Met. Mater. Int., Vol. 19, No. 3 (2013), pp.

527~532
doi: 10.1007/s12540-013-3022-x

Direct Synthesis of Zirconium Powder by Magnesium Reduction

1 1 2 3,*
Dong-Won Lee , Jung-Yeul Yun , Sung-Won Yoon , and Jei-Pil Wang

1
Powder Technology Research Group, Korea Institute of Materials Science (KIMS),
Changwon, Kyungnam 641-010, Korea
2
School of Architecture, Seoul National University of Science and Technology,
Seoul 139-743, Korea
3
Department of Metallurgical Engineering, Pukyong National University, Busan 608-739, Korea
(received date: 25 February 2012 / accepted date: 25 June 2012)

The direct synthesis of zirconium powder has been conducted through an analysis of the chemical reac-
tion between evaporated ZrCl4 and molten magnesium over a range of reduction temperatures, concentra-
tion of hydrochloric acid, and stirring time. The observed results indicated that the purity of zirconium
powder increased with increased stirring time, and Mg and MgCl2 were removed by 10 wt% of hydro-
chloric acid solution. The pure zirconium powder was obtained by stirring again for 5 h using 5 wt% of
hydrochloric acid solution. It was noted that the mean particle size increased when the reaction tempera-
ture was increased, and the size of the powder at 1,123 K and 1,173 K was found to be 10 µm and 15 µm,
respectively. In addition, the purity of the powder was also improved with temperature, and its purity
finally reached up to 99.5% at 1,250 K. Overall, pure zirconium powder was obtained after a stirring stage
for 5 hours using 5 wt% of hydrochloric acid solution.
Key words: chemical synthesis, powder processing, zirconium, purification, metals

1. INTRODUCTION (Hydrogenation-Dehydrogenation) process [5-8]. This pro-

Zirconium(Zr) has been known to have excellent corro-
sion resistance, better than any other materials. Moreover,
because of its great mechanical properties and thermal con-
ductivity, it has been widely applied to industrial fields such
as nuclear power plants, cell phones, synthetic fibers, and
petrochemical industries. Most notably, zirconium powder is
now used as a raw material for Getter of vacuum tubes, cat-
alyst of airbags, and various chemical manufactures [1]. In
architectural industries, it also has potential application. It
can be used like titanium as a surface coating media for an
anti-corrosive roof or wall against acid rain [2-4]. Therefore,
this study has concentrated on the synthesis of high purity
powder, since the purity of zirconium powder as a raw mate-
rial can significantly affect the characteristics of the final
products.
The most well known process for manufacturing metal
powders is a gas atomizing process. However, this process
has shown technical limits because some materials with high
melting temperature are not suitable for this process. Thus,
the current process being widely used to manufacture zirco-
nium powder is a dehydrogenation process, namely the HDH
*Corresponding author: jpwang@pknu.ac.kr
©KIM and Springer, Published 10 May 2013
cess consists of preparing a sponge zirconium as a starting
material which is produced through a reaction between zir-
conium chloride (ZrCl4) and magnesium (Mg). Then, zirco-
nium hydride (ZrH2) is obtained through a reaction with the
sponge zirconium and hydrogen (H2). Finally, zirconium
hydride (ZrH2) is crushed and dehydrogenated to become a
zirconium powder (Zr). This process also has some weak
points. For example, (1) it requires a multi-step process
including a milling process which can lead to the contamina-
tion of products. Therefore, (2) hydrogen gas (H2) should be
used, because (3) the crushed powders have a high oxygen
concentration due to a large specific surface area caused by
the irregular shapes of the milled particles.
In this study, an efficient process modified from the con-
ventional process of magnesiothermic reduction, namely the
Kroll process [9], which has been applied to produce zirco-
nium sponge, was attempted to directly manufacture zirco-
nium powder. Zirconium chloride is reduced by magnesium
and vacuum distillation is used to remove the excess magne-
sium (Mg) and magnesium chloride (MgCl2) existing within
the zirconium metal cake or powder form. However, as this
process is performed at around 1,273 K, the zirconium metal
powder left behind is found to be severely cohesive and
becomes a form of zirconium sponge. Thus, conventional
vacuum distillation was found to be not suitable for manu-
528 Dong-Won Lee et al.
facturing a powder form of metallic zirconium. In this study,
a new process for removing Mg and MgCl2 using the route
of chemical dissolution at room temperature, was suggested.
In this study, the effects of reduction temperature and the
concentration of HCl solution will therefore be examined in
an attempt to control the size and purity of zirconium powder.
2. EXPERIMENTAL PROCEDURES
A schematic diagram of the experimental apparatus for the
fabrication of zirconium metal powder is shown in Fig. 1.
Two reactors were prepared at the machine shop, which
were made of SUS 316L. One was placed on the top to con-
tain 400 g of ZrCl4 powder, and 120g of Mg was put into the
other on the bottom. Each reactor was connected with a
cylindrical pipe made of the same material used in the reac-
tors. The chamber was insulated by a vacuum pump up to
about 1.33 Pa, and then UHP argon gas was injected to
maintain 111 kPa inside the chamber. This process was car-
ried out three times to fully remove all oxygen out of the
chamber. The powder of ZrCl4, with an evaporation temper-
ature of 603 K, was located on the upper reactor and heated
to about 773 K in order to transform it into gas phase. The
lower part of the reactor, including pure magnesium, was
melted in the range of 1,073 to 1,223 K.
When the ZrCl4 powder was vaporized at a specific tem-
perature above boiling point, its gas flowed down due to the
force of gravity and it then reacted with the molten magne-
sium on the bottom. In the lower part of the reactor, Mg was
going to form MgCl2 through the Cl-reduction process with
ZrCl4, and the component of pure zirconium was left inside
the molten magnesium. Reaction time for the reduction was
Fig. 1. Schematic diagram of the reactor inside chamber.
about 30 min with 5 h holding at the same temperature for
complete formation of stable zirconium particles inside the
liquid magnesium. After the entire process, a mixture of
solid Zr particles and liquid Mg and MgCl2 was obtained
from the lower reactor. Once the temperature was cooled down
to room temperature, zirconium powder could be recovered
from the mixture by dissolving it into 10% of hydrochloric
acid (HCl) solution. The powder obtained was stirred again
for 10 h using 1-5% of hydrochloric acid solution since it
was still found to contain minor impurities of about 1-2% of
MgCl2 and/or Mg(OH). Finally, a cleaning process was con-
ducted in pure distilled water whilst stirring for 30 min, three
times. The metal powder of zirconium was characterized for
its microstructure, crystal structure, and chemical composi-
tion by X-ray Diffraction (XRD), X-ray Fluorescence Spec-
trometry (XRF), Oxygen Nitrogen Determinator, Scanning
Electron Microscopy (SEM), and Energy Dispersive X-ray
Spectroscopy (EDX).
3. RESULTS AND DISCUSSION
The main concept of the current study conducted to manu-
facture zirconium powder is similar to the well-known magen-
siothermic reduction, namely, the Kroll process for production
of sponge zirconium and titanium [10-12]. In the Kroll pro-
cess, powders of zirconium chloride are injected directly into
liquid magnesium with a high feed rate, of about several
kilograms per minute, to form an agglomerated zirconium
product inside the liquid magnesium. And after reductive
reaction, the residual magnesium and magnesium chloride
mixed with zirconium product are removed by vacuum at
about 1000 °C, in which the zirconium becomes the pre-sin-
tered sponge shape.
In this study, three processes were changed to be different
than the previous study. First, the zirconium chloride would
be injected only as vaporized pure ZrCl4 gas to enhance the
purity of the product. The purity of the final product can be
degraded by the ZrO2 impurity of ZrCl4 placed in molten
magnesium, since ZrCl4 may always have small amounts of
ZrO2. Secondly, a very low feed rate, about 15 g/min, of
ZrCl4 gas was selected for the formation of as small as pos-
sible zirconium nuclei particles. The third was to employ the
dissolution treatment instead of vacuum distillation to
remove the Mg and MgCl2 mixed with zirconium particles at
room temperature to obtain the powder state. The schematic
concept of the modified process employed in this study is
described in Fig. 2, and compared with the conventional one.
Before conducting the main reaction experiment, a study
on the evaporation of ZrCl4 in argon atmosphere was required
to determine the proper temperatures at elevated temperature
using a thermogravimetric apparatus (T.G.A.), which is shown
in Fig. 3. It shows that ZrCl4 was found to start evaporating
at about 500 K and the evaporation of ZrCl4 might be com-
 Direct Synthesis of Zirconium Powder by Magnesium Reduction 529

Fig. 2. Schematic concept to produce zirconium powder by magnesiothermic reduction.

pletely finished at 660 K since there was no more weight

loss. On the other hand, it was found that the weight loss
after the complete evaporation of ZrCl4 did not take place
below about 10% of weight change, which turned out to be
ZrO2 when analyzed by XRD. It could be explained that
small amounts of ZrO2 were originally contained in the ZrCl4
powder, or that the inside of the chamber was contaminated
by oxygen during the evaporation, which led to the oxidiza-
tion of ZrCl4 to ZrO2. In this study, a modified process was
attempted so that pure ZrCl4 was therefore injected into mag-
nesium.
According to the resulting data shown in Fig. 3, the metal
powder of ZrCl4 was completely transformed to a gas phase
after 660 K, and 773 K was therefore designated as the desired
temperature in the upper part of reactor. The gas phase of
ZrCl4 vaporized at 773 K reacted with molten magnesium
placed in the lower part of reactor, and the equation for this
reaction is shown as follows: Fig. 3. Weight change of ZrCl4 with temperature in argon atmosphere.

ZrCl4(g) + 3Mg(l)→Zr(s) + Mg(l) + 2MgCl2(l)
∆G°1073−1173K = −68.03−69.05 kcal
According to the reaction equation (1), a chloride reduc-
tion process could take place between a gas form of ZrCl4
and molten Mg leading to the production of zirconium (Zr)
and small amounts of magnesium (Mg) in a molten solution
of magnesium chloride (MgCl2). During the experiment
inside the chamber, UHP argon gas was continuously injected
to maintain an inside pressure of 111 kPa (1.1 atm), since the
pressure inside the chamber might fall below 1 atm due to
the consumption of ZrCl4 gas by condensation at the cham-
ber wall. The constant positive pressure therefore helped to
(1) prevent air leaking. Once the reaction was finished, the
chamber was cooled down to room temperature and a solid
form of MgCl2 was produced. A solid mixture of MgCl2, Zr,
and Mg was flushed by 10 wt% of hydrochloric acid solu-
tion four times so as to remove MgCl2 and Mg. The Zr pow-
der obtained after the washing process was observed to still
have several impurities such as O, Fe, Mg, and Cl, which
accounted for around 2 wt% out of the total amount. Among
the impurities in the Zr powder stated previously, oxygen
might be expected to exist as a phase of ZrO2 film on the sur-
face of Zr powder. Moreover, iron could be diffused into the
530
molten specimen from the reactor surface, and Mg and Cl
might still remain after flushing with the hydrochloric acid
solution (HCl) as several phases of MgCl2, Mg, MgO, and
Mg(OH)2. Therefore, a second cleaning process with 1-5
wt% of hydrochloric acid solution was consequently conducted
to remove more impurities from the Zr powder. MgCl2 espe-
cially was easily dissolved into water, since its solubility was
relatively high with 54 g/100 ml. Furthermore, other impuri-
ties were removed during the second cleaning stage with the
following reactions from (2) to (5) resulting in enhancing the
purity of the Zr metal powder.
Mg + 2HCl = MgCl2 + H2 ∆G°300K = −401 kJ mole
MgO + 2HCl = MgCl2 + H2O ∆G°300K = −69 kJ mole
MgO + H2O = Mg(OH)2 ∆G°300K = −27 kJ mole
Mg(OH) + 2HCl = MgCl2 + 2H2O
∆G°300K = −42 kJ mole
The resulting purity of the Zr powder after dissolution
treatment is shown in Fig. 4 in terms of different stirring time
and solution concentration. According to the results in Fig. 4,
the purity of zirconium powder was increased with increas-
ing stirring time, regardless of the concentration of HCl solu-
tion. Overall, it was found that maximum purity was achieved
after about 5 h of the stirring process and more time was found
to be no longer necessary to improve the powder’s purity.
Figure 5 representatively illustrates X-ray patterns of zir-
conium powder reduced in magnesium at 1,123 K, since
Fig. 4. The change of purity at each HCl-solution as a function of stir-
ring time.
Table 1. Purity of zirconium powder reduced in magnesium at 1,123 and 1,173 K
N/O Analyzer Elemental Analyzer
Temp.
O H
1,123 K 0.32 <0.001
1,173 K 0.08 <0.001
Dong-Won Lee et al.
(2)
(3)
(4)
(5)
Fig. 5. X-ray diffraction patterns of zirconium powder reduced in
magnesium at 1,123 K.
XRD patterns of the powder obtained from each temperature
had shown the same results. Based on the XRD results, only
zirconium peaks were observed, which means that pure zir-
conium powder was successfully achieved. In addition, each
specimen of the powder obtained at 1,123 K and 1,173 K
was examined by X-ray fluorescence (XRF), N/O analyzer,
and elemental analyzer, respectively, and the results are
shown in Table 1. It was observed that the powder conducted
at 1,173 K had a much lower quantity of oxygen than at
1,123 K, while it had a higher content of iron at 1,173 K than
the content at 1,123 K. The low oxygen content shown in the
sample at 1,173 K can be explained by the coarsened particle
resulting from high reduction temperature. That is, a large
particle has low specific surface area, which means that a
large particle has low oxygen content since most oxygen nat-
urally exists as a form of oxide on the surface of metal parti-
cles. Alternatively, a high concentration of iron observed at
1,173 K might result from an iron component diffusing from
the inner wall of the SUS reactor due to the relatively high
reduction temperature.
The results of powder shape and chemical composition
examined by scanning electron microscopy (SEM) and energy-
dispersive X-ray spectroscopy (EDX) at 1,123 K and 1,173 K
are shown in Fig. 6. As shown in photos (a) and (b), the size
of the powder was observed to be about 5 µm and 20 µm on
average, and the shape of each powder was found to be
almost spherical. In accordance with reduction temperatures,
XRF
C Fe Mg Cl Zr
<0.001 0.15 0.11 0.05 99.37
<0.001 0.32 0.07 0.03 99.5
 Direct Synthesis of Zirconium Powder by Magnesium Reduction
Fig. 6. The shape of zirconium powder by SEM and chemical compo-
sition by EDX: (a) 1,123 K (b) 1,173 K, and (c) 1,173 K.
the size of the powder at 1,123 K was much larger than at
1,173 K, since the initially formed zirconium particles in
molten Mg could be agglomerated together at a relatively
high temperature. In addition, EDX analysis of the specimen
at 1,173 K illustrated that other impurities besides Zr were
not detected which means that high-purity zirconium pow-
der was successfully achieved. In addition, the zirconium
particles could also be successfully produced by the same
process at 1,223 K. There were however some difficulties at
this temperature as the zirconium powders were severely
agglomerated as large clusters, and moreover, the liquid mag-
nesium was intensely evaporated, which led to significant
loss in the end. Therefore, it is not suitable to do this experi-
ment at 1,223 K for the manufacture of zirconium powder.
The mean particle size and the effect of temperature on the
Fig. 7. Mean particle size and purity of zirconium powder as a func-
tion of temperature.
531
purity of zirconium powder are shown in Fig. 7. It is noted
that the mean particle size increased as reaction temperature
increased. In addition, the purity of the powder also improved
with temperature and its purity finally reached up to 99.5%
at 1,250 K. In order to further improve the purity of the zir-
conium powder it might be possible to change the SUS reac-
tor into a zirconium reactor in order to reduce the iron
content in molten magnesium. However, the proposed pro-
cess using a reactor manufactured of zirconium metal might
not be feasible due to the relatively high price of zirconium
metal. Further studies will continue in order to improve the
purity of zirconium powder and to seek alternative ways to
replace the SUS reactor with economically feasible reactors
such as the lamination of zirconium on the inner surface of
the SUS reactor and/or placing cylindrical zirconium-clad-
ding inside the existing reactor.
4. CONCLUSIONS
Zirconium powder was successfully obtained by improving
the existing process for manufacturing a zirconium sponge.
Evaporated ZrCl4 was directly reacted with molten magne-
sium producing zirconium and magnesium chloride in mag-
nesium solution. After the reaction was completed at room
temperature, Mg and MgCl2 were removed by 10 wt% of
hydrochloric acid solution. Finally, pure zirconium powder
was obtained by stirring again for 5 h using 5 wt% of hydro-
chloric acid solution. It was noted that the appropriate tem-
peratures for reduction were found to be in the range of
1,123 K and 1,173 K, and the size of the powder at these
temperatures was shown to be 10 µm and 15 µm, respectively,
with about 99.5% of purity acquired.
ACKNOWLEDGMENTS
This study was supported by the R&D Center for Valuable
Recycling (Global-Top Environmental Technology Devel-
opment Program) funded by the Ministry of Environment
(Project No.:11-A06-MR) and KIMS (Korea Institute of
Materials Science).
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