Materials and Design 31 (2010) 3084–3089

Contents lists available at ScienceDirect

Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Short Communication

Improving fracture toughness and hardness of Fe2B in high boron white cast iron
by chromium addition
Zhifu Huang a,*, Jiandong Xing a, Cheng Guo b
a
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, PR China
b
School of Mechanical Engineering, Xi’an Jiaotong University, Xi’an 710049, PR China

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

Article history: The effect of chromium containing 0%, 0.49%, 1.02%, 2.1%, 3.2% (in wt.%) on the morphology, fracture
Received 18 September 2009 toughness and micro-hardness property of Fe2B in high boron white cast iron was investigated. The
Accepted 6 January 2010 results indicated that, with an increase of chromium addition, the morphology of Fe2B becomes larger
Available online 11 January 2010
and changes from the block to rod shape, its micro-hardness increases and the fracture toughness
increases first and then decreases. Compared with the fracture toughness (3.8 MPa m1/2) of Fe2B without
chromium addition, the toughness at 2.1 wt.% chromium addition can be improved by above one time,
achieving 7.8 Mpa m1/2, and the result was also qualitatively testified by the micro-cracks in Fe2B based
on scanning electron microscope micrographs.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction fracture toughness, but also be helpful to its micro-hardness.

High boron white cast iron is a new kind of wear resistance
materials, which takes hard Fe2B as strengthening phase, and com-
pared with high chromium white cast iron, solves the problem of
low toughness of matrix, due to lower carbon content [1]. This kind
of material began to attract people’s attention at the end of the
1980s and has been developed in several countries since then
[2]. The prominent advantages of high boron white cast iron is that
the matrix and boride could be independently controlled by boron
and carbon contents, respectively, resulting that the strengthening
and toughening matrix and adequate volume fraction of hard Fe2B
could be obtained at the same time, which is a great improvement
and can make it possible to design the microstructure that we
needed.
At present, many researches have paid more attention to the
process that ameliorates the morphology and distribution of Fe2B
by means of adding titanium, rare earth cerium, chromium and
high temperature treatment, and so on, to improve the toughness
of high boron white cast iron [3–5]. However, as we know, Fe2B
is a very brittle phase [6], which occurs peeling and breaking dur-
ing the abrasion with the low stress, leading to a decrease in the
toughness and wear resistant property of this cast iron [7]. So, it
is significant to attempt to improve the toughness of Fe2B for real-
izing the use of high boron white cast iron in abrasive-wear fields.
The result provided by Bin et al. [8], using first principle calcu-
lation based on density functional theory, indicated that a spot of
chromium dissolution in Fe2B phase may not only improves its
* Corresponding author. Tel./fax: +86 29 82665479.
E-mail address: hzf@mail.xjtu.edu.cn (Z. Huang).
Therefore, in present study, we attempt to improve the fracture
toughness and hardness of Fe2B in high boron white cast iron by
chromium addition.
2. Experimental procedure
The alloy was melted in a 10 kg-capacity medium frequency
induction furnace, with commercial industrial pure iron, Fe–Mn,
Fe–Si, Fe–Cr, and Fe–B master alloys. After deoxidization by alumi-
num wire, the melt was poured at 1743 K into the CO2-silicate
mould to produce the Y-type block. The main chemical composi-
tions of the high boron alloy are listed in Table 1. According to
the Fe–B equilibrium diagram (Fig. 1) [9], it can be known that
the white cast iron possesses hypereutectic compositions, which
meet with the design goal of obtaining the primary Fe2B with large
size after solidification, to ensure the convenience and accuracy of
the micro-hardness and fracture toughness measurement.
The test samples were cut from the lower part of the Y blocks.
For metallographic observation and micro-hardness test measure-
ment, all samples were etched in 5% nital. The microstructures of
the samples were examined with a Neophot 32 optical microscope
(OM) and FEI Quanta 200 FEG scanning electron microscope (SEM)
equipped with energy dispersive X-ray spectrometry (EDS).
X-ray diffraction (XRD) was performed to identify microstruc-
tures. XRD was carried out on a MXP21VAHF diffractometer with
Cu Ka radiation at 40 kV and 200 mA as X-ray source. The sample
was scanned in the 2h range of 10–90°in a step-scan mode (0.02°
per step).
The hardness and fracture toughness of test samples were mea-
sured with a MX1000 type micro-hardness tester under a load of

0261-3069/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2010.01.003
 Z. Huang et al. / Materials and Design 31 (2010) 3084–3089 3085

Table 1
The main chemical compositions of the specimens with different chromium
additions.

Cr B C Fe
Specimen 1 – 4.92 0.12 Balance
Specimen 2 0.49 5.14 0.15 Balance
Specimen 3 1.02 4.94 0.16 Balance
Specimen 4 2.10 1.89 0.14 Balance
Specimen 5 3.20 5.03 0.15 Balance

Fig. 2. Schematic view of indentation mark and crack length.

Fig. 1. Equilibrium phase diagram of Fe–B alloy.
1000 g. Test results were repeated five times under the same con-
ditions to ensure the reproducibility of the hardness and fracture
toughness.
The fracture toughness of Fe2B is of critical importance in
mechanical applications [10,11]. The use of the Vickers indentation
method to assess fracture toughness of brittle materials has been
developed particularly for glass and ceramics [12]. The Vickers dia-
mond indenter is a standard item used on a dedicated hardness
tester or a universal test machine. In many cases, the crack length
can be measured optically [13–15]. Eq. (1) used for calculating the
fracture toughness is as follows:
K c ¼ XP=c3=2
where X is the residual-indentation coefficient [16,17], P is the ap-
plied load and c is the indention half crack length as defined in Fig. 1
[18]. Crack lengths are immediately measured by an optical
micrometer attached to the micro-hardness tester. X depends on
the hardness-to-elasticity modulus ratio (H/E) of the Fe2B phase
in this study. It equals to 0.064 (E/H)1/2. The value of E is approxi-
mately 336 GPa [17]. The sketch map of the test process is shown
in Fig. 2.
3. Results and discussion
3.1. Microstructure
Fig. 3 shows the microstructures of high boron white cast iron
with different chromium addition, where the white block or rod
shape field is Fe2B or (Fe, Cr)2B phase (Figs. 1 and 4), which is obvi-
ously decided by whether chromium enters into the lattice of Fe2B
or not. From Fig. 3, it also can be seen that, with an increase of
chromium addition, the morphology of the Fe2B changes obviously,
i.e. Fe2B becomes larger, and changes from block to rod shape. The
reason is that different chromium addition in the Fe2B makes its
solidification process change. However, the more influence mech-
anism is not known in this paper and requires farther investigation
in the later days. Additionally, From Fig. 4, it can be seen that chro-
mium compound does not form, favoring the solution of chromium
atom into Fe2B to increase the probability of its toughening and
hardening.
3.2. Hardness and fracture toughness
Fig. 5 shows EDS variation curves of chromium fraction (wt.%)
in Fe2B and a-Fe phase (Figs. 1 and 4) in high boron white cast iron
with different chromium addition. From this figure, it can be seen
that, with an increase in the chromium addition in cast iron, the
ð1Þ chromium fraction both in Fe2B and a-Fe increases, and chromium
fraction in Fe2B is higher than that in a-Fe in the same chromium
addition in the cast iron. It indicates that most of chromium may
enters the crystal lattice of the Fe2B, also favoring an increase of
the hardness and fracture toughness of Fe2B.
Fig. 6 shows that, with an increase in the chromium fraction, the
hardness of Fe2B increases, and fracture toughness increases first
and then decreases. Compared with the fracture toughness
(3.8 MPa m1/2) of Fe2B without chromium addition, the toughness
canbeimprovedbyaboveonetimeadding2.1 wt.%chromium,achiev-
ing 7.8 MPa m1/2. The result indicates that the increasing chromium
solutioncontentintheFe2Bisbeneficialtotheincreaseofthehardness
and fracture toughness of the Fe2B. However, the excessive solution
content decreases the toughness.
During the solidification of the Fe2B crystal, a certain amount of
chromium atoms (with larger atom radius than Fe atom) enter
crystal lattice of Fe2B and replace the part Fe atoms, resulting in
an increase of the bond energy of B–B along the direction [0 0 2]
in Fe2B crystal [19–21], which causes an increase of the hardness
and fracture toughness under the appropriate chromium addition
condition. However, why do the more chromium additions de-
3086 Z. Huang et al. / Materials and Design 31 (2010) 3084–3089

Fig. 3. The microstructures of Fe2B in high boron white cast iron with different chromium addition (wt.%): (a) 0%, (b) 0.49%, (c) 1.02%, (d) 2.10%, (e) 3.20%.

crease fracture toughness of Fe2B? The reason may be that, with tion forms, resulting in a decrease of the fracture toughness,
the increase of the chromium addition in Fe2B, the lattice distor- inversely, resulting in an increase of the micro-hardness. The rea-
tion of Fe2B increases, the more lattice defect such as the disloca- son is in accordance with the reference [16], which presented the
 Z. Huang et al. / Materials and Design 31 (2010) 3084–3089
Fig. 4. XRD pattern of high boron white cast iron with 3.20 wt.% chromium
addition.
Fig. 5. EDS variation curves of chromium fraction in Fe2B and a-Fe in high boron
white cast iron with different chromium additions.
Fig. 6. Variation curves of the fracture toughness and micro-hardness of Fe2B with
different chromium additions.
effect of Cr and Mn additions on the fracture toughness of boride
layers formed on the low-alloy steels.
3087
Fig. 7. The variation curves of the bond energy and shared electron pair of B–B in
Fe2B along the direction of [0 0 2].
Furthermore, based on the Fe2B’s crystal possessing body-cen-
tered tetragonal structure [22], and the Bond Length difference
(BDL) analysis method and Empirical electron theory of solids
and molecules (EET) [23,24], the shared electron pairs and bond
energy of B–B along the direction [0 0 2] in Fe2B crystal with an
increase in the chromium addition were calculated, and the re-
sult was shown in Fig. 7. From this figure, we can know that
the shared electron pairs of B–B increases, however, the bond
energy of B–B increases first and then decreases slightly due to
the orbital hybridization between chromium and boron atom
in Fe2B crystal, hereinto, the bond energy under with 2.1 wt.%
chromium addition was improved by about 30% more than that
of B–B under without chromium addition. In addition, it also can
be seen that the variation trends of the shared electron pairs and
the bond energy of B–B are in accordance with those of the
hardness and toughness of Fe2B (see Fig. 6), respectively. Further
referring to the analysis and computation results from the docu-
ments [25–29], it can be concluded that the variations of the
shared electron pairs and the bond energy of B–B may be funda-
mental reasons of the variations of the hardness and facture
toughness of Fe2B with increasing the chromium addition,
respectively.
Additionally, Fig. 8 shows the SEM micrographs of some micro-
cracks in the Fe2B with indentation marks. It can be seen that mi-
cro-cracks lies in the Fe2B without chromium addition (Fig. 8a),
and with the increase of chromium addition, the cracks decrease
obviously in 0.49 wt.% and 1.02 wt.% condition (Fig. 8b and c); fur-
ther adding chromium content to 2.1 wt.%, the cracks almost dis-
appear (Fig. 8d), only one shorter crack lies in the corner of
indentation mark. However, with an increase in the chromium,
the cracks appear, such as in the 3.2 wt.% condition (Fig. 8d).
The SEM observation is in accordance with the test result of the
fracture toughness of Fe2B, i.e. the better the fracture toughness
of Fe2B is, the less the crack is. Furthermore, from the sizes of
the indentation marks shown in Fig. 8, it can be seen that the
mark size in Fe2B solid-soluted by Cr atoms is smaller than that
in the Fe2B without Cr. Especially Cr addition in the high boron
white cast iron is higher than 2.1 wt.%, the size is much smaller.
The result is consistent with an increase in the hardness shown
in Fig. 6.
In this study, since the solidification condition and preparation
process of samples with different chromium additions, the more or
less cracks also may represent qualitatively how about the fracture
toughness of Fe2B is. Therefore, it can be indicate that the fracture
toughness of Fe2B is improved obviously by adding appropriate
chromium element.
3088 Z. Huang et al. / Materials and Design 31 (2010) 3084–3089

Fig. 8. SEM micrographs of high boron white cast iron with different chromium additions (wt.%): (a) 0%, (b) 0.49%, (c) 1.02%, (d) 2.10%, (e) 3.20%.

4. Conclusions
(i) With an increase of chromium addition, the morphology of
the Fe2B changes obviously in high boron white cast iron,
i.e. Fe2B becomes larger and changes from the block to rod
shape.
(ii) With an increase in the chromium in cast iron, the chro-
mium fraction both in Fe2B and a-Fe increases, moreover,
the chromium fraction in Fe2B is higher than that in a-Fe
under the same chromium addition condition.
(iii) With increasing chromium addition, the hardness of Fe2B
increases, and fracture toughness of Fe2B increases first
and then decreases.
(iv) Compared with the fracture toughness of Fe2B without chro-
mium addition, the fracture toughness with 2.1 wt.% chro-
mium addition can be improved by above one time,
achieving 7.8 MPa m1/2, and the result was also qualitatively
testified by the cracks in Fe2B based on SEM micrographs.
Acknowledgement
This work was supported by a grant from the National High
Technology Research and Development Program of China (863 Pro-
gram), (No. 2007AA03Z510), Principal Science Research Founda-
tion of Xi’an Jiaotong University (No. XJJ2008036) and China
Postdoctoral Science Foundation (No. 20080431233).
 Z. Huang et al. / Materials and Design 31 (2010) 3084–3089 3089

References [15] Lawn B. Fracture of brittle solids. 2nd ed. Cambridge: Cambridge University
Press; 1993. p. 257.
[16] Ucisik AH, Bindal C. Fracture toughness of boride formed on low-alloy steels.
[1] Zhongli L, Yanxiang L, Xiang C, Kaihua H. Microstructure and mechanical
Surf Coat Technol 1997;94–95:561–5.
properties of high boron white cast iron. Mater Sci Eng A 2008;486:112–6.
[17] Cutler RA. Engineering properties of borides, engineering materials handbook,
[2] Hanguang F, Zhiqiang J. A study of abrasive resistance cast Fe–B–C alloy. Acta
ceramic and glass, vol. 4. Metal Park (OH, USA): ASM Int.; 1991. p. 787–803.
Metall Sin 2006;42:545–8 [in Chinese].
[18] Sen S, Ozbek I, Sen U, Bindal C. Mechanical behavior of borides formed on
[3] Hanguang F, Qiang X, Kuang Jiacai, Zhiqiang J, Jiandong X. Effect of rare earth
borided cold work tool steel. Surf Coat Technol 2001;135:173–7.
and titanium on the microstructures and properties of low carbon Fe–B cast
[19] Li Musen, Fu Shaoli, Xu Wandong, Zhang Ruilin, Yu Ruihuang. Valence electron
steel. Mater Sci Eng A 2007;466:160–5.
structure of Fe2B phase and its eigen-brittleness. Acta Metall Sin 1995;31(5):
[4] Zhongli L, Xiang C, Yanxiang L, Kaihua H. Effect of chromium on microstructure
201–7.
and properties of high boron white cast iron. Metall Mater Trans A 2008;39(3):
[20] Xiao B, Xing JD, Ding SF, Su W. Stability, electronic and mechanical properties
636–41.
of Fe2B. Phys B – Condens Matter 2008;403(10–11):1723–30.
[5] Hanguang F, Lifen Y, Zhiqiang J, Jiandong X. Effect of quenching temperature on
[21] Zhou CT, Xing JD, Xiao B, Feng J, Xie XJ, Chen YH. First principles study on the
the microstructure and mechanical properties of Fe–B–Ti alloy. Int J Mater Res
structural properties and electronic structure of X2B (X = Cr, Mn, Fe, Co, Ni, Mo
2007;98(6):521–5.
and W) compounds. Comput Mater Sci 2009;44(4):1056–64.
[6] Ozkan Ozsdemir, Metin Usta, Cuma Bindal, Hikmet Ucisik A. Hard iron boride
[22] Pearson WB. A handbook of lattice spacing and structures of metals and
(Fe2B) on 99.97 wt% pure iron. Vacuum 2006;80:1391–5.
alloys. New York: Pergamon; 1958. p. 20–51.
[7] Liming H. Study on the wear resistance property of Fe–B–C wear resistance
[23] Zhang RL. Empirical electron theory of solids and molecules. 2nd
alloy. Master dissertation, Xi’an Jiaotong University; 2007. p. 21–55 [in
ed. Changchun: Jilin science and technology press; 1993. p. 12–30 [in Chinese].
Chinese].
[24] Xu B, Li MS. Effect on decreasing the eigen-brittleness of boride layer on its
[8] Bin X, Jiandong X, Ding SF, Su W. Phys B – Condens Matter 2008;403(10–11):
friction and wear behavior. Chinese J Mech Eng 2002;38(11):131–4 [in
1723–30.
Chinese].
[9] Baker H. Alloy phase diagrams. ASM handbook, vol. 3. Materials Park (OH):
[25] Liu Zh, Li Zhi, Liu WD. Electron structure and properties of the interface. 2nd
ASM International; 1992. p. 281.
ed. Beijing: Science and Technology Press; 2002. p. 11–29, 222–239 [in
[10] Lawn BR, Fuller ER. Equilibrium penny-like cracks in indentation fracture. J
Chinese].
Mater Sci 1975;10:2016–24.
[26] Nishiyama Yusuke, Shoji Mitsuo, Koizumi Kenichi, Maruno Yusuke. Theoretical
[11] Bindal C, Ucisik AH. Fracture toughness of borides formed on low alloy steel.
studies on dissociation of metal–carbon bond in Cobalamin: formulation and
Surf Coat Technol 1997;94–95:561–5.
calculation. Polyhedron 2005;24(16–17):2745–50.
[12] Sen U, Findik F, Avci E, Bindal C. Spinoidal decomposition in an SiO2–Na2O
[27] Gao Lihua, Gao Faming. Chemical bond properties and hardness estimation of
glass. In: 2nd International ceramic congress, Turkish Ceramic Society,
rare earth garnets. Mater Chem Phys 2009;113(1):145–9.
Proceeding Book, Istanbul, Turkey, vol. 1, 24–28 October 1994. p. 436–44.
[28] Zhang Xinghong, Luo Xiaoguang, Han Jiecai, Li Jinping, Han Wenbo. Electronic
[13] Sen U, Sen S, Bindal C, Yilmaz F. The comparison of the surface properties
structure, elasticity and hardness of diborides of zirconium and hafnium: first
borides AISI 4140 and SiSI D2 steels. In: 10th International metallurgy and
principles calculations. Comput Mater Sci 2008;44(2):411–21.
materials congress, US-EAT Chamber of Metallurgical Engineers, Istanbul,
[29] Gilman John J. Physical chemistry of intrinsic hardness. Mater Sci Eng A
Turkey. Proceedings Book; 2000. p. 911–9.
1996;209(1–2):74–81.
[14] Malzbender J, de With G, den Toonder JMJ. Elastic modulus, indentation
pressure and fracture toughness of hybrid coatings on glass. Thin Solid Films
2000;366:139–49.