Trans. Nonferrous Met. Soc.

China 23(2013) 538−542

Preparation of ultrafine rhenium powders by

CVD hydrogen reduction of volatile rhenium oxides

Meng BAI, Zhi-hong LIU, Le-jun ZHOU, Zhi-yong LIU, Chuan-fu ZHANG
School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China
Received 11 November 2011; accepted 3 May 2012

Abstract: A novel CVD process for the preparation of ultrafine rhenium powders was investigated using ammonium perrhenate as
starting materials. In the process, volatile rhenium oxides, such as ReO4 and Re2O7, were vaporized under a controlled oxidizing
atmosphere via the pyrolysis of ammonium perrhenate, and carried into reduction zone by carrier gas, and there reduced into rhenium
powders by hydrogen gas. Thermodynamic calculations indicated that Re2O7 could be prevented from further decomposition through
controlling the oxygen partial pressure higher than 10−1.248 Pa in the pyrolysis of ammonium perrhenate. This result was further
validated via DSC−TGA analysis of ammonium perrhenate. The typical rhenium powders prepared by the CVD method proposed
show irregular polyhedron morphology with particle size in the range of 100−800 nm and a D50 of 308 nm. The specific surface area
and oxygen content were measured to be 4.37 m2/g and 0.45%, respectively.
Key words: ultrafine rhenium powders; ammonium perrhenate; chemical vapor decomposition; oxygen partial pressure

of manufacturing rhenium products via conventional

1 Introduction powder metallurgy.
Plasma technique can prepare rhenium powders of
Rhenium is a refractory metal that has unknown spherical morphology and good fluidity, but it is
ductility to brittle transition temperature and a high extremely cost ineffective [11−13]. In addition, rhenium
modulus of elasticity. Components formed from rhenium or its alloy coating can be obtained from rhenium halides
can withstand repeated heating and cooling cycles by means of CVD method [14−16], but highly
without incurring mechanical damage. For these and anticorrosive materials must be used for manufacturing
other reasons, rhenium and its alloys are widely used in the equipments used in the processes due to strong
such areas as national defense, aerospace, electronics and corrosiveness of rhenium halides.
petrochemistry [1−3]. Due to the melting point of In this work, a novel CVD process for preparing
rhenium up to 3180 °C, rhenium components are usually ultrafine rhenium powders using ammonium perrhenate
manufactured by powder metallurgy techniques using as raw material was investigated. The process was
rhenium powder as raw material [4]. Therefore, the carried out in a tube furnace including evaporation and
preparation of rhenium powders of excellent reduction zones, and essentially consisted of
performance is a prerequisite in rhenium industry. evaporation−reduction of volatile rhenium oxides. In the
At present, there are two principal methods of evaporation zone, highly volatile rhenium oxides were
preparing rhenium powders commercially: one is direct generated via the pyrolysis of ammonium perrhenate
hydrogen reduction of ammonium perrhenate through under a controlled oxygen pressure, at which volatile
gas−solid reactions [5−7]; while the other is electrolysis rhenium(VII) oxide can be prevented from further
[8−10]. Both of them are simple and easy to implement decomposition into low valent rhenium oxides to
in large scale. However, the rhenium powders made by volatilize. Gaseous rhenium oxides were carried out by
these two methods have some drawbacks such as mixed oxygen and nitrogen gases into the reduction zone,
irregular morphology, broad size distribution, low tap and there reduced into rhenium powders by hydrogen
density and poor fluidity, which results in the difficulty gas.

Corresponding author: Zhi-hong LIU; Tel: +86-731-88830478; E-mail: [email protected]

DOI: 10.1016/S1003-6326(13)62496-6
 Meng BAI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 538−542 539

2 Experimental 3 Results and discussion

2.1 Materials 3.1 Theoretic analysis

Ammonium perrhenate used for the preparation of In the experiment, when ammonium perrhenate is
rhenium powders was obtained from Jiangxi Copper placed in the evaporation zone at 673 K under a mixed
Company in China, and its purity was larger than 99.5%. oxygen and nitrogen atmosphere, it will decompose
The gases of oxygen, nitrogen and hydrogen used in the thermally into gaseous Re2O7 volatilizing according to
experiments were with purity of 99.999%. following equation:
2NH4ReO4+(3/2)O2=Re2O7(g)+4H2O(g)+N2(g) (1)
2.2 Methods
As shown in Fig. 1, CVD reactor used for the Rhenium is a kind of multi-valence metal and there
experiment was a tube furnace composed of evaporation are four rhenium oxides present in Re−O system: ReO4,
and reduction zones, which were connected through a Re2O7, ReO3 and ReO2, the vapor pressures of which at
hole in the partition wall, and controlled at 673.15 K and different temperatures are shown in Fig. 2. Re2O7
1273.15 K, separately. obtained by thermal decomposition of ammonium
In the experiment, a measured amount of perrhenate may be further oxidized into ReO4 or
ammonium perrhenate in a quartz boat was placed in the deoxidized into ReO3, ReO2 and even Re at high
evaporation zone, and pyrolyzed into volatile rhenium temperatures.
(VII) oxide at 673.15 K under a controlled oxygen Re2O7+1/2O2(g)=2ReO4 (2)
pressure, at which volatile rhenium (VII) oxide, Re2O7,
Re2O7=2ReO3+(1/2)O2(g) (bellow 800 K) (3)
can be prevented from further decomposition into low
valent rhenium oxides, ReO3 and ReO2, which are Re2O7=2ReO2+(3/2)O2(g) (above 800 K) (4)
difficult to volatilize. The gaseous rhenium oxides that ReO3=2ReO2+(1/2)O2(g) (5)
were carried by mixed oxygen and nitrogen gases went
2ReO2=2Re+2O2(g) (6)
into the reduction zone, and in this zone, they were
reduced into rhenium powders by hydrogen gas. From Fig. 2, it can be seen that high valent rhenium
oxides, ReO4 and Re2O7, with the boiling points of 493 K
2.3 Characterizations and 635.4 K, respectively, are easier to volatilize than
DSC−TGA analyses of ammonium perrhenate were low valent rhenium oxides, ReO3 and ReO2, with the
carried out using a Q600 integrated thermal analyzer. boiling points of 887 K and 1636 K, individually.
The morphology of the rhenium powders was inspected Therefore, reactions (3) to (6) should be prevented from
by SEM using a JSM−6360LV scanning electron taking place by controlling oxygen potential of the
microscope. The structures of the samples were system, in order to transfer rhenium oxides in gaseous
evaluated by XRD using a Rigaki-TTR Ⅲ X-ray form at a desired temperature into the reduction zone.
diffractometer with Cu Kα (0.154184 nm) source. The Figure 3 shows the oxygen potential diagram of
particle size distributions of the rhenium powders were Re−O system, which was calculated by using HSC
determined by using a Malvern Nano-ZS particle size Chemistry 5.0 software. From Fig. 3, it can be seen that
analyzer. The oxygen content of the rhenium powders Re2O7 can be prevented from deoxidizing into ReO3 or
was measured by using a LECO TCH−600 N/O analyzer. ReO2 by controlling the oxygen pressure above 1013.25
Specific surface area (BET) was measured by using a Pa in the experimental temperature range of 673.15−
quantachrome monosorb specific surface area analyzer. 1273.15 K.

Fig. 1 CVD apparatus for preparing ultra-fine rhenium powders

540 Meng BAI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 538−542

Fig. 4 DSC−TGA curves of NH4ReO4 in air at heating rate of

Fig. 2 Vapor pressure of rhenium oxides at different 10 K/min
temperatures [17,18]

Fig. 5 DSC−TGA curves of NH4ReO4 in nitrogen at heating

rate of 10 K/min

Fig. 3 Oxygen potential diagram of Re−O system

3.3 Effects of oxygen flow on residue of NH4ReO4
pyrolyzing
In the reduction zone, ReO4 and Re2O7 are reduced
The experiments were carried out in the CVD
at 1273.15 K by H2 introduced from the right side of the
apparatus shown in Fig. 1. Under the conditions of
tube furnace.
temperature 673 K and nitrogen flow 60 L/h, 20 g
ReO4(g)+4H2(g)=Re+4H2O(g) (7) NH4ReO4 sample in the quartz boat placed in the
evaporation zone was pyrolyzed for 1 h at different
Re2O7(g)+7H2(g)=2Re+7H2O(g) (8)
oxygen flow rates. The residual mass of NH4ReO4
pyrolyzed in the boat changed with the variation of
3.2 DSC−TGA analysis of ammonium perrhenate in oxygen flow rates, as shown in Table 1. Figure 6 shows
air and nitrogen gas the XRD patterns of residues of NH4ReO4 pyrolyzing at
The DSC−TGA curves of NH4ReO7 obtained in air oxygen flow rates of 40 and 20 mL/min under the
and nitrogen gas at heating rate of 10 K/min are shown in conditions mentioned above.
Fig. 4 and Fig. 5, respectively. Figure 4 reveals that
under oxygen atmosphere (in air), NH4ReO7 pyrolyzed Table 1 Residue mass of 20 g NH4ReO4 pyrolyzing at different
wholly into Re2O7 volatilizing at about 673 K, in oxygen flow rates
according with theoretic analysis mentioned in section Oxygen flow rate/(mL·min−1) 100 80 60 40 20
3.1. From Fig. 5, it can be seen that under inert Residual mass/g 0 0 0 5.87 12.83
atmosphere (in N2), the products of NH4ReO7
decomposition volatilize wholly till up to 1373 K, due to From Table 1 and Fig. 6, it can be seen that the
volatile Re2O7 further decomposing into low valent ReO3 oxygen pressure has a great effect on the decomposition
and/or ReO2, which are difficult to volatilize, as shown of the products in the process of NH4ReO4 pyrolyzing.
in Fig. 2. Under the experimental conditions, NH4ReO4 was
 Meng BAI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 538−542 541
decomposed into Re2O7 volatilizing wholly at oxygen
flow rates greater than 60 mL/min; while NH4ReO4 was
partially decomposed into ReO3 (JCPDS 65—9764) or
the mixture of ReO3 and ReO2 (JCPDS 17—0600) at
oxygen flow rates of 40 mL/min and 20 mL/min,
respectively.

Fig. 6 XRD patterns of residues of NH4ReO4 pyrolyzing at

oxygen flow rates of 40 and 20 mL/min

3.4 Characterization of typical rhenium powders Fig. 8 SEM images of typical rhenium powders prepared by
prepared CVD method: (a) Higher magnification; (b) Lower
Rhenium powders were prepared by using the CVD magnification
apparatus shown in Fig. 1 under the conditions as
follows: nitrogen gas flow rate 60 L/h, oxygen gas flow
rate 60 mL/min, temperature of evaporation zone 673 K,
surplus coefficient of hydrogen gas 6, and temperature of
reduction zone 1273 K. The rhenium powders prepared
under the conditions mentioned above were
characterized by XRD, SEM, size distribution, specific
surface area (BET) and oxygen content analyses.
As shown in Fig. 7, XRD result demonstrated that
the powders prepared by the CVD method proposed
were in the form of metallic rhenium (JCPDS 05—0702).
From the SEM photographs and the particle size
distribution results shown in Fig. 8 and Fig. 9, separately,

Fig. 9 Particle size distribution of rhenium powders prepared

by CVD method

it can be seen that the rhenium powders have irregular

polyhedron morphology with particle sizes in the range
of 100−800 nm and a D50 of 308 nm. The specific
surface area and oxygen content of the powders were
measured to be 4.37 m2/g and 0.45%, respectively.

4 Conclusions

1) A novel CVD method of preparing ultrafine

rhenium powders was proposed and investigated. It uses
Fig. 7 XRD pattern of typical rhenium powders prepared by ammonium perrhenate as starting material and
CVD method essentially consists of evaporation−reduction of highly
542 Meng BAI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 538−542
volatile rhenium oxides (Re2O7). Powder Technology, 2003, 416(4): 273−282.
2) In the preparation process, to convey rhenium [7] SHEN You-yuan, YI Xiao-ming, LIAO Bin-bin. A preparation
method of high purity rhenium powders: CN02114247.5 [P].
oxides produced through thermal decomposition of
2002-07-08. (in Chinese)
ammonium perrhenate, in gaseous form at a desired [8] SCHREBLER R, CURY P. Electrochemical and nano-
temperature into reduction zone, the further electrogravimetric studies of the nucleation and growth mechanisms
decomposition of volatile Re2O7 into low valent rhenium of rhenium on polycrystalline gold electrode [J]. Electrochimica Acta,
oxides of difficulty to volatile, such as ReO3 and ReO2, 2001, 46: 4309−4318.
[9] SCHREBLER R, MERINO M, CURY P, ROMO M, CORDOVA R,
should be prevented from.
GOMEZ H, DALCHIELE E A. Electrodeposition of Cu−Re alloy
3) Thermodynamic analysis and experiments thin films [J]. Thin Soild Films, 2001, 388: 201−207.
demonstrated that the further decomposition of Re2O7 [10] NAOR A, ELIAZ N, GILEADI E. Electrodeposition of
into ReO3 and ReO2 can be prevented from by rhenium−nickel alloy from aqueous solutions [J]. Electrochimica
controlling the oxygen pressure of the process. Acta, 2009, 54(25): 6028−6035.
4) The typical rhenium powders prepared by the [11] JUREWICZ J W, GUO Jia-yin. Process for plasma synthesis of
rhenium nano and micro powders, and for coating and near net shape
CVD method proposed have irregular polyhedron
deposits thereof and apparatus therefore: US: 2005/0211018A1 [P].
morphology with particles sizes in the range of 100−800 2005-09-29.
nm and a narrow size distribution. [12] LEONHAROT T, HAMISTER M, MOURE N, DOWNS T.
Advancements in powder metallurgy rhenium [C]// KUBEL.
References Advances in Powder Metallurgy and Particulate Materials. New
Orleans: Metal Powder Industries Federation, 2001: 408−422.
[13] LEONHARDT T, HICKMAN R. Consolidation methods for
[1] NAOR A, ELIAZ N, GILEADI E, TAYLOR R. Properties and
spherical rhenium and rhenium alloys [J]. Powder Metallurgy, 2003,
applications of rhenium and its alloys [J]. The AMMTIAC Quarterly,
46(2): 148−153.
2010, 5(1): 11−14.
[14] GONCHAROV O Y, FAIZULLIN R R, SHADRIN M G,
[2] LOU Zhe-ning, XIONG Ying, SONG Jun-jun, SHAN Wei-jun, HAN
KANUNNIKOV M F. Chemical vapor deposition of Mo, Re, and Ta
Guang-xi, XING Zhi-qiang, KONG Yu-xia. Kinetics and mechanism
films [J]. Inorganic Materials, 1999, 35(10): 985−987.
of Re(VII) extraction and separation from Mo(VI) with trialkyl
[15] HU C Y, CHEN S, YANG J M, DENG D G, GAO Y Q, YIN Y M,
amine [J]. Transactions of Nonferrous Metals Society of China, 2010,
WANG Y, LI J H. Diffusion study in interface of iridium/rhenium
20: 10−14.
composite prepared by CVD [J]. Rare Metal Materials and
[3] BUSBY J T, LEONARD K J, ZINKLE S J. Radiation-damge in
Engineering, 2003, 32(10): 796−798. (in Chinese)
molybdenum−rhenium alloys for space reactor applications [J].
[16] LI Jing-hua, HU Chang-yi, GAO Yi-qun. Study of rhenium tube
Journal of Nuclear Materials, 2007, 366: 388−406.
prepared by chemical vapour deposition [J]. Aerospace Materials &
[4] TRYBUS C L, WANG C M, PANDHEERADI M, MEGLIO C A.
Technology, 2001(4): 54−56. (in Chinese)
Powder metallurgical processing of rhenium [J]. Advanced Materials
[17] FRENKEL M, KABO G J, MARSH K N, ROGANOV G N,
& Processes, 2002, 160(12): 23−26.
WILHOIT R C. Thermodynamics of organic compounds in the gas
[5] STEFAN L, HELMUT A. Hydrogen as a reducing agent:
state [M]. Vol: 1-2. Texas: TRC, 1994.
State-of-the-art science and technology [J]. JOM, 2007, 59(6):
[18] ZHOU Ling-zhi, CHEN Shao-chun. Extractive metallurgy of
20−16.
scattered metals [M]. Beijing: Metallurgical Industry Press, 2008:
[6] MNNHEIM R L, GARIN J L. Microstructural characterization of
141−150. (in Chinese)
rhenium powder obtained at various temperatures [J]. Advanced

采用 CVD 法还原挥发性铼的氧化物制备超细铼粉
白 猛，刘志宏，周乐君，刘智勇，张传福

中南大学 冶金科学与工程学院，长沙 410083

摘 要：研究了一种以高铼酸铵为原料，采用化学气相沉积(CVD)制备超细铼粉的新方法。通过控制氧分压，使
得 NH4ReO7 分解为具有挥发性的 ReO4、Re2O7，再采用载气将其输运至还原区，经氢气还原生成超细铼粉。热力
学计算表明，在 NH4ReO7 分解过程中，控制氧分压高于 10−1.248 Pa 时，Re2O7 将不会分解为低价氧化物，DSC−TGA
分析结果也证实了这一点。采用该方法制备的铼粉，粒度为 100~800 nm，D50 为 308 nm，比表面积为 4.37 m2/g，
氧含量为 0.45%。
关键词：超细铼粉；高铼酸铵；化学气相沉积；氧分压
(Edited by Hua YANG)