Materials Science and Engineering A 532 (2012) 511–521

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Materials Science and Engineering A

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

Supersolidus liquid-phase sintering of ultrahigh-boron high-carbon steels for

wear-protection applications
A. Röttger a,∗ , S. Weber a,b , W. Theisen a
a
Lehrstuhl Werkstofftechnik, Ruhr-Universität Bochum, 44801 Bochum, Germany
b
Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Berlin, Germany

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

Article history: Powder metallurgy (PM) represents an alternative to conventional casting processes for the production of
Received 15 September 2011 wear-resistant materials. PM hard alloys for wear-protection applications feature both higher strength
Received in revised form 27 October 2011 and fracture toughness compared to cast hard alloys due to their more finely grained microstructure.
Accepted 29 October 2011
However, densification by hot-isostatic pressing (HIP), the conventional PM-compaction method, is rela-
Available online 11 November 2011
tively expensive and thus partially counteracts low-cost processing. To increase the economic efficiency of
the processing route, supersolidus liquid-phase sintering (SLPS) was investigated. In addition, expensive
Keywords:
Ni- and Co-base hard alloys were substituted by boron-rich Fe-base hard-facing alloys.
Boron
Steels
In this study, three ultrahigh-boron hard-facing alloy powders were densified by SLPS and HIP. The
Wear resistance sintering temperatures were optimized by means of sintering experiments that were supported by ther-
SLPS modynamic calculations. Both densification states were investigated and compared with respect to the
HIP microstructure and the tribological and mechanical properties of the compacted hard-facing alloys. It
was shown that the mechanical and tribological properties are strongly influenced by the microstruc-
ture. Although the microstructure is affected by the chemical composition, it can also be adapted by the
densification process. SLPS-densified hard-facing alloys have a coarse microstructure that imparts not
only a high wear resistance but also a detrimental effect on the mechanical properties.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
White cast irons are widely used for wear protection appli-
cations in the mining, mineral processing, and cement industries
owing to their high hardness, high wear resistance, low price,
and easy production [1–3]. These characteristics arise from a
microstructure consisting of primary and/or eutectic hard phases
that are finely distributed in an austenitic, pearlitic, or marten-
sitic matrix [4,5]. White cast iron with added boron has recently
been receiving more attention owing to the higher hardness of
borides compared to carbides and the lowering effect of boron on
the solidus temperature of steels. This means that steels containing
sufficient boron can be processed at lower temperatures. One main
attribute of boron-containing steels is the low solubility of boron in
␥-Fe and ␣-Fe and the formation of hard Fe-rich borides of the type
M2 B, M3 (C,B), and M23 (C,B)6 [5–7]. As a result, it is not necessary to
add hard-phase forming elements such as Mo, V, and Nb to obtain
an Fe-base alloy with a large amount of hard phases.
∗ Corresponding author. Tel.: +49 0234 32 22366; fax: +49 0234 32 14104.
E-mail addresses: roettger@wtech.rub.de (A. Röttger), weber@wtech.rub.de
(S. Weber), theisen@wtech.rub.de (W. Theisen).
Only a few authors have dealt with boron additions higher
than 1 mass%. This is due to the fact that an increasing boron
content decreases the fracture toughness [8–11]. The microstruc-
ture of ultrahigh-boron, high-carbon alloys is characterized by
primary solidified metal cells (hypoeutectic) or hard phases
(hypereutectic) that are surrounded by a low-melting and almost
brittle eutectic. This fine eutectic, in particular, promotes crack
propagation because its fracture toughness is lower than that
of the metal matrix, which results in insufficient mechani-
cal properties. Godfrey et al. investigated Ti-base MMCs with
added boron that were processed by hot-isostatic pressing.
Their results indicated spheroidization of the hard phases dur-
ing HIP treatment, which promotes an increase in mechanical
strength [5,12,13]. Furthermore, boron addition inhibits strong
coarsening of the microstructure due to precipitation of borides
at the grain boundaries [12]. If a high wear resistance and
good mechanical properties are required, the HIP process seems
to be a promising processing route for boron-containing PM
alloys.
The addition of a small amount of boron to PM steels has been
reported to have a major effect on the densification behavior dur-
ing supersolidus liquid-phase sintering (SLPS) [14–16]. Sercombe
investigated the effect of a small boron addition on the sinter-
ing behavior of a freeformed maraging PM steel. He showed that

0921-5093/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2011.10.118
512 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521
the optimized sintering temperature (OST) could be decreased by
increasing the boron content from 0 mass% to 0.4 mass% [17]. Boron
forms a low-melting eutectic with Fe and therefore promotes the
formation of a liquid phase at lower temperatures. However, boron
forms stable phases with Mo, Ti, and Cr. This alters the phase
composition of the steel matrix, which may have an effect on the
mechanical and tribological properties after heat treatment. Based
on the results of Sercombe and Lal et al., boron-containing PM
steels are suitable materials for SLPS densification to achieve wear-
resistant materials with a low porosity [17–20].
The aim of the present paper is to study the densification
behavior of three ultrahigh-boron, high-carbon gas-atomized Fe-
base powders by means of supersolidus liquid-phase sintering
and hot-isostatic pressing. The SLPS process was used to achieve
fast densification due to the presence of low-melting, boron-rich
eutectics. In addition, Weber et al. mentioned the possibility of
influencing the size and shape of the hard phases in a ledebu-
ritic cold-work tool steel by means of SLPS processing with the
aim of adjusting the diameter of the hard phase to the wear sys-
tem [21,22]. In contrast, spheroidization of hard phases due to a
decrease in the surface energy during HIP is well known. It increases
the mean free path of the metal matrix between two adjacent hard
phases, which thus improves the mechanical properties. Therefore,
this work investigated the influence of the densification process
on the microstructure and on the mechanical and tribological
properties.
2. Experimental procedure
2.1. Materials
Three ultrahigh-boron, high-carbon steels were used as
gas-atomized powders. Two of these were commercially avail-
able hypereutectic high-boron steels, X200CrNiBMo10-4-3-3 and
X360NiBCrCu4-2, and the third was a self-developed hypoeutec-
tic high-boron steel X60CrB2-2. The chemical composition of the
bulk samples after HIP was measured by optical emission spark
spectroscopy (QSG750 spectrometer OBLF) (Table 1). Prior to SLPS
and HIP densification, the gas-atomized steel powders were ana-
lyzed with respect to their microstructure, particle size, and particle
distribution by means of laser diffraction.
2.2. Thermodynamic calculations
Determination of the optimized sintering and HIP temperatures
was supported by thermodynamic equilibrium calculations using
the Calphad method. Software package Thermo-Calc version R
(Thermo-Calc AB, Stockholm, Sweden) and database TCFE6.2 were
used to calculate the solidification path, phase diagrams, and the
chemical composition of each phase in the equilibrium state. The
calculations were performed with a phase set reduced to LIQUID,
BCC A2, FCC A1, CEMENTITE, M7C3, M2B tetr, Cr2B orth, M23C6,
and M6C.
2.3. Thermal analysis, sintering, and HIP
Thermal analysis was performed to confirm the Thermo-Calc
results concerning the sintering window. Differential thermal
analysis (DTA) was performed by heating small amounts of gas-
atomized steel powder (∼100 mg) in alumina crucibles at a heating
rate of 10 K min−1 in an argon gas atmosphere.
The optimized sintering temperatures were investigated exper-
imentally by sintering at different temperatures above the solidus
temperature (TSOL ). The metal powder was filled into alumina pre-
forms and precompacted to tap density. Sintering was performed
in a batch furnace (∅ = 50 mm, L = 120 mm) under a vacuum (0.5 Pa)
with a temperature accuracy of ±5 K. The specimens were first
heated to 300 ◦ C to degas the metal powder and to drive out
residual vapor. They were then heated to the sintering tempera-
ture at a rate of 20 K min−1 . The isothermal holding time at the
sintering temperature was 10 min for all specimens. SLPS was fol-
lowed by a slow furnace cooling at a rate of approx. 15 K min−1 .
After sintering at the different temperatures, the specimens were
characterized by means of metallographic analysis, hardness mea-
surements, and determination of the density by the Archimedes
method.
Besides SLPS-densification, the gas-atomized powders were
compacted by hot-isostatic pressing (HIP) for 2 h in an argon atmo-
sphere at a temperature of 1000 ◦ C and a pressure of 100 MPa.
Ferritic steel capsules were filled with gas-atomized steel pow-
der, which was then precompressed to tap density by vibration.
The capsules were evacuated for 30 min and finally sealed by TIG
welding.
2.4. Heat treatment
To achieve a martensitic microstructure, the HIP- and SLPS-
densified specimens were austenitized at 850–1050 ◦ C, quenched
in water, and double-tempered in a temperature range from 100 to
600 ◦ C for 2 h.
2.5. Metallography and microscopy
Microstructural examinations were carried out using optical and
scanning electron microscopy (SEM). Specimens were sectioned,
ground on abrasive paper, and polished with a 1 ␮m diamond
suspension. If necessary, the specimens were etched with 3%
Nital. X-ray diffraction was used for phase analysis. Measurements
were performed with a Siemens-D500 X-ray diffractometer using
chromium K␣ radiation and a step size of 0.02◦ 2 in a range of
40–165◦ 2. The diffractograms were evaluated by the program
ADM and the JCPDS database.
2.6. Hardness measurements and abrasive wear tests
Macro- and microhardness measurements were carried out on
the cross-section of the respective specimen using a Vickers inden-
ter and a load of 294.3 N or 49.15 N. The wear resistance of the
heat-treated specimens was investigated by a pin-on-paper test
against the abrasives flint (SiO2 ) and corundum (Al2 O3 ). This type
of test involves rotating a cylindrical specimen with a diameter of
∅ = 6 mm against an abrasive paper with an average particle size
of 80 mesh (∼200 ␮m) or 220 mesh (∼66 ␮m). The dimension-
less value of the wear resistance was calculated on the basis of the
weight loss m of the specimen during testing, the specimen’s con-
tact surface A, the coating density COAT , and the distance travelled
L (Eq. (1)).
A · L · COAT
−1
Wab = (1)
m
2.7. Four-point bending tests
The mechanical properties were analyzed by four-point bending
tests using specimens with a length of 70 mm and a cross-section
of 5 mm × 5 mm. The testing method was based on DIN EN 53452
with a cross-head speed of 0.5 mm min−1 . The deflection of the
specimens was measured by cross-head displacement and an
extensometer.
 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521 513

Table 1
Chemical composition of the steel powders measured by optical emission spark spectrometry.

Steel C B Cr Ni Mo Si Mn (P + S) Cu Fe

X200CrNiBMo10-4-2-2 2.12 3.54 11.96 3.95 3.28 2.01 0.15 0.12 1.17 Bal.
X360NiBCrCu4-2 3.60 2.40 1.20 4.30 – 0.40 1.40 0.23 1.80 Bal.
X60CrB2-2 0.56 1.73 2.02 0.21 – 0.65 0.82 0.04 0.01 Bal.

3. Results Cr-rich M7 C3 in addition to Mo-rich ␥-Fe-M3 B2 and Fe-rich ␥-Fe-

3.1. Powder characterization
The microstructure of the steel powders in the gas-atomized
state is shown in Fig. 1. The hypereutectic steels exhibit hard phases
on the surfaces of the powder particles. The microstructure of the
cross-section of steel powder X220CrNiBMo10-4-3-3 in the gas-
atomized condition features primary solidified Cr–Fe-rich M2 B and
M3 (C,B) eutectics (Fig. 1a and b). The microstructure of carbon-rich
hypereutectic steel X360NiBMoCr4-2 contains globular and pri-
mary solidified M3 (C,B), which are surrounded by a ␥-Fe-M3 (C,B)
eutectic (Fig. 1c and d). In contrast, a dendritic microstructure on
the surfaces of the powder particles can be seen for hypoeutectic
steel X60CrB2-2 (Fig. 1e and f). The microstructure of the cross-
section is characterized by ␥-Fe dendrites that are surrounded by
a ␥-Fe-M2 B eutectic.

Fig. 1. Microstructure of the particle surface and of the cross-section of the steel particles: (a) and (b) steel X200CrNiBMo10-4-3-3; (c) and (d) steel X360NiBCrCu4-2; (e)
and (f) steel X60CrB2-2.
514 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521

Fig. 2. Sum distribution and probability density functions of steel powders

X200CrNiBMo10-4-3-3, X360NiBCrCu4-2, and X60CrB2-2.

The steel powder particles were analyzed with regard to par-

ticle size and distribution using laser diffraction. The probability
density functions of the steel powders are given in Fig. 2. The sum
distribution functions of the steel powders are characterized by a
multimodal function featuring two or three inflection points. Thus,
several particle maxima are present. The median particle size of the Fig. 3. Sintering temperature versus density curve of steel X360NiBCrCu4-2.

hypereutectic steel powders is almost uniform and was measured

to be x50,r = 70–71 ␮m. In contrast, the median particle size of the of liquid phase formed by eutectic M3 (C,B) was calculated to be
hypoeutectic powder was found to be x50,r = 142 ␮m. 22 vol.%. A further increase in sintering temperature led to com-
plete melting of the primary M3 (C,B), which occurred within a
3.2. Estimation of optimized sintering temperatures T of 47 ◦ C Therefore, an intentional adjustment of the amount
of liquid phase to approx. 30–40 vol.% cannot be achieved due to
Thermodynamic calculations were performed to obtain an temperature fluctuations of ±8.5 ◦ C at the nominal temperature of
initial assessment regarding the sintering window. The melting 1140 ◦ C. Powder of X200CrNiBMo10-4-3-3 was completely den-
sequence and the amount of liquid phase formed were calculated sified by SLPS processing. Although the measured porosity after
as a function of the temperature. However, these thermodynamic sintering at 1120 ◦ C was less than 1 vol.%, a higher sintering tem-
calculations describe the behavior in the equilibrium state, which perature of 1150 ◦ C was chosen to achieve a higher matrix hardness
is not the case in reality. DTA measurements were performed to (Fig. 4). The sintering temperature versus density curve of steel
estimate the differences between the calculated thermodynamic X60CrB2-2 is characterized by a small gradient with an increase
values and their experimental counterparts. TSOL and TLIQ were
determined as the main signals, and the values were compared with
the calculated results (Table 2).
As shown in Table 2, thermodynamic calculations can be used
for an initial estimation of the overall sintering interval. However,
a higher solidus temperature was found by DTA measurements.
The differences in temperature between the calculated and the
experimental TSOL and TLIQ were 30–100 ◦ C. To obtain sintered
specimens with a dense and fine-grained microstructure without
a distinctive distortion, the optimized sintering parameters must
be determined within a narrow temperature window. Therefore,
sintering experiments were performed at different sintering tem-
peratures. Furthermore, the sintered specimens were investigated
with respect to their density and microstructure.
Sintering curves for alloys X200CrNiBMo10-4-3-3,
X360NiBCrCu4-2, and X60CrB2-2 are depicted in Figs. 3–5.
The sintering curves confirm a minor densification of the powder
particles at sintering temperatures below TSOL . The density of the
sintered specimens correlates with the tap density of the powders
before sintering. Thus the sintering mechanisms in the solid state
led to slight skeletonization due to the formation of sintering
bridges. A high degree of densification was not observed.
On reaching TSOL , the density of the material rapidly increased.
In this case, only the M3 (C,B) phase was observed in the microstruc-
ture of hard-facing alloy X360NiBCrCu4-2 (Fig. 3). As a result,
eutectic M3 (C,B) generated a liquid phase, which surrounded the
previously primary solidified hard phase M3 (C,B). The amount Fig. 4. Sintering temperature versus density curve of steel X200CrNiBMo10-4-3-3.
 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521 515

Table 2
Calculated and experimental TSOL and TLIQ .

Steel Scheil calculations Equilibrium calculations DTA measurements

TSOL (◦ C) TLIQ (◦ C) TSOL (◦ C) TLIQ (◦ C) TSOL (◦ C) TLIQ (◦ C)

X60CrB2-2 1092 1328 1095 1328 1143 –

X220CrNiBMo10-4-3-3 1017 1223 1047 1223 1074 1153
X360NiBCrCu4-2 984 1122 1053 1122 1112 1177

Table 3
Optimized sintering parameters and hardness of the investigated steels.
Steel Optimized sintering Hardness
temperature (OST) (◦ C) (HV30)
X60CrB2-2 1220 635 ± 5
X360NiBCrCu4-2 1140 848 ± 18
X200CrNiBMo10-4-3-3 1150 919 ± 11
in density with increasing sintering temperature, although a low
solidus temperature of TSOL = 1143 ◦ C was measured by DTA and the
optimized sintering temperature was estimated to be TOST = 1220 ◦ C
(Fig. 5). An overview of the optimized sintering parameters is given
in Table 3.
3.3. Microstructural investigations
The microstructure of the compacted steel powders in the SLPS,
HIPed, and heat-treated state are depicted in Figs. 6–8. Phase
analysis of the hard-facing alloys in the SLPS and heat-treated
states was carried out by XRD measurements (Fig. 9). In the
case of steel X200CrNiBMo10-4-3-3 in the SLPS state, the metal
matrix contains mainly squared and lamellar hard particles of
type M2 B and M7 C3 . In addition, EDX and X-ray diffraction anal-
ysis showed eutectic Mo-rich (M3 B2 ) and Fe-rich (M3 (C,B)) hard
phases in an austenitic microstructure (Fig. 9b). The microstruc-
ture of steel X200CrNiBMo10-4-3-3 in the HIPed, quenched, and
tempered state exhibited the same hard-phase composition in a
martensitic–austenitic microstructure. The microstructure of the
SLPS and HIPed state showed differences with respect to the shape
and size of the hard phases. The hard phases (M2 B, M7 C3 , M3 B2 and
M3 (C,B)) in the HIPed state have a lamellar-to-globular shape and
Porosity a higher amount of eutectic phases.
(%) In the case of steel X360NiBCrCu4-2 in the SLPS state, the
0.53 lamellar-to-globular hard phases of type M3 (C,B) are distributed
0.02 in the microstructure and surrounded by a fine lamellar boron
0.39 cementite (M3 (C,B)) eutectic (Fig. 9c). The HIPed microstructure is
characterized by smaller and globular M3 (C,B) hard-phase grains.
Furthermore, eutectic boron cementite was detected at the triple
points of grain boundaries of globular M3 (C,B).
The hypoeutectic steel X60CrB2-2 in the SLPS and heat-treated
state is characterized by globular metal cells that are surrounded by
a Fe-rich M2 B network. XRD measurements indicate that the metal
matrix has a martensitic microstructure (Fig. 9a). The microstruc-
ture in the HIPed and heat-treated state shows globular Fe-rich hard
phases of type M2 B that are finely distributed in a mainly marten-
sitic microstructure. Furthermore, a eutectic microstructure of the
phases M23 (C,B)6 and ␣-Fe is observed.
3.4. Heat treatment
The mechanical and tribological properties of Fe-base alloys
can be adjusted by a heat treatment. In the case presented,
quenching and tempering were performed to increase the strength
and hardness of the metal matrix. Tempering curves of the
hypereutectic steels are depicted in Fig. 10. Steel X200CrNiBMo10-
4-3-3 possesses a high post-quenching hardness of 950 ± 56 HV30.
Higher tempering temperatures decreased the hardness from
864 ± 45 HV30 at 100 ◦ C to 792 ± 10 HV30 at 400 ◦ C. The hard-
ness increased again when the tempering temperature exceeded
400 ◦ C (peak of secondary hardness). Subsequently, SLPS as
well as HIPed specimens were tempered at 520 ◦ C, at which
temperature a secondary peak hardness of 859 ± 18 HV30 was
measured.
Steel X360NiBCrCu4-2 has a lower post-quenching hardness of
768 ± 34 HV30 compared to steel X200CrNiBMo10-4-3-3. Higher
tempering temperatures continuously decreased the hardness of
steel X360NiBCrCu4-2. The optimized tempering temperature was
estimated to be 200 ◦ C.
Hypoeutectic steel X60CrB2-2 was austenitized at TAUS = 850 ◦ C,
950 ◦ C, and 1050 ◦ C to investigate the influence of the solute car-
bon content in ␥-Fe on the post-quenching hardness. Increasing
the austenitizing temperature increased the hardness (Fig. 10). In
addition, the hardness of steel X60CrB2-2 decreased continuously
with increasing tempering temperature. The hardness as well as the
optimized heat treatment parameters for different densification
treatments are summarized in Table 4.

3.5. Mechanical and tribological properties

3.5.1. Hardness measurements

Fig. 5. Sintering temperature versus density curve of steel X60CrB2-2.
Owing to their high metalloid content in conjunction with a
large amount of hard-phase-forming elements, the hard alloys
investigated in this work are suitable for wear-protection appli-
cations. A high wear resistance requires a high matrix hardness
as well as a large amount of hard phases dispersed in the metal
516 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521

Fig. 6. Microstructure of steel X220CrNiBMo10-4-3-3 in the (a) SLPS and (b) HIPed state.

Fig. 7. Microstructure of steel X360NiBCrCu4-2 in the (a) SLPS and (b) HIPed state.

Fig. 8. Microstructure of steel X60CrB2-2 in the (a) SLPS and (b) HIPed state.

matrix. The hardness of the hard phases was measured by the Vick- 1823 ± 40 HV0.05 with respect to the solute chromium/iron ratio.
ers indentation method, and the volume fraction of the hard phases The hardness of the M7 C3 phase decreased with increasing
was calculated by the Calphad method (Table 5). The chromium- iron content. Furthermore, chromium-rich M2 B (HV0.05) exhib-
rich carbide of type M7 C3 exhibited the highest hardness of ited a slightly lower hardness, which was estimated to be

Table 4
Hardness and optimized heat treatment parameters of the steels for different densification treatments.

Material Densification route Heat treatment Hardness (HV30)

X60CrB2-2 HIP TAUS = 1050 ◦ C, 2 × 2 h, 200 ◦ C 663 ± 3

X60CrB2-2 SLPS TAUS = 1050 ◦ C, 2 × 2 h, 200 ◦ C 605 ± 5
X360NiBCrCu4-2 HIP TAUS = 1000 ◦ C, 2 × 2 h, 200 ◦ C 951 ± 1
X360NiBCrCu4-2 SLPS TAUS = 1000 ◦ C, 2 × 2 h, 200 ◦ C 805 ± 4
X200CrNiBMo10-4-3-3 HIP TAUS = 1000 ◦ C, 2 × 2 h, 520 ◦ C 870 ± 5
X200CrNiBMo10-4-3-3 SLPS TAUS = 1000 ◦ C, 2 × 2 h, 520 ◦ C 949 ± 3
 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521
Table 5
Hardness and volume fraction (calculated by Calphad at T = 950 ◦ C) of the various phases in the investigated steels.
Phase X60CrB2-2
Vol. fraction Hardness (HV0.05)
M7 C3 – –
M2 B 18.85 1654 ± 73
M3 (C,B) – –
M23 (C,B)6 12.66 1275 ± 82
1654 ± 73 HV0.05 in steel X60CrB2-2 and 1579 ± 81 HV0.05 in steel
X200CrNiBMo10-4-3-3. The lowest hardness of 905 ± 84 HV0.05
(eutectic) to 1044 ± 38 HV0.05 (primary) was measured in the
boron cementite.
3.5.2. Abrasive wear tests
The wear resistance of the steels was investigated by means of
a pin-on-paper test using abrasives SiO2 (1000–1200 HV0.05) and
Al2 O3 (2000–2250 HV0.05) with different particle sizes (220 mesh
(66 ␮m) and 80 mesh (200 ␮m)). The results indicated a decrease
in wear resistance with increasing abrasive particle size and abra-
sive hardness (Fig. 11). Abrasive Al2 O3 , in particular, had a higher
hardness than the hard phases in the metal matrix. As a result, the
abrasives are able to scratch and groove the hard particles. In the
case of larger abrasive particle sizes, chipping and ploughing wear
mechanisms became more active. In addition, the specimens in
the SLPS state had a higher wear resistance than the HIP-densified
specimens, except for steel X360NiBCrCu4-2.
The highest wear resistance was exhibited by steel
X200CrNiBMo10-4-3-3 in the SLPS and HIPed state. In the
SLPS state, hypoeutectic steel X60CrB2-2 had a higher wear
resistance compared to hypereutectic steel X360NiBCrCu4-2. In
the HIPed state, steels X60CrB2-2 and X360NiBCrCu4-2 exhibited
inverse behavior of the wear resistance.
3.5.3. Four-point bending test
The bending strength of the hard-facing alloys in the quenched
and tempered state was characterized by means of a four-point
bending test. The results are listed in Table 6. The measured
Fig. 9. Phase identification by means of X-ray diffraction of steels (a) X60CrB2-
2, (b) X200CrNiBMo10-4-3-3, and (c) X360NiBCrCu4-2 in the SLPS, quenched and
tempered state.
517
X360NiBCrCu4-2 X200CrNiBMo10-4-3-3
Vol. fraction Hardness (HV0.05) Vol. fraction Hardness (HV0.05)
– – 13.25 1823 ± 40
1.16 – 43.25 1579 ± 81
93.24 1044 ± 38 11.59 905 ± 84
– – – –
bending strength was higher in the HIP-densified specimens, apart
from alloy X200CrNiBMo10-4-3-3. The highest bending strength
(1141 ± 109 MPa) and deflection of the specimens (2.58 ± 0.23%)
was found in hypoeutectic steel X60CrB2-2 in the HIPed state. In
general, the values of the bending strength and deflection of the
hypereutectic steel specimens were low.
The fracture surface of the hard alloys after the four-point bend-
ing test is depicted in Fig. 12. SLPS-densified alloy X60CrB2-2 is
mainly characterized by cleavage fracture across the M2 B network
structure (Fig. 12b). In contrast, HIP-densified X60CrB2-2 is char-
acterized by a more ductile fracture with a honeycomb structure
inside the metal matrix (Fig. 12a). The fracture surface of the hyper-
eutectic steels in the SLPS state shows a brittle fracture across the
coarse hard phases of type M3 (C,B), M7 C3 , and M2 B without a rec-
ognizable ductile fracture in the metal matrix (Fig. 12d and f). In the
case of hard alloy X200CrNiBMo10-4-3-3 in the HIPed state, crack
propagation occurred along the former powder particle surfaces,
which is why separate particles can be recognized in the fractured
surface (Fig. 12e).
4. Discussion
4.1. Powder compaction by SLPS processing
SLPS requires the formation of a sufficient amount of liquid
phase in order to reach a dense microstructure [23]. If the sin-
tering temperature is too low, the amount of liquid phase is
insufficient and partial powder compaction takes place instead.
In contrast, excessively high temperatures promote distortion
and strong growth of carbides and grains that have a negative
impact on the material’s strength. Furthermore, a wide solidifica-
tion interval is required to reach a reproducible and stable process
with regard to temperature fluctuations that affect the amount of
Fig. 10. Tempering curves of the hypereutectic steels X200CrNiBMo10-4-3-3 and
X360NiBCrCu4-2 as well as the hypoeutectic steel X60CrB2-2 austenitized at differ-
ent temperatures.
518 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521
Fig. 11. Abrasive wear resistance of the investigated steels against coarse abrasives (flint and corundum) in the (a) SLPS state and the (b) HIPed state.
liquid phase formed. Enough liquid phase must be formed to ensure
sufficient decomposition of the powder particles (fast compaction)
and complete wettability of the decomposed particles. Therefore,
knowledge of the material-specific TSOL and the solidification path
constitute key parameters for achieving fast and full powder com-
paction along with high mechanical and tribological properties.
The first liquid phase forms above TSOL . The low-melting eutectic
was found to be M3 (C,B) and ␥-Fe in all alloys. As the temperature
increases, the evolution of the formed liquid phase depends on the
chemical composition of the hard alloys, which affects both the
type and the melting sequence of the phases. The type of eutectic
formed depends on the boron/carbon ratio as well as additional
alloying elements such as Cr, Mo, Mn, and Si. The influence of
metalloids and their stabilizing effect on Fe-rich borides and car-
boborides can be described by the boron/carbon ratio [B/(B + C)]. If
a low B/(B + C) ratio is present in the steel, a M3 (C,B)-type phase
is stabilized. Exceeding a B/(B + C) ratio of 0.5–0.65, stabilizes the
␶-phase (M23 (C,B)6 ) and carboborides of type M3 (C,B). The high-
est B/(B + C) ratios (>0.7) lead to the formation of borides of type
M2 B. In addition, alloying elements such as Cr and Mo have a sta-
bilizing effect on the M2 B phase due to the formation of borides
with a similar crystallographic structure. In contrast, the elements
Si and Mn possess a high solubility in the M3 (C,B) phase and inhibit
formation of M2 B. In the case of hypoeutectic alloy X60CrB2-2,
chromium-iron-rich borides of type M2 B dissolve in the temper-
ature range between 1096 and 1140 ◦ C. Above a temperature of
1140 ◦ C, the liquid phase is only provided by the ␥-Fe phase. Due to
the low carbon/boron ratio (B/(B + C) ∼ 0.4) of alloy X360NiBCrCu4-
2, only carboborides of the type M3 (C,B) are stabilized. Therefore,
the microstructure mainly consists of a M3 (C,B) eutectic that sur-
rounds the primary M3 (C,B). The eutectic M3 (C,B) starts to melt
above TSOL . At higher temperatures, primary M3 (C,B) melts, thus
promoting the formation of the liquid phase. However, there is
a narrow melting interval (TLIQ − TSOL = 47 K), which is attributed
to the presence of only the hard phase of type M3 (C,B). The hard
alloy X220CrNiBMo10-4-3-3 possesses a high boron/carbon ratio
of 0.63 and a large amount of hard-phase-forming elements such
as Cr and Mo. The high boron/carbon ratio in combination with a
high chromium content stabilizes the Cr–Fe-rich phases M2 B and
Table 6
Bending strength  B (MPa) and specimen deflection p (%) of hard-facing alloys X60CrB2-2, X200CrNiBMo10-4-3-3, and X360NiBCrCu4-2.
Material X60CrB2-2
 B (MPa) p (%)
State
HIP 1142 ± 109 2.58 ± 0.23
SLPS 519 ± 24 1.21 ± 0.01
M7 C3 . The low-melting eutectic was found to be boron cementite
along with a Mo-rich M3 B2 eutectic. The larger amount of different
hard phases leads to a wider melting interval of TLIQ − TSOL = 79 ◦ C.
This more distinct melting interval increases the reproducibility of
the sintering process and thus there are smaller differences in the
amount of liquid fraction as a result of temperature fluctuations.
Owing to measuring errors when using thermocouples, an
almost constant amount of liquid phase must be formed over a wide
range of temperatures. The amount of formed liquid phase should
be selected in dependence on strong capillary forces, decomposi-
tion of the powder particles, and prevention of material distortion
by viscous material flow. On the basis of these requirements, appro-
priate steels for SLPS-densification are hypoeutectic alloys with a
sufficient amount of low-melting eutectics such as Fe-rich M3 (C,B),
M2 B, and Cr-rich M7 C3 . In hypoeutectic steels, the amount of
formed liquid phase can be easily modified by adapting the amount
of low-melting eutectics by increasing the content of carbon and
boron metalloids. In the case of hypereutectic alloys, the required
wide solidification interval can be expanded by adapting the alloy
composition by means of a successively built-up solidification path
of different phases that melt at different temperatures. In the case
presented, steel X200CrNiBMo10-4-3-3 features a wider solidifi-
cation path than steel X360NiBCrCu4-2. This means that greater
temperature fluctuations can be tolerated.
As shown in Table 3, optimized sintering temperatures for alloy
X60CrB2-2 were found to be about 80 ◦ C above TSOL . The required
higher temperatures can be explained by the dendritic microstruc-
ture. A considerable amount of liquid phase is produced within the
interdendritic spaces. The locally bound liquid phase within the
interdendritic space does not support powder compaction. Thus
a larger amount of liquid phase is required to obtain fully com-
pacted specimens. As the temperature increases, the dendrites start
to decompose, thus leading to a redistribution of the individual
dendrite fragments.
4.2. Heat treatment
The hardness, toughness, and content of retained austenite
in the metal matrix influence the tribological and mechanical
X200CrNIBMo10-4-3-3 X360NiBCrCu4-2
 B (MPa) p (%)  B (MPa) p (%)
219 ± 31 0.50 ± 0.06 381 ± 43 0.91 ± 0.11
279 ± 14 0.61 ± 0.08 238 ± 14 0.59 ± 0.04
 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521
Fig. 12. Influence of the processing route on the fracture behavior: (a) X60CrB2-2 HIP, (b) X60CrB2-2 SLPS, (c) X360NiBCrCu4-2 HIP, (d) X360NIBCrCu4-2 SLPS, (e)
X200CrNiMoB10-4-3-3 HIP and (f) X200CrNIBMo10-4-3-3 SLPS.
properties. After SLPS- and HIP-densification, additional quench-
ing and tempering are necessary to adjust the material’s properties
to achieve a high hardness and a sufficient toughness and thus a
high wear resistance.
The highest post-quenching hardness of 950 ± 56 HV30 was
measured in hard alloy X200CrNiBMo10-4-3-3. A lower hard-
ness of 768 ± 34 HV30 was measured in alloy X360NiBCrCu4-2,
although it had a higher metalloid content and therefore a
higher hard phase content. The lower overall hardness can be
explained by a higher hardness of the chromium- and iron-
rich hard phases of the type M7 C3 (1823 ± 40 HV0.05) and M2 B
(1654 ± 73 HV0.05) in steel X220CrNiBMo10-4-3-3 compared to
the M3 (C,B) phase (1044 ± 38 HV0.05), which was only present in
steel X360NiBCrCu4-2.
The lowest hardness was measured in hypoeutectic steel
X60CrB2-2, irrespective of the chosen austenitizing and tempering
temperatures. However, the hardness increased with increas-
ing austenitizing temperature. This can be explained by the
higher solute carbon content in the ␥-Fe phase. As shown in
519
Fig. 13, an insufficient amount of carbon (0.295 mass%) was
present in the metal matrix for an austenitizing temperature of
TAUS = 850 ◦ C. Increasing the austenitizing temperature raised the
solute carbon content in the ␥-Fe phase (TAUS950 = 0.408 mass%;
TAUS1050 = 0.540 mass%), as calculated by Calphad method. Thus
an insufficient carbon content was present in the ␥-Fe phase for
austenitizing temperatures less than TAUS < 1000 ◦ C. As a result, an
austenitizing temperature of 1050 ◦ C was selected, which gave a
high hardness of 684 ± 7 HV30.
A comparison of the tempering curves of alloys X60CrB2-2 and
X360NiBCrCu4-2 shows a stronger decrease in hardness for the
hypoeutectic steel with increasing tempering temperature. The
greater loss of hardness can be attributed to a lower volume fraction
of hard phases, and the metal matrix becomes noticeably softer.
To achieve the required hardness and sufficient toughness, low
tempering temperatures of 200 ◦ C were determined to be the best
compromise.
Alloy X200CrNiBMo10-4-3-3 is characterized by an additional
increase in hardness for a tempering temperature above 400 ◦ C.
520 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521
Fig. 13. Solute carbon content in mass% in ␥-Fe as a function of the temperature.
This secondary peak hardness can be attributed to the alloying ele-
ments chromium and molybdenum, which promote precipitation
of secondary carbide. In the case of X360NiBCrCu4-2, the hard-
ness decreased with increasing tempering temperature due to the
absence of secondary carbide-forming elements.
4.3. Tribological properties of hard-facing alloys
Hard alloys are used to produce wear-resistant coatings on
substrate materials. In the case presented, the investigated alloys
contained a larger amount of hard phases finely distributed in the
metal matrix, thus protecting the metal matrix against grooving,
scratching, and chipping by the abrasives. Key factors influencing
the resistance to abrasive wear are the type, size, and amounts of
the hard phases.
As shown in Fig. 11, the highest wear resistance against the
Al2 O3 and SiO2 abrasives was exhibited by alloy X200CrNiBMo10-
4-3-3 in both densification states. This behavior is attributed to the
simultaneous presence of large volume fractions of M2 B and Cr7 C3
phases that have a high hardness. Both hard phases had a higher
hardness than the SiO2 abrasive, which resulted in sufficient wear
resistance. The hardness of the Al2 O3 abrasive meets or exceeds the
value of the hard phases of type M2 B and M7 C3 . Thus, the materials
showed a lower resistance to abrasive wear by Al2 O3 .
In addition, not only the volume fraction of hard phases pro-
motes sufficient wear resistance, as shown by the results of
hard-facing alloy X360NiBCrCu4-2. This alloy contained the largest
amounts of hard phases; however, their hardness was lower than
that of the abrasives and thus insufficient, so that these hard phases
M3 (C,B) were grooved and scratched by the abrasives. Otherwise,
a high wear resistance was achieved with steel X360NiBCrCu4-
2 in the HIPed state. This behavior can be attributed to the size
and type of the hard phase. In the HIPed state, the microstruc-
ture of alloy X360NiBCrCu4-2 contained mainly primary and coarse
M3 (C,B) that resisted ploughing and detachment. Hard-facing alloy
X360NiBCrCu4-2 had a softer microstructure in the SLPS state as a
result of a larger amount of fine eutectics.
With the exceptions of the alloy X360NiBCrCu4-2, a higher abra-
sive wear resistance in the SLPS state compared to the HIPed state
was measured. This is attributed to the smaller particle size of
the hard phases dissolved in the metal matrix in the HIPed state
for alloys X200CrNiBMo10-4-3-3 and X60CrB2-2. Sufficient wear
resistance requires a minimum diameter of the hard phase, which
should be equal to the scratch width of the acting abrasives. If not,
the hard phase will be removed together with the metal matrix
by a chipping mechanism. Therefore, the higher wear resistance of
specimens in the SLPS state can be discussed in terms of a larger
hard phase diameter. The coarser microstructure acts more effec-
tively against larger abrasives and therefore prevents removal of
the metal matrix and the hard phases by chipping.
4.4. Mechanical properties
The results of the four-point bending test clearly show that the
amount of hard phases, their distribution, size, and hardness affect
the mechanical strength under a bending load. The highest bend-
ing strength was exhibited by hypoeutectic alloy X60CrB2-2 in the
HIPed state, in which the hard phases possess a globular shape.
The lower bending strength in the SLPS state can be attributed
to a network-like structure of the hard phases of the type M2 B,
and thus crack propagation is promoted by the brittle hard phases
(Fig. 12b). In the case of HIP-densification, the globular shape of the
hard phases results in longer distances between two adjacent hard
phases and thus cracks are propagated through the more ductile
metal matrix (Fig. 12a).
In the case of the hypereutectic steels, lower bending strengths
were measured due to the presence of a large amount of hard
phases in the metal matrix. Furthermore, alloy X200CrNiBMo10-4-
3-3 exhibited a lower bending strength in the HIPed state compared
to the SPLS state. This is attributed to an inadequate densification
state, and thus crack propagation mainly occurs along the former
particle surfaces (Fig. 12e). Therefore, more pronounced diffusion
processes are necessary to increase adhesion to the former gas-
atomized powder particles. Greater adhesion between the powder
particles during HIP processing can be achieved using a higher
temperature, pressure, or a longer processing time. However, the
use of higher temperatures is limited due to the presence of the
low-melting M3 (C,B)/M2 B eutectics in the ternary Fe–C–B system.
Therefore, only higher pressures and a longer processing time are
feasible.
5. Outlook
This work has shown that the densification route influences
the microstructure and therefore the mechanical and tribologi-
cal properties of hard-facing alloys. The results of the four-point
bending test, in particular, indicate a more ductile fracture of the
hypoeutectic steels in the HIPed state. Compared to specimens
with SLPS-densification, fracturing was shifted to higher bending
stresses due to spheroidization of the hard phases, which is asso-
ciated with an increase in the size of the mean free path across the
metal matrix between two adjacent hard phases. Further research
is focusing on the spheroidization of hard phases and the develop-
ment of wear-resistant hypoeutectic steels with a high mechanical
strength based on an alloying strategy and a material-adapted
heat treatment. Spheroidization and a more uniform distribution
of hard phases can be achieved by injecting the melt with small
amounts of hard-phase-forming elements that act as crystalliza-
tion nuclei for low-melting hard phases. Furthermore, the melting
behavior of hard-facing alloys can be influenced by alloy design-
ing to achieve a dense and fine-grained microstructure by means
of SLPS-densification.
It may be possible to increase spheroidization of the hard
phases after SLPS-densification by high-temperature annealing.
Preliminary tests confirm spheroidization of the hard phases with
simultaneous development of a fine-grained microstructure after
 A. Röttger et al. / Materials Science and Engineering A 532 (2012) 511–521
Fig. 14. Microstructure of hard-facing alloy X60CrB2-2 in (a) SLPS state and (b) after annealing at 950 ◦ C for 4 h.
extended annealing at the austenitization temperature (Fig. 14). In
addition, specimens can be quenched from the annealing temper-
ature to achieve a martensitic microstructure.
6. Conclusion
The present paper focuses on the microstructural evolution and
the mechanical as well as tribological properties of three ultrahigh-
boron, high-carbon steels that were densified by means of SLPS and
HIP processing. The main results are:
1. Hypereutectic as well as hypoeutectic Fe–C–B steels can be fully
densified by SLPS and HIP processing.
2. Sintering experiments at temperatures slightly higher than TSOL
confirmed a large increase in density and hardness, which is
attributed to the formation of a liquid phase.
3. SLPS processing produced specimens with a density close to
the bulk value. The amount of liquid phase, which is nec-
essary for fast densification without material distortion, was
estimated by means of thermodynamic calculations and sin-
tering experiments. Hypereutectic alloys exhibited a narrower
interval between TSOL and TLIQ compared to hypoeutectic steel
X60CrB2-2.
4. Sintering temperatures 50–70 ◦ C higher than TSOL must be cho-
sen to achieve a dense microstructure and a high hardness,
simultaneously. Differences between calculated and experimen-
tal TSOL and TLIQ were determined to be 30–100 ◦ C.
5. In contrast to literature data, a larger amount of liquid phase of
30–50 vol.% was required to reach fully compacted specimens.
6. Steel X200CrNiBMo10-4-3-3 exhibited a secondary hardness
peak due to the presence of the elements chromium and molyb-
denum. In the case of steels X60CrB2-2 and X360NiBCrCu4-2, the
hardness decreased on increasing the tempering temperature.
7. Specimens in the SLPS state had a higher wear resistance than
HIP-densified specimens. This is attributed to a larger hard par-
ticle size that counteracts chipping and ploughing by abrasives
more effectively.
521
8. The highest bending strength found for hypoeutectic steel
X60CrB2-2 in the HIPed state. This is attributed to the globular
shape of the hard phase of type M2 B.
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