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Materials Letters 62 (2008) 857 – 860

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Effect of niobium on the as-cast microstructure of hypereutectic

high chromium cast iron
Xiaohui Zhi, Jiandong Xing, Hanguang Fu ⁎, Bing Xiao
State Key Laboratory for Mechanical Behavior of Materials, School of Materials Science and Engineering, Xi'an Jiaotong University,
Xi'an 710049, Shaanxi Province, PR China
Received 18 May 2007; accepted 29 June 2007
Available online 13 July 2007

Abstract

The effect of niobium element on the as-cast microstructure of the hypereutectic high chromium cast irons containing 4.0 wt.% C and 20.0 wt.%
Cr was studied by means of the optical microscopy, the scanning electron microscopy, the X-ray diffraction, the energy dispersive X-ray
spectrometry, the electron probe microanalyzer and the Leica image analyzer. With the addition of Nb, NbC carbides are formed in the hypereutectic
high chromium cast irons, the carbides are refined and the shape of the primary M7C3 carbides becomes isotropic. The addition of niobium reduces the
carbon content of the liquid due to the formation of the first precipitated NbC, thus reduces the volume fraction and size of the primary M7C3 carbides.
© 2007 Elsevier B.V. All rights reserved.

Keywords: High chromium cast irons; Niobium; Carbide; Refinement; Microstructure; Metals and alloys

1. Introduction The mechanical properties of the hypereutectic HCCIs can be

The wear resistant high chromium cast irons (HCCIs) are
used in a variety of applications where the stability in an
aggressive environment is a principal requirement, including
the mineral processing, cement manufacturing, slurry pumping
and pulp and paper manufacturing industries [1–6]. HCCIs may
be the hypoeutectic, eutectic or hypereutectic compositions [7].
Their exceptional abrasive resistance results primarily from the
presence of hard M7C3 type carbides, either as eutectic carbides
or primary carbides, although the toughness of the matrix also
contributes to the wear resistance. In most cases, HCCIs are
used as the hypoeutectic compositions containing 10–30 wt.%
Cr and 2.0–3.5 wt.%C [6]. The hypereutectic HCCIs are
considered to have more volume fractions of the hard and wear
resistant M7C3 carbides than the hypoeutectic HCCIs, and are
often the preferred alloy for many hardfacing applications [7,8].
However, the hypereutectic HCCIs generally are not favored for
casting, due to high scrap and high rejection rate which are
mainly caused by the coarser and larger primary carbides [7].
⁎ Corresponding author. School of Materials Science and Engineering, Xi'an
Jiaotong University, 28 Xianning West Road, Xi'an, Shaanxi Province 710049,
PR China. Tel.: +86 29 82665479; fax: +86 29 82663453.
E-mail address: fhg64@263.net (H. Fu).
0167-577X/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2007.06.084
improved by alloy design and structure control techniques [2].
Llewellyn et al [6] reported the microstructure and abrasive
properties of slurry pump parts made by hypereutectic HCCIs
through improved foundry techniques. Atamert and Bhadeshia
[9,10] found that the shape of the normally elongated and rather
brittle M7C3 carbide was altered to a more equiaxed morphology
using silicon. In an earlier paper [11], we researched the effect of
titanium on the morphology of primary M7C3 carbides in
hypereutectic HCCIs and discovered that titanium element could
refine the primary M7C3 carbides in hypereutectic HCCIs. At
present study, the effect of niobium on the solidification
microstructure of hypereutectic HCCIs was studied and the
refinement mechanisms of niobium on the carbide were also
discussed.
2. Experimental
The studied alloys were prepared in a 20 kg-capacity
medium frequency induction furnace. Initial charge materials
were clean low silicon pig iron and steel scrap. Ferro-alloys
such as Fe-63%Cr and Fe-30%Nb were added to a slag-free
molten steel so as to minimize the oxidation loss and the slag
formation. The melt was subsequently super-heated to 1560 °C
and transferred into a pre-heated teapot ladle. After removal of
858 X. Zhi et al. / Materials Letters 62 (2008) 857–860

Table 1 It can be seen that the smaller the D is, the finer the carbides
Chemical composition (wt.%) of the alloys and the average carbide diameters D are. With this arrangement, 20 images of each specimen at
at the location of 1.0 mm under the surface
magnification of 200 times are randomly selected and processed
Sample C Cr Nb D(um) for the calculation of D using the LEICA Qwin image analysis
1 4.0 20.0 0.0 10.5 system on the deep etched specimens. The investigation
2 3.97 19.87 0.5 9.3 techniques used for structure characterization also included X-
3 3.94 19.70 1.0 8.6
ray diffraction (XRD), energy dispersive X-ray spectrometry
4 3.90 19.50 1.5 5.8
(EDS) and the electron probe micro-analyzer (EPMA). The
optical microscopy used was a Neophot 32. The scanning
electron microscopy used was a JEOL JSM-6100 and a Philips
any dross and slag, the melt was poured at 1450 °C into the XL-30 microscope equipped with an energy dispersive X-ray
CO2-silicate moulds. The dimensions of the specimen are spectrometer (Link IS-IS). EPMA was carried on a JXA-8800R
60 mm × 60 mm × 20 mm. The chemical compositions of the electron probe micro-analyzer. XRD was carried on a
alloys are listed in Table 1. MXP21VAHF diffractometer with Copper Kα radiation at
The specimens were polished, etched with 5% nital. The 40 kV and 200 mA as an X-ray source. The sample was scanned
microstructures at the location of 1.0 mm under the surface of in the 2θ range of 20°–85° in a step-scan mode (0.02° per step).
samples are characterized using an optical microscope (OM)
and a scanning electron microscopy (SEM). The micrographs 3. Results and discussion
correspond to the transverse section of the columnar carbides.
The average carbide diameters D at the position are used to 3.1. Solidification structure of the hypereutectic HCCIs
determine the refining effect of niobium on the carbides, which
Fig. 1 is the optical micrographs at the location of 1.0 mm below the
is given by the following equation:
surface. The average diameters D with different niobium addition are
rffiffiffiffiffiffiffi listed in Table 1 From Fig. 1 and Table 1, it can be seen that carbides are
A
D¼2 ð1Þ refined gradually and the shape of the primary M7C3 carbides became
Np more isotropic with the increase of niobium element.
The X-ray diffraction pattern of Fig. 2 shows the presence of NbC in
where: A — the area of the carbides; N — the number of the the as-cast hypereutectic HCCI. Fig. 3a and 3c shows the secondary
carbides in one image. electron image (SEM) and backscattered electron (BSE) micrographs

Fig. 1. The microstructures at 1.0 mm under the surface: a) sample1; b) sample2; c) sample3; d) sample4.
 X. Zhi et al. / Materials Letters 62 (2008) 857–860
Fig. 2. The X-ray diffraction pattern of as-cast sample4.
of sample 4, respectively. Fig. 3b is the EDS spectrum of NbC carbide
(point C in Fig. 3a). The data are fully corrected for atomic number,
absorption, and fluorescence using Proza (Phi-Rho-Z) correction
method. The method also picks up information from the matrix, so
there are also some chromium and iron elements in the EDS spectrum
of NbC. The white particles in Fig. 3c are NbC. Fig. 3d is the
distribution of niobium element in sample 4 analyzed by EPMA. From
Fig. 3c and 3d, it can be discovered that the distribution of niobium
elements is not homogeneous in the as-cast hypereutectic HCCI, and
niobium element is mainly distributed over the NbC particles.
Fig. 3. The SEM and distribution of niobium in as-cast sample4: a) SEM micrographs (A — NbC, B — M7C3); b) EDS spectra of NbC of point C in Fig. 3a); c) BSE
micrographs; d) distribution of Nb analyzed by EPMA.
859
3.2. The refinement mechanism of niobium on the carbide
Niobium is a strong carbide forming element, so, according to the
following equation, NbC particles are formed before the precipitation
of primary carbides when niobium is added into the melts [12]:
½Nb þ ½C  ¼ NbC ðsÞ ð2Þ
The XRD in Fig. 2 and the EDS and SEM in Fig. 3 show the
presence of NbC phase in the hypereutectic HCCIs. The addition of
niobium reduces the carbon content of the liquid due to the formation
of the first precipitated NbC, thus reduces the volume fraction and size
of the primary M7C3 carbides. Niobium element preferentially
partitions into NbC in the Fe–C–Cr alloys and its concentration in
the matrix and M7C3 carbides is very low [13–15], which was also
proved by Fig. 3d. So, niobium element may also enrich at the grain
boundary of carbides during the solidification and impede the
preferential direction growth of the M7C3 carbides and result in finer
carbides.
4. Conclusions
The carbides in the hypereutectic HCCIs are apparently
refined and the shape of the primary M7C3 carbides becomes
isotropic with the addition of niobium element. Moreover, NbC
carbide is present in the hypereutectic HCCIs and is identified
860 X. Zhi et al. / Materials Letters 62 (2008) 857–860

via XRD and EDS analysis when niobium element is added into [5] R.W. Durman, Int. J. Miner. Process. 22 (1988) 381.
the HCCIs. [6] R.J. Llewellyn, S.K. Yick, K.F. Dolman, Wear 256 (2004) 592.
[7] A. Wiengmoon, T. Chairuangsri, A. Brown, R. Brydson, D.V. Edmonds,
J.T.H. Pearce, Acta Mater. 53 (2005) 4143.
Acknowledgments [8] Vickers Australlia Limited, Tough, wear and abrasion-resistant, high
chromium hypereutectic white iron. Pat. International WO84/04760.
The authors would like to thank the financial support for this [9] S. Atamert, H.K.D.H. Bhadeshia, in: S.A. David, J.M. Vitek (Eds.), Recent
Trends in Welding Science and Technology (TWR'89), ASM Internation-
work from the National Natural Science Foundation of China
al, Ohio, U. S. A., 1989, p. 273.
(50571078). [10] S. Atamert, H.K.D.H. Bhadeshia, Proceedings of Heat Treatment 1987,
The institute of metals, London, 1988, p. 39, July.
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