relatively lower carbon content in the W10 iron (see Table 1) can stim-
ulate the formation of M23C6.
Thus far, M6C with the fish-bone morphology as observed by Yu and
Matsubara [6] and Heydari et al. [9] has not been found in the present
study, which can be attributed to the difference in chemical composi-
tion and hence solidification reactions of their alloys. Furthermore,
MxC, where x = 3 or less (e.g. W3C, W6C2.54, W2C, WC1 − x and WC)
[7–9], has not been found in the as-cast irons in the present study. The
reason for the absence of these carbides can be attributed to the high
M/C ratio of the irons in the present study, so that M6C and M23C6
(M3.8C) carbides with higher M/C ratios were promoted instead of
those carbides with lower M/C ratios. The as-cast irons studied by
Mousavi Anijdan et al. [7] and by Lv et al. [8] contained 3 wt.%C, which
is higher than those in the present study. Also, it should be noted that
W2C or WC was normally found after heat treatment [8,9], but not in
the as-cast condition.
3.4. Hardness
Table 4 shows Vickers macrohardness of the irons in the present
study together with Vickers microhardness of particular phase or
structure. The formation of primary M7C3 and highly alloyed austen-
ite/martensite matrices are the main reasons responsible for the hard-
ness increase of the W1 and W4 irons. The highest macrohardness of
671 kgf/(mm)2 (HV30/15) was obtained from the W10 iron due mainly
to the formation of relatively hard M23C6 and M6C aggregates in this
iron, which is comparable to the maximum bulk hardness obtained by
Lv et al. [8]. This indicated the potentially improved wear performance
of the irons with W addition.
4. Conclusions
4.1 Detailed information on microstructure of W-containing 28
wt.%Cr–2.6 wt.%C irons with 0–10 wt.%W addition and the Cr/C
ratio about 10 is reported. The irons with 1 to 10 wt.%W were hy-
pereutectic containing primary M7C3. The matrices consisted of
austenite partially transformed to martensite. Multiple carbides
were observed in the irons with 4 wt.%W or higher. In the iron
with 4 wt.%W, M6C (ca. 0.44 vol.%) was found as the final reac-
tion in solidification sequence. In the iron with 10 wt.%W,
M23C6 (ca. 40 vol.%) was found and formed possibly by a
peritectic reaction encapsulating the M6C structure as the final
reaction in solidification sequence. With increasing the W con-
tent from 1 to 10 wt.%, the volume fraction of primary M7C3
and the total carbides in the as-cast irons increased, but those
of eutectic carbides decreased.
4.2 W addition promoted the formation of W-rich M7C3, M6C and
M23C6. Streaking in selected area electron diffraction patterns
and comparatively low Fe/Cr and W/Cr atm% ratios in EDS

Table 4
Vickers hardness of microstructural constituents of the irons.

Alloy Macro-hardness HV30/15 (kgf/(mm)2) Phase/structure Micro-hardness HV0.1/15 (kgf/(mm)2)

R 495 Austenite/martensite 423

Eutectic (γ + Μ7C3) 631
W1 550 Austenite/martensite 480
Primary M7C3 1355
Eutectic (γ + Μ7C3) 669
W4 527 Austenite/martensite 414
Primary M7C3 1358
Eutectic (γ + M7C3/M6C) 701
W10 671 Austenite/martensite 452
Primary M7C3 1774
M23C6 aggregates 889
M6C aggregates 754
60 S. Imurai et al. / Materials Characterization 99 (2015) 52–60
spectra are characteristics of M7C3. The M23C6 possesses higher
Fe/Cr and W/Cr atm% ratios than those in the M7C3. Si content
and high W content over about 11 atm%W (40 wt.%W) are im-
portant characteristics of the M6C. MxC carbides, where x = 3
or less, has not been found due possibly to the high M/C ratio
of the as-cast irons in the present study.
4.3 The highest as-cast macrohardness of 671 kgf/(mm)2 (HV30/15)
was obtained from the iron with 10 wt.%W, indicating potentially
improved wear performance of the as-cast irons with W addi-
tion. The main reasons for hardness increase are the formation
of primary M7C3 and aggregates of M23C6 and M6C.
Acknowledgment
The authors acknowledge the permission for accessing electron mi-
croscopy facilities of the Electron Microscopy Research and Service Cen-
ter, Faculty of science, Chiang Mai University. The Thailand Graduate
Institute of Science and Technology Scholarship of the National Science
and the Technology Development Agency, the National Research Uni-
versity Project under Thailand's Office of the Higher Education Commis-
sion, the Research Administration Center of Chiang Mai University, and
the Materials Science Research Center, Faculty of Science, Chiang Mai
University are thanked for funding support.
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