Acta Biomaterialia 6 (2010) 1033–1038

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Acta Biomaterialia
journal homepage: www.elsevier.com/locate/actabiomat

Microstructure and magnetic susceptibility of as-cast Zr–Mo alloys

Suyalatu, Naoyuki Nomura *, Kei Oya, Yuko Tanaka, Ryota Kondo, Hisashi Doi,
Yusuke Tsutsumi, Takao Hanawa
Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan

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

Article history: The microstructures and magnetic susceptibilities of Zr–Mo alloys were investigated to develop a Zr alloy
Received 24 June 2009 with a low magnetic susceptibility for magnetic resonance imaging (MRI). The microstructure was eval-
Received in revised form 8 September 2009 uated with an X-ray diffractometer (XRD), an optical microscope (OM) and a transmission electron micro-
Accepted 15 September 2009
scope (TEM), and the magnetic susceptibility was measured with a magnetic susceptibility balance. The
Available online 20 September 2009
a0 phase with acicular structure was dominant in Zr–1Mo alloys, while the x and b phases with the equi-
axed and relatively flat (no acicular) microstructure was dominant in Zr–3Mo. The mixed microstructural
Keywords:
features of Zr–1Mo and Zr–3Mo were observed in Zr–2Mo, which consists of the a0 , x and b phases. The b
Zr–Mo alloy
Magnetic susceptibility
phase is stabilized when the Mo content exceeds over 3 mass% Mo. As-cast Zr–Mo alloys showed a min-
x Phase imum value of magnetic susceptibility at 3 mass% Mo, and the value abruptly increased up to 10% Mo
a0 Phase before remaining stable up to 15 mass% Mo. XRD, OM and TEM revealed that the minimum value of
b Phase the susceptibility was closely related to the appearance of the athermal x phase in the b phase. As the
Mo content decreases from 3 mass%, the a0 phase appears with the x and b phases. On the other hand,
as the Mo content increases from 3 mass%, the b phase increases and the x phase decreases. Thus the
appearance of the a0 and b phase leads to an increase in magnetic susceptibility. The magnetic suscepti-
bility of as-cast Zr–3Mo alloy was almost one-third that of Ti–6Al–4V, which is commonly used for med-
ical implant devices. Zr–Mo alloys are useful for medical devices used under MRI.
Ó 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

1. Introduction substitute most metallic medical devices by polymers or ceramics.

Magnetic resonance imaging (MRI) is widely used as an impor-
tant diagnostic tool for the whole body, especially for orthopedic
and brain surgery. This method has remarkable advantages in
obtaining various cross-sectional views and diagnose of the human
body with no invasion and no exposure of the human body to X-
ray radiation. However, MRI diagnosis is inhibited when metals
are implanted in the body, since metallic implants, such as stain-
less steels, Co–Cr alloys and Ti alloys, become magnetized in the in-
tense magnetic field of the MRI instrument and artifacts occur on
the image [1,2]. Such artifacts can disturb the images of organs
and tissues around the implant, preventing exact diagnosing. The
area affected by the artifacts is related to the magnetic susceptibil-
ity of the implants [3–5] and decreases with decreasing magnetic
susceptibility. Operations under open MRI have also been carried
out. For such operations, devices with low magnetic susceptibility
are also required.
On the other hand, metals are absolutely necessary materials
for medical implants and devices because of their mechanical
properties, such as strength and toughness, which are superior to
those of polymers and ceramics. It is currently impossible to
* Corresponding author. Tel./fax: +81 352808007.
E-mail address: nnomura.met@tmd.ac.jp (N. Nomura).
Therefore, metals with low magnetic susceptibility should be
developed for medical treatments as MRI becomes increasingly
popular.
Of the various metals used, we focus on Zr because it has less
magnetic susceptibility than Ti [6], low cytotoxicity [7] and high
corrosion resistance due to the passive oxide formation on the sur-
face. However, its mechanical reliability is not sufficient for unal-
loyed Zr to be used in structural biomaterials. As an alloying
element to Zr, we employed Mo because it is an effective strength-
ening element for Zr [8], shows low cytotoxicity [7] and also shows
low magnetic susceptibility.
Fig. 1 shows a Zr–Mo binary alloy phase diagram [9]. In Zr-rich
compositions, the a(hexagonal close-packed, hcp) + Mo2Zr phase
region exists at lower temperatures while the b(body-centered
cubic, bcc) and b + Mo2Zr are stable at higher temperatures. The
magnetic susceptibility of an alloy depends on the composition
and phase constitution [10]. Therefore, in order to develop Zr–
Mo alloys having low magnetic susceptibility, the relationship
between the magnetic susceptibility and phase constitution for
the alloys must be evaluated.
Zr-based alloys have recently been used as orthopedic biomate-
rials [11,12], such as artificial knee joints. Investment casting is
one of the preferred techniques for fabricating orthopedic biomate-
rials because the shape can be very sophisticated, depending on the

1742-7061/$ - see front matter Ó 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actbio.2009.09.013
1034 Suyalatu et al. / Acta Biomaterialia 6 (2010) 1033–1038
Fig. 1. Zr–Mo binary alloy phase diagram [9].
design. Thus, it is essential to evaluate the magnetic susceptibility of
Zr-based alloys in the as-cast condition. The purpose of this study
was to evaluate the effect of the composition and phase constitution
of as-cast Zr–Mo binary alloys on the magnetic susceptibility.
2. Materials and methods
2.1. Specimen preparation
Zr–Mo alloys (Zr–0, 0.5, 1, 2, 3, 4, 7.5, 10, and 15 mass% Mo)
were prepared from zirconium sponge (99.6 mass%) and molybde-
num briquette (99.7 mass%). The alloys were prepared by cold
hearth melting with a non-consumable tungsten electrode in an
Ar atmosphere. Each ingot, weighing about 50 g, was remelted 10
times with inversion. The ingots were remelted with a centrifugal
casting furnace and cast into a sand mold consisting mainly of
ammonium phosphate and alumina. The mold, which had a diam-
eter of 48 mm and a height of 74 mm, was not preheated and was
kept at room temperature. After casting, the mold was quenched in
water. The dimension of the cast was a bar with 3 mm in diameter
and 25 mm in length. The surface layer that had reacted with the
mold was removed by sandblasting and polishing with Emery pa-
pers. A pure Mo (99.95 mass%) bar with the same dimensions was
also prepared as a control without melting because of its high
melting point (2896 K). In addition, a commercially available Co–
Cr–Mo alloy (F-75), CP Ti (grade 2), Ti–6Al–4V and Ti–6Al–7Nb
were obtained and shaped with the same dimensions. Their mag-
netic susceptibilities were measured for comparison.
2.2. Microstructural characterization
The constituent phase was analyzed using an X-ray diffractome-
ter (XRD) with Cu Ka under 45 kV and 40 mA. The microstructures of
Zr–Mo alloys were characterized with an optical microscope (OM)
and a transmission electron microscope (TEM). The specimens for
the OM and XRD were polished with emery papers up to #1500
and then electropolished with a solution of 10% HClO4 and 90%
CH3OH at 20–35 V and 223 K. TEM observations were performed
at an operating voltage of 100 kV.
2.3. Magnetic susceptibility
The magnetic susceptibilities of as-cast Zr–(0–15)Mo alloys
were measured using a magnetic susceptibility balance with a
magnetic field of 0.35 T at room temperature. The direction of
applied magnetic field was normal to the longitudinal direction
of the casting bar. The magnetic susceptibility was measured at
least three times for each casting bar.
3. Results
3.1. Microstructure and constituent phase of as-cast Zr–Mo alloys
Fig. 2 shows OM images of as-cast Zr–(0–10)Mo alloys. An acic-
ular structure was observed in coarse equiaxed grains in Zr, Zr–
1Mo and Zr–2Mo. The size of acicular structure in Zr–2Mo seems
to be smaller than that in Zr–1Mo. Zr–2Mo consists of a mixture
of acicular structure regions and relatively flat regions. In Zr–
3Mo, equiaxed grains were observed and the acicular structure dis-
appeared. Microstructures similar to that of Zr–3Mo were observed
in Zr–5Mo and Zr–10Mo. The grain size decreased with increasing
Mo content.
Fig. 3 shows the XRD profiles of as-cast Zr–(0–10)Mo alloys.
Only the peaks originated from the a phase were observed in
Zr and Zr–1Mo. In Zr–2Mo, the a, x and b phases were con-
firmed. In Zr–3Mo and Zr–5Mo, the a phase disappeared and
the x and b phases were observed. It is difficult to determine
the x and/or b phases at x(1 1 0)/b(1 1 0), x(2 0 1)/b(2 0 0),
x(3 0 0)/b(2 1 1) and x(2 2 0)/b(2 2 0) because they overlap with
each other. However, it is noteworthy that the peaks only from
the x phase in Zr–5Mo showed a lower intensity compared to
those in Zr–3Mo. This indicates that the volume fraction of the
x phase in Zr–3Mo is higher than that in Zr–5Mo. In Zr–
10Mo, the peaks from the b phase were observed to be
dominant.
Fig. 4 shows TEM images of as-cast (a) Zr and (b) Zr–1Mo. Zr–
1Mo was found to consist of an acicular structure, which was
formed by martensitic transformation during cooling. This mar-
tensitic substructure consisted of isolated platelets containing
twins [7]. Therefore, this structure corresponds to the a0 phase.
In as-cast Zr, relatively large grains with lower dislocation density
were observed and the martensitic substructure found in Zr–1Mo
was not confirmed.
Fig. 5 shows TEM images and selected area diffraction pat-
terns of as-cast Zr–3Mo. The acicular structure observed in Zr–
1Mo was not found, while the existence of x phase was clearly
confirmed in the diffraction patterns. The existence of distinct x
phases and a second phase could not be found in the bright-field
image. It is considered that athermal x phase was formed dur-
ing cooling.
3.2. Magnetic susceptibility of as-cast Zr–Mo alloys
Fig. 6 shows the magnetic susceptibility of as-cast Zr–Mo alloys.
The magnetic susceptibility of Zr–Mo suddenly decreased from 0 to
0.5–1 mass% Mo and then gradually decreased until 3 mass% Mo.
After showing the minimum value at 3 mass% Mo, the magnetic
susceptibility abruptly increased from 3 to 7.5 mass% Mo, then re-
mained stable from 10 to 15 mass% Mo. The magnetic susceptibil-
ity of pure Mo (bcc) was 7.3  107 cm3 g1, which is considerably
lower than that of pure Zr. These results suggest that the magnetic
susceptibility of Zr–Mo alloys does not always decrease with
increasing Mo content. Fig. 7 shows the magnetic susceptibilities
of Zr–3Mo and metals used for medical devices. It should be noted
that the magnetic susceptibility of the Zr–3Mo alloys is almost
one-third that of Ti–6Al–4V. This result indicates that the Zr–Mo
alloy suppresses the artifacts in MRI.
 Suyalatu et al. / Acta Biomaterialia 6 (2010) 1033–1038
Fig. 2. Optical micrographs of as-cast Zr–Mo alloys. (a) Zr, (b) Zr–1Mo, (c) Zr–2Mo, (d) Zr–3Mo, (e) Zr–5Mo and (f) Zr–10Mo.
4. Discussion
4.1. Microstructures and the constituent phase of as-cast Zr–Mo alloys
Microstructural observation and XRD analysis reveals that the
microstructures of the as-cast Zr–Mo alloys strongly depend on
the composition. The a0 phase with acicular structure was dominant
in Zr–1Mo alloys (Figs. 2 and 3(b)), while the x and b phases, with
equiaxed and relatively flat (no acicular) microstructures, were
dominant in Zr–3Mo (Figs. 2 and 3(d)). It is noteworthy that the
mixed microstructural features of Zr–1Mo and Zr–3Mo were ob-
served in Zr–2Mo (Fig. 2(c)), which consists of the a0 , x and b phases
(Fig. 3(c)). Thus, the relatively flat regions in the OM image may cor-
respond to the mixture of x and b phases. Fig. 8 shows the non-
equilibrium phase diagram for x forming alloys [13] and the phase
constitutions obtained in this study. When the Mo content is less
than about 3 mass%, the Ms is higher than the xs. This indicates that
the a0 phase is formed first, followed by the formation of the x
phase from the retained b phase when the temperature passes
through the xs during cooling. When the Mo content exceeds about
3 mass%, the xs is higher than the Ms, causing the x phase to de-
crease while the b phase is retained. In addition, the retained b
phase is dominant over 10 mass% Mo, suggesting that the xs is low-
er than room temperature at this composition.
1035
4.2. Relationship between the constituent phase and the magnetic
susceptibility of as-cast Zr–Mo alloys
Collings [10] reported that the magnetic susceptibility depends
on the constituent phases and their volume fractions. The magnetic
susceptibility of the Zr–Mo alloy system (vZr–Mo) is expressed as
follows:
vZr—Mo ¼ V a0  va0 þ V b  vb þ V x  vx ð1Þ
where va0 , vb and vx are the magnetic susceptibilities of the a0 , b
and x phases, respectively, and V a0 , Vb and Vx are the volume frac-
tions of the a0 , b and x phases, respectively. Table 1 summarizes the
phase constitution of as-cast Zr–Mo alloys. When the Mo content
decreased in the range from 10 to 3 mass% Mo, the x phase clearly
appeared in the b phase and the magnetic susceptibility suddenly
decreased, showing a minimum value in 3 mass% Mo. The XRD pro-
files suggest that the volume fraction of the x phase in Zr–3Mo is
larger than that in Zr–5Mo. Therefore, the magnetic susceptibility
of the x phase is lower than that of the b phase, as shown in Eq. (1).
When the Mo content in the range from 3 to 1 mass% Mo is con-
sidered, the x phase clearly decreased and the a0 phase appeared,
and the magnetic susceptibility suddenly increased linearly. The
XRD profiles suggest that the volume fraction of the a0 phase in
Zr–1Mo is larger than that in Zr–2Mo. Therefore, the magnetic
1036 Suyalatu et al. / Acta Biomaterialia 6 (2010) 1033–1038

Fig. 3. XRD profiles of as-cast Zr–Mo alloys. (a) Zr, (b) Zr–1Mo, (c) Zr–2Mo, (d) Zr–3Mo, (e) Zr–5Mo, and (f) Zr–10Mo.

Fig. 4. TEM images of as-cast (a) Zr and (b) Zr–1Mo.

susceptibility of the x phase is lower than that of the a0 phase, as susceptibility corresponds to that of the a0 phase. Given that
shown in Eq. (1) as well. Zr–(0.5–1)Mo possesses the bcc structure (b phase), the magnetic
In Zr–(0.5–1)Mo, the magnetic susceptibility shows almost the susceptibility can be estimated by the extrapolation line from the
same values. Since the a0 phase was dominant in these alloys, this susceptibility of Zr–10Mo and Zr–15Mo, both of which consist of
 Suyalatu et al. / Acta Biomaterialia 6 (2010) 1033–1038 1037

Fig. 5. TEM images of as-cast Zr–3Mo alloy. (a) Bright-field image and (b) selected area diffraction patterns.

Fig. 8. Non-equilibrium phase diagram of as-cast Zr–Mo alloys [13] and the phase
Fig. 6. Magnetic susceptibility of as-cast Zr–Mo alloys. constitution obtained in this study.

Table 1
Phase constitution of as-cast Zr–Mo alloys.

Alloys Phase
Zr–0.5Mo a0
Zr–1Mo a0
Zr–2Mo a0 , x, b
Zr–3Mo x, b
Zr–7.5Mo b, x
Zr–10Mo b
Zr–15Mo b

the b phase. However, the line passes through higher values than
the values measured at Zr–(0.5–1)Mo. Therefore, the magnetic sus-
ceptibility of the a0 phase is considered to be lower than that of the
b phase. The relationship between the magnetic susceptibility of
each phase can be concluded as follows:

vb > va0 > vx

The magnetic susceptibility of pure Zr consisting of a phase was
higher than that of Zr–(0.5–1)Mo consisting of a0 phase, indicating
that the magnetic susceptibility of a phase is higher than that of a0
Fig. 7. Magnetic susceptibilities of Zr–3Mo and metals used for medical devices. phase. When the magnetic susceptibility of Zr–0.5Mo is estimated
1038 Suyalatu et al. / Acta Biomaterialia 6 (2010) 1033–1038
using each magnetic susceptibility of Zr and Mo, the estimated va-
lue (1.36  106 cm3 g1) is higher than that of the measured value
(1.11  106 cm3 g1). Therefore, it is difficult to explain the reason
from the viewpoint of the magnetic susceptibility of Zr and Mo.
The reason for the difference is not clear because a phase and a0
phase have the same crystal structure (hcp). TEM observation of
Zr–1Mo revealed that defects such as dislocation, stacking faults
and twins, which were not observed in pure Zr, were formed in
the fine acicular structure. Further investigations are required to
clarify whether these defects influence the magnetic susceptibility.
From the viewpoint of mechanical reliability, unfortunately
the x phase lacks ductility and toughness. Although the magnetic
susceptibility of as-cast Zr–3Mo alloys shows a minimum value,
Zr–(0.5–1)Mo alloys consisting of the a0 phase would be the best
candidates for medical devices used under MRI.
5. Conclusion
The microstructures and magnetic susceptibilities of Zr–Mo al-
loys were investigated and the relationship between the phase
constitution and magnetic susceptibility was discussed. The
microstructure and the phase constitution depend on the alloy
composition. The a0 phase, with an acicular structure, was domi-
nant in Zr–1Mo alloys, while the x and b phases, with equiaxed
and relatively flat (no acicular) microstructures, were dominant
in Zr–3Mo. The mixed microstructural features of Zr–1Mo and
Zr–3Mo were observed in Zr–2Mo, which consists of the a0 , x
and b phases. The b phase is stabilized when the Mo content ex-
ceeds 3 mass% Mo. As-cast Zr–Mo alloys showed a minimum value
of magnetic susceptibility at 3 mass% Mo. The minimum value of
the susceptibility was closely related to the appearance of the
athermal x phase in the b phase. With decreasing or increasing
Mo content from 3 mass%, the a0 phase or b phase appears with
the x phase, leading to an increase in magnetic susceptibility.
The magnetic susceptibility of each phase is concluded to be
vb > va0 > vx . The magnetic susceptibility of as-cast Zr–3Mo alloy
was almost one-third that of Ti–6Al–4V, which is commonly used
for medical implant devices. Zr–Mo alloys are thus useful for med-
ical devices used under MRI.
Acknowledgements
The authors would like to thank Dr. S. Ichinose for the TEM
observations. This work was partially supported by a Grant-in-
Aid for Fundamental Scientific Research (Kiban B: No. 18300160)
from the Ministry of Education, Culture, Sports, Science and Tech-
nology of Japan, and by a Grant-in-Aid from Iketani Science and
Technology Foundation.
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