Materials Science and Engineering A 528 (2010) 770–775

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Materials Science and Engineering A

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

Effect of heat treatment on microstructure and mechanical properties of high

boron white cast iron
Chen Xiang ∗ , Li Yanxiang
Key Laboratory for Advanced Materials Processing Technology, Ministry of Education, Department of Mechanical Engineering, Tsinghua University, Beijing 100084, 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 different tempering temperatures on the microstructure and mechanical properties of high
Received 7 August 2010 boron white cast iron after air quenching was studied. The experimental results indicate that the high
Accepted 29 September 2010 boron white cast iron comprises a dendritic matrix and interdendritic boride M2 B that distributed in
the form of continuous network and the matrix is composed of fine pearlite at as-cast condition. After
austenitising at 920 ◦ C and air quenching, the matrix of high boron cast iron is changed from pearlite to
Keywords:
lath-type martensite, and the morphology of boride is still kept in the form of continuous network. After
High boron white cast iron
tempered at 200 ◦ C or a higher temperature, a secondary precipitation with a size of tens of nanometers
Boride
Secondary precipitation
is found in the matrix, and the size and the amount of this secondary precipitation increase with the
Wear resistant increasing of tempering temperature. TEM analysis shows that the secondary precipitates have a crystal
structure of M23 (B,C)6 . With the increasing of tempering temperature after air quenching, the hardness
decreases, and the impact toughness firstly increases to a maximum value and then decreases. The opti-
mum structure that has a combination of high hardness and high impact toughness can be obtained when
the tempering temperature is lower than 400 ◦ C.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction centage of borides could be getting simultaneously, which make

White cast iron has been a kind of commonly used wear resis-
tant material for a long history, owing to its good wear resistance,
low price and easy production. In recent years, the iron-based
alloy which takes borides as the wear-resistant phase is becoming
an issue of great concern. Compared with carbides, borides have
higher hardness and thermal stability [1], which provide borides
the potentials to be a kind of good wear resistant phases. This kind
of material began to draw people’s attention at the end of eighties
of the 20th century and had been developed in several countries
since then [2–10]. Aso et al. [3–5] studied the solidification, solid-
state phase diagram and phase transformation of Fe–Cr–C–B alloys.
Lakeland [6,7] applied some patents on the glass moulds and rolls
that were fabricated by Fe–Cr–B cast irons. Egorov et al. [8] studied
the effects of carbon content on the hardness and thermal stability
of iron-based alloys that takes borides as the wear resistant phase.
High boron white cast iron is a new kind of wear resistant mate-
rials [9–12]. One of the greatest merits of the high boron white cast
iron is the matrix and borides amount could be controlled respec-
tively by adjusting the carbon and boron content in the alloy. As a
result, high strength and tough matrix and adequate volume per-
∗ Corresponding author. Fax: +86 1062773637.
E-mail address: xchen@mail.tsinghua.edu.cn (X. Chen).
it possible to design the microstructure according to the need of
industrial applications.
In this paper, the influences of tempering temperature on the
microstructure and mechanical properties of high boron white cast
iron after air quenching were studied.
2. Experimental procedures
The chemical composition of the tested alloy is presented in
Table 1
.
The high boron white cast iron was melted in a 100 kg medium-
frequency coreless induction furnace with siliceous lining, with
charge materials of steel scrap, graphite, Fe–B, Fe–Mn, Fe–Cr, Fe–Si
master alloys and copper. As boron is an active element, oxygen and
nitrogen in the melt should be effectively removed to ensure the
yield of boron. Aluminum wire and Fe–Ti master alloy were added
to remove oxygen and to fix nitrogen before Fe–B alloy was added.
Then the melt was superheated to 1550 ◦ C. After holding at the tem-
perature for 5 min, the melt was poured into Y block sand moulds.
All samples were cut from the lower part of the Y blocks. The
surface of samples must be removed by 3 mm to eliminate any oxi-
dized layer for the measurement of the hardness. Heat treatments
of all samples were carried out in an electrical resistance furnace.
The samples were held at 920 ◦ C for 2 h, quenched in air, and then
tempered at different temperatures for 1 h and then cooled in air.

0921-5093/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2010.09.092
 X. Chen, Y. Li / Materials Science and Engineering A 528 (2010) 770–775 771

Fig. 1. As-cast microstructure of high boron white cast iron: (a) optical microscope micrograph, (b) SEM micrograph and (c) the three-dimensional morphology of the boride
after deep etching.

Fig. 3. EDX spectra of boride in as-cast high boron white cast iron.

Fig. 2. X-ray diffraction pattern of as-cast high boron white cast iron.

Table 1
Chemical composition of high boron white cast iron (wt.%).

B C Si Mn Cr Cu Ti Al P S Fe

1.44 0.25 1.0 1.04 1.32 0.39 0.04 0.03 0.0021 0.0025 Balance
772 X. Chen, Y. Li / Materials Science and Engineering A 528 (2010) 770–775

Fig. 4. Boride in formula of M2 B (Z = [0 0 1]) in as-cast high boron white cast irons: (a) bright field image of transmission electron microscopy, (b) corresponding diffraction
pattern and (c) interpretation of diffraction patterns.

The samples after heat treatment were polished using 0.25 ␮m 3. Results and discussion
diamond paste. The microstructures of the samples were examined
on a Neophot 32 Optical Microscope (OM) and a FEI Quanta 200 3.1. As-cast microstructures of the alloy
FEG Scanning Electron Microscope (SEM) equipped with energy
dispersive X-ray spectrometer (EDX) using an accelerating volt- The as-cast microstructures of high boron white cast iron are
age of 15 kV after etching with 10 vol% HNO3 + 3 vol% HCl + 10 vol% shown in Fig. 1. It can be seen from Fig. 1 that the high boron white
saturated FeCl3 + 77 vol% ethanol solution. X-ray diffraction anal- cast iron comprises a dendritic matrix (Fig. 1(a) and (b)) and an
ysis was performed on a D/max-RB X-Ray Diffractometer (XRD). interdendritic eutectic compound that distributed in the form of
The specimens were scanned using Cu K␣ radiation at 40 kV continuous network (Fig. 1(c)). The morphology of boride in high
and 300 mA. The scanning speed (2Â) was 6◦ min−1 . The speci-
mens for Transmission Electron Microscope (TEM) were sliced into
0.5 mm thick plate and subsequently ground down to a thickness of
50 ␮m on a wet 800 grit silicon carbide abrasive paper. The spec-
imens were punched into diameter 3 mm foils. These foils were
finally electropolished in a twin-jet electro-polishing apparatus
at room temperature and at 30–35 V using a standard chromium
trioxide–acetic acid solution. Thin foils were examined in a JEOL
JEM-2011 Transmission Electron Microscope at an operating volt-
age of 100 kV.
After heat treatment, the samples were machined to
20 mm × 20 mm × 110 mm. Hardness was tested on a HR-150A
Rockwell hardness machine. For hardness test, the step between
any two marks of indentation is larger than 5 mm because a
sufficient step between these marks must be selected to min-
imize the interaction of the plastically deformed zones. Five
readings were taken on each sample in a random way and
the average of them is reported. Impact tests were done using
a 150-J capacity machine at room temperature. The impact
toughness values reported in this paper are averages of three
Fig. 5. Microstructure of as-cast high boron white cast iron held at 450 ◦ C for 3 h,
tests.
and then cooled in air.
 X. Chen, Y. Li / Materials Science and Engineering A 528 (2010) 770–775 773

Fig. 6. Microstructure of high boron white cast iron after air quenching: (a) no tempering, (b) tempered at 250 ◦ C for 1 h, (c) tempered at 450 ◦ C for 1 h, (d) tempered at 650 ◦ C
for 1 h, and (e) boride, tempered at 250 ◦ C for 1 h.

boron white cast iron is much like that of carbide in high chromium
white cast iron.
The solubility of boron in iron is remarkably low, either in
austenite (0.02 wt.% at 1149 ◦ C) or in ferrite (lower than 0.0021 wt.%
below 910 ◦ C) [13], compared with relatively high carbon solubility
of 2.11 wt.% (at 1148 ◦ C) in austenite and 0.0218 wt.% (at 727 ◦ C) in
ferrite [14], which makes boride form when the boron addition is
more than its solubility limit in ferrous alloy. Fig. 2 is a typical X-
ray diffraction spectrum of the high boron cast iron. Fig. 3 illustrates
the energy dispersive X-ray spectrometer of the boride. According
to the XRD pattern, the eutectic compound in the high boron cast
iron is of M2 B type, where M represents iron, chromium or man-
ganese in terms of the EDX spectra of boride. TEM analysis (Fig. 4)
also shows that the boride has a crystal structure of M2 B.
It also can be seen from Fig. 1 that the matrix of the
high boron white cast iron is composed of fine pearlite. The
boron is supersaturated in the as-cast matrix. The supersatu-
rated boron in the matrix cannot be detected by EDX, but it can
be proved by the experiment of tempering of high boron cast
iron at high temperatures. Fig. 5 shows the microstructure of
high boron white cast iron tempered at 450 ◦ C for 3 h, and then
cooled in air. It can be seen from Fig. 5 that there are a large amount
of secondary particles with a size of several tens of nanometers
precipitated. Guo et al. [15,16] studied on the Fe–Cr–B cast iron
and found that a high concentration of secondary particles precipi-
tated from the dendritic matrix grains when the as-cast or solution
treated alloys were tempered and the particles precipitated were
the mixture of different kinds of boro-carbides.
774 X. Chen, Y. Li / Materials Science and Engineering A 528 (2010) 770–775

Fig. 7. Secondary precipitated boro-carbides in formula of M23 (B,C)6 (Z = [1̄ 1 2]) in high boron white cast irons after air quenching and tempered at 650 ◦ C for 3 h: (a) bright
field image of transmission electron microscopy, (b) corresponding diffraction pattern and (c) interpretation of diffraction patterns.

3.2. Microstructure after heat treatment It can be seen that as the tempering temperature increases, the
hardness decreases, and the impact toughness firstly increases to
The scanning electron microscopy microstructures after heat a maximum value and then decreases. At tempering temperatures
treatments of high boron white cast iron are shown in Fig. 6. It can lower than 400 ◦ C, the hardness slowly declines with the increasing
be seen from Fig. 6 that the matrix of high boron cast iron is changed of the tempering temperature. When the tempering temperature
from pearlite to lath-type martensite (Fig. 6a), and the boride is still is greater than 400 ◦ C, the decreasing of the hardness of the high
distributed in the form of continuous network (Fig. 6e). boron cast iron develops rapidly. The optimum impact toughness
Without tempering, there is no secondary precipitation (Fig. 6a). is obtained at about 450 ◦ C. Considering the combination of hard-
After tempered at 200 ◦ C, there is no still secondary precipitation ness and impact toughness of the high boron white cast iron, the
exists (Fig. 6b). While after tempered at 450 ◦ C, a large amount of tempering temperature should not be exceeding 400 ◦ C.
secondary precipitation with the size of several tens of nanometers
appears (Fig. 6c), and the martensite begins to decompose. More-
over, both the amount and the size of this secondary precipitation
increase with the increasing of the tempering temperature and
the martensite has decomposed totally after tempered at 650 ◦ C
(Fig. 6d).
TEM analysis (Fig. 7) shows that these particles have a crys-
tal structure of M23 (B,C)6 , where M may be iron, chromium and
manganese. Those secondary precipitated particles form during
tempering at high temperature. Furthermore, XRD analysis has
shown that there is no cementite precipitated in the matrix (Fig. 8).
It is due to the boron is a segregation element and supersaturated in
the matrix. The boron will segregate to the grain boundaries or sub-
grain boundaries and then result in a large number of secondary
phase precipitations when tempered at high temperatures.

3.3. Effect of tempering temperature on the mechanical

properties of high boron cast iron

The influences of tempering temperature on the hardness and

impact toughness of high boron cast iron at different temperatures Fig. 8. X-ray diffraction pattern of high boron white cast iron after air quenching
after air quenching are shown in Figs. 9 and 10. and tempered at 200 ◦ C.
 X. Chen, Y. Li / Materials Science and Engineering A 528 (2010) 770–775
Fig. 9. The hardness of high boron white cast iron tempered at different tempera-
tures after air quenching.
Fig. 10. The impact toughness of high boron white cast iron tempered at different
temperatures after air quenching.
The difference in the microstructure after air quenching at dif-
ferent temperatures has led to the variation of the mechanical
properties of high boron cast iron. Without tempering, there is no
decomposition of the martensite and the high boron white cast
iron can maintain a high hardness. The hardness decreases with the
decomposition of martensite. With the release of quenching stress
775
within the martensite and the precipitation of saturated solution of
boron and carbon, the impact toughness increases when the tem-
pering is lower than 450 ◦ C. With the decomposition of martensite
and the precipitation and growth of a large amount of secondary
phase, the impact toughness begins to decrease. This means that the
secondary precipitates in the matrix are detrimental to the impact
toughness of high boron white cast iron.
4. Conclusions
The microstructure of the high boron white cast iron comprises
a dendritic matrix and interdendritic boride eutectic M2 B that dis-
tributed in the form of continuous network at as-cast condition.
The as-cast matrix is composed of fine pearlite. After air quench-
ing at 920 ◦ C, the matrix of high boron cast iron is changed from
pearlite to lath-type martensite, and the morphology of boride is
still distributed in the form of continuous network. After tempered
at 200 ◦ C or a higher temperature, a secondary precipitation with a
size of tens of nanometers appears. Both the amount and the size
of this secondary precipitation increase with the increasing of the
tempering temperature. TEM analysis shows that the secondary
precipitates have a crystal structure of M23 (B,C)6 . As the temper-
ing temperature increases, the hardness decreases, and the impact
toughness firstly increases to a maximum value and then decreases.
An optimum structure that has high hardness, good impact tough-
ness can be obtained when the tempered at about 400 ◦ C.
Acknowledgment
The authors acknowledge financial support from the National
Natural Science Foundation of China (No. 50974080).
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