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JOURNAL OF RARE EARTHS, Vol. 32, No. 11, Nov. 2014, P.

1073

Impurities especially titanium in the rare earth metal gadolinium


before and after solid state electrotransport
MIAO Ruiying ()*, ZHANG Xiaowei (), ZHU Qiong ( ), ZHANG Zhiqi (), WANG Zhiqiang (),
YAN Shihong (), CHEN Dehong (), ZHOU Lin ( ), LI Zongan ()
(National Engineering Research Center for Rare Earth Materials, General Research Institute for Nonferrous Metals, Grirem Advanced Materials Co. Ltd., Beijing 100088, China)
Received 23 May 2013; revised 4 August 2014

Abstract: Gadolinium was prepared by conventional procedures of fluorination, reduction, distillation and solid state electrotransport
(SSE). The electronegativities of the metals were found to have an important influence on the electrotransport process and result of
the impurity element. Meanwhile, titanium particles in the distilled gadolinium as major metallic impurities were studied by high
resolution transmission electron microscopy (HRTEM) before and after solid state electrotransport. The results showed that impurities
especially titanium transported from anode to cathode during SSE. In the metal before SSE, there were impurities of titanium in strip
shape or embedded round shape. After SSE processing, titanium particles in the metal smaller than 50 nm in the cathode, but existed 6
to 10 times bigger in the anode.
Keywords: impurities; titanium; rare earth metal; gadolinium; solid state electrotransport

Gadolinium has no large-scale applications but has a


variety of specialized uses, such as applications in the
luminescence, electricity, magnetism, nuclear and especially in medicine.
High purity metals are desired when used for magnetostrictive and magnetic refrigerant materials, and when
used for searching their intrinsic or unknown properties.
However, the high purity metal cannot be achieved easily
with regard to the highly active rare earth metals. During
the past decades, preparation of the rare earth metals was
introduced in detail by the researchers of the Ames
Laboratory[1]. In recent decades, rare earth has been becoming a hot topic[24]. Solid state electrotransport (SSE)
had been applied to rare earth metals since 1961[1], and
the first material was yttrium. In 1972[5], electrotransport
velocities of O, N and C in gadolinium were determined
by Peterson and coworkers at Ames Laboratory. During
these decades, purifications of all possible rare earth
metals by SSE were studied by researchers at Ames
Laboratory and University of Birmingham, United
Kingdom[1,623] and interstitial impurities such as O, N
and C were main topics in these papers. This may be attributed to the obvious effect of transport. Compared to
the interstitial impurities, metallic impurities were less
focused on. As for titanium, still less.
In this paper, SSE was studied from a particular perspective. Firstly, gadolinium was prepared from common

gadolinium oxide (99%), and the final metal was obtained by fluorination, reduction, distillation and solid
state electrotransport. And after that, the compositions of
the metals before and after SSE were characterized by
glow discharge mass spectrometry (GDMS). The microstructures of metallic impurities especially titanium in the
metal and the metal itself were characterized by HRTEM,
as well.

1 Experimental
1.1 Fluorination
Gd2O3 was fluorinated by continuously mixing with
HF gas at 600 C for 8 h in accordance with the following formula[24,25]:
Gd2O3(s)+3HF(g)=GdF3(s)+3H2O (g)
(1)
GdF3(s)+H2O(g)=GdOF(s)+2HF (g)
(2)
Here, formula (2) is a side reaction. To avoid the side
reaction, multiple fluorinations are recommended. If high
purity is desired, multiple fluorinations are essential.
1.2 Reduction
The product in the above step was reduced by calcium
particles in the carbon tube furnace in the titanium crucible at 1500 C for half an hour in the argon atmosphere[26].

Foundation item: Project supported by Major State Basic Research Development Program of China (973 Program: 2012CBA01207) and the National
High Technology Research and Development Program of China (863 Program: 2011AA03A409)
* Corresponding author: MIAO Ruiying (E-mail: ruiyingmiao@163.com; Tel.: +86-10-89583403-235)
DOI: 10.1016/S1002-0721(14)60185-X

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JOURNAL OF RARE EARTHS, Vol. 32, No. 11, Nov. 2014

In the process, the product Gd and CaF2 were layered


according to the density difference as shown in Table 1.
Thus the metal obtained layered in the bottom of the crucible and the slag layered in the top. Both of them could
be easily separated.

(HRTEM, Tecnai G2 F30 S-TWIN) coupled with energy


dispersed spectroscopy (EDS) was used to acquire the
microstructures and morphologies of the metals.

Table 1 Some of the physical constants in the reduction


Material

m.p./C

b.p./C

Density

GdF3

1231

2277

7.1

Gd

1313

3273

7.89

Ca

842

1484

1.55

CaF2

1418

2534

3.18

* m.p.: melting point; b.p.: boiling point

1.3 Melting and distillation


The metal obtained was melted in the vacuum tantalum furnace at 1800 C for half an hour, and distilled at
1725 C for 20 h[17,27]. In the melting process, those volatile and high vapor-pressure impurities were eliminated.
And the distillation removed most of those non- volatile
and low vapor-pressure impurities from the metal.
1.4 Solid state electrotransport (SSE) processing
Solid state electrotransport device was designed and
manufactured according to Refs. [28,29]. In this process,
ultra high vaccum is essential[10,30]. In this study, the degree
of vacuum was 5107 Pa, approximately 41010 Torr.
The specimens used in the electrotransport measurement were rods with 11 cm in length and 0.8 cm in diameter machined from the distilled metal.
The experiment was carried out in the current density
of 450 A/cm2 at 1250 C, above the temperature of the
crystal transformation (1235 C) of gadolinium from a
structure of hexagonal close packing (h.c.p.) to structure of body-centered cubic (b.c.c.)[31]. This transformation would result in the decrease of the efficiency of
space filling and thus in the increasing of the volume for
the crystal transformation part.
1.5 Characterization
For chemical analysis, all of the samples obtained were
characterized by glow discharge mass spectrometry (GDMS).
High resolution transmission electron microscopy

2 Results and discussion


2.1 Photos of the gadolinium rod during the SSE
processing
Photos of the gadolinium rod during the solid state
electrotransport processing are shown in Fig. 1.
Non-uniform temperature distribution could be seen
from Fig. 1(b). During the processing, the highest temperature appeared in the lower part of the rod. The ends
of the rod are at a lower temperature than the center. The
maximum difference can be 260 C. This difference can
make the impurities at the ends migrate more slowly than
those in the center[10].
It is known that the electrotransport mobilities and diffusion coefficients for solutes such as C, N and O are
considerably higher in (b.c.c.) form than in (h.c.p.)
form, as shown in Fig. 2[31]. Because of the temperature
difference of the whole rod, there should be two forms of
gadoliniums that exist in our processing rod. From the
dynamic-view, the transport mobilities and diffusion coefficients of the solutes are different in them. From the
thermodynamic-view, the structure of the different parts
with different forms should be different, as well. In this
paper, the rods after SSE displayed different degrees of
bending at the brightest part. It might be interpreted that
the brightest part of the rod had a structure of b.c.c.,
which had low efficiency of space filling. Thus the volume of the b.c.c. part would increase, and meanwhile
other part of the bar with h.c.p. form would remain unchanged during the process. This function would cause
the bending of the whole rod, and even cause break in
some serious cases. It is consistent with the results of
Spedding and his research team[32]. In his paper, the atomic
volume increased sharply when b.c.c. formed. Thermal
expansion coefficient is an average of 8.9 at 400C for
gadolinium with same crystal form. The coefficient in
c-axis (13.0) is more than twice as much as in the direction of a-axis (6.3).

Fig. 1 Photos of the gadolinium rod during SSE processing


(a) Before electrotransport; (b) During heating process; (c) During thermal insulation

MIAO Ruiying et al., Impurities especially titanium in the rare earth metal gadoliniumbefore and

2.2 Metallic impurities in the gadolinium rod


For chemical analysis, the product rod was separated
into several parts. The part close to anode was defined as
A, and the bending part was defined as B as shown on
the right side in Fig. 1.
The electronegativity and concentration of the rare
earth metallic impurities in the gadolinium before and
after SSE are listed in Table 2; the alkali and alkali earth
metallic impurities are listed in Table 3, and the other
metallic impurities are listed in Table 4.
Tables 2, 3, and 4 show that SSE was effective not
only for the interstitial impurities but for some of the
metallic impurities in gadolinium.
There is an interesting phenomenon that if the electronegativity of the element is higher than that of the rare
earth metal, the effect of SSE is more obvious. From Table 2, the electronegativity of gadolinium is 1.2. For the
rare earth elements, their activities are closely after the
elements of alkali metal and several alkali earth metals.
Therefore, their electronegativity is bigger than those of
the elements of alkali and alkali earth metals and smaller
than those of almost all other elements. From Table 2,
the effect of SSE processing is less obvious on the elements having smaller electronegativity.
At the same time, in Table 3, the effect of SSE processing on the alkali and several alkali earth metals having
smaller electronegativity is less obvious. And opposite
Table 2 Electronegativity and concentration (g/g) of rare
earth metallic impurities in the metal before and
after SSE
Element

La

Electronegativity

Ce

1.1 1.12

Gd

Dy

Ho

Er

Tm

Lu

1.2

1.22 1.23 1.24 1.25 1.27

Initial

14

1.3

Matrix

24

17

0.53

1.7

Part A

15

2.1

Matrix

30

21

0.83

2.2

9.4

Part B

18

2.1

Matrix

11

8.8

0.26 0.83

1.5

Table 3 Electronegativity and concentration (g/g) of several alkali and alkali earth metallic impurities in
the metal before and after SSE
Element

Li

Na

Ca

Electronegativity

0.98

0.93

0.82

1.00

Initial

0.11

0.54

0.08

4.2

Part A

0.02

0.53

0.1

2.3

Part B

0.02

<0.05

1.9

Table 4 Electronegativity and concentration (g/g) of other


metallic impurities in the metal before and after
SSE
Element

Al

Ti

Electronegativity 1.61 1.54

Cr

Mn Fe

Nb Mo

Ta

Pb

1.66 1.55 1.83 1.6 2.16 1.5 2.36 2.33

Initial

340 1900

17

23

90

2.5 170 110 3.7 5.2

Part A

320 1200

8.5

13

58

1.7

Part B

200 500 <0.005 0.01 0.87 0.87 5.7 40 0.91 0.26

97 80 3.7 4.7

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effect, such as Na even appeared. It might be interpreted


as follows. For the element having smaller electronegativity accompanied with the weaker attraction of the nucleus to the outer electron, the strong energy of the electric field may result in the ionization of the metallic particle, and thus the diffusion in the direction backward the
electrons occurred.
As for other metals, their electronegativities are larger,
that is, their nuclei have larger attraction than outer electrons. When current passes through, namely, when the
electrons flow through directionally, strong driving force
to the outer electrons of those metals will drive them go
ahead in the same direction as the electrons, and strong
attraction between the nucleus and the outer electrons
will make the nucleus go ahead with two kinds of the
electrons. The larger electronegativity is, the more obvious this tendency is.
With regard to elements of those interstitial impurities,
such as C, N and O, with the largest electronegativities
except halogen have very small size in comparison with
the metallic impurities. These particles may diffuse fast
following the interstitialcy mechanism without the electric field in the close-packed structure at high temperatures. They will diffuse faster because of their largest
electronegativities in the strong electric field. These two
effects working together led to the high removal rate of
O, which is more than 98% (890 g/g before SSE, and
10 after SSE).
2.3 Existence form of impurities
Many different small fragments of the separated part A
and B were chosen and processed into samples for TEM
to find out the existence of impurities in the metal. In order to validate the reliability of the results, repeated tests
had been conducted several times.
2.3.1 Existence form of impurities in samples before SSE
Fig. 2 shows the different morphologies of titanium in
the rod before SSE.
HRTEM images show titanium of strip shaped (2(a)
and (b)) or embedded round shaped (2(c)) structure existing in the metal.
In Fig. 2, the titanium particles appeared in gadolinium
with strip shaped (about 100 nm400 nm) or embedded
round shaped (about 400 nm in diameter) structure. Fig.
3 displays the EDS results corresponding to Fig. 2. They
showed that the white inclusions were mainly composed
of titanium. Other elements such as iron, copper,
chromium and molybdenum coexisted within them.
For Fig. 3(b), the concentration of gadolinium was
higher than that of titanium mainly because the inclusion
was covered by the substrate. These white inclusions
presented different appearances. Fig. 4 shows the micro-morphology of the gadolinium substrate before SSE.
From Fig. 4, lots of tiny pits were seen in the metal. EDS

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JOURNAL OF RARE EARTHS, Vol. 32, No. 11, Nov. 2014

Fig. 2 TEM micro-morphology of strip shaped (a, b) and embedded round shaped (c) titanium in gadolinium before SSE

Fig. 3 EDS results (a) (corresponding to Fig. 2(a)), (b) and (c) (corresponding to Figs. 2(b) and 2(c)))

Fig. 5 Morphology of titanium (a, raised ellipse shape and b,


superimposed footprint shape) of part A after SSE in
gadolinium
Fig. 4 TEM The micro-morphology of the gadolinium substrate
before SSE

results showed small amount of Ti, Mo and Cr existing


inside. Titanium impurities here should be introduced by
the crucible material. Other impurities such as iron and
chromium were probably introduced by titanium crucible,
too. As for copper, it might be contaminated during sample preparation.
2.3.2 Occurrence of impurities in sample of part A after
SSE
HRTEM images of titanium of part A after SSE are
shown in Fig. 5.
From Fig. 5, titanium particles appeared some raised
ellipse shape (300 nm400 nm) and superimposed footprint shape (small footprint: about 400 nm600 nm).
EDS results (Fig. 6) show that these different inclusions
of titanium in part A were mainly composed of titanium,

and small amount of iron, copper, chromium and molybdenum, etc. And there were only minor differences in
the content of both structures. The ellipse shaped inclusion illustrated in Fig. 5(a) may be evolved by the embedded round shape illustrated in Fig. 2(c). The superimposed footprint shaped inclusion might be evolved by
the strip shape illustrated in Fig. 2(a) or (b).
Fig. 7 demonstrates the micro-morphology and the
electronic diffraction pattern of the gadolinium substrate
of part A.
Fig. 7(a) shows the morphology of the gadolinium
substrate of part A. There were small obvious pits inside
the metal. Fig. 7(b) gives the electronic diffraction pattern of the gadolinium substrate. In this section, the crystal
structure was close-packed structure of h.c.p. EDS results
indicate a substantial amount of Cr, Fe and Mo inside.
3.3.3 Occurrence of impurities in sample of part B after SSE
The morphology of titanium of part B is illustrated

MIAO Ruiying et al., Impurities especially titanium in the rare earth metal gadoliniumbefore and

1077

Fig. 6 EDS results (a) (corresponding to Fig. 4 (a) and (b) (corresponding to Fig. 4(b))

Fig. 7 Micro-morphology (a) and the electronic diffraction pattern (b) of the gadolinium substrate of part A

in Fig. 8. There were two small spots less than 50 nm and


one strip less than 50 nm in width. Their EDS results are
shown in Fig. 9. Fig. 9 shows EDS results of the two
white spots. They mainly consist of titanium and gadolinium. And the gadolinium content was higher than that
of the inclusions of part A. It may be interpreted as the
diameter of the electron beam of EDS was bigger than
that of the inclusion itself. As for the strip shaped inclusion, it is very similar to the one in the rod before SSE.
The possible reason was that this shaped inclusion was a
perfect single crystal. Energy for destroying the single
crystal is higher than that for polycrystalline. Therefore the
transport of single crystal is more difficult. Thus it is very
likely that the inclusion has existed there before SSE.
During SSE, transport of polycrystalline is preferred.

Fig. 8 Micro-morphology of the titanium (white raised and strip


shaped) of part B in gadolinium

With regard to the titanium particles, they increased in


size from 100 nm400 nm and 400 nm before SSE to
300 nm400 nm and more than 400 nm600 nm of part
A after SSE, and decreased to less than 50 nm of part B
after SSE. This can be attributed to the effect of the SSE.
In the process, titanium and other particles migrated with
the effect of the electric, temperature and concentration
field. The titanium particles of strip shape and embedded
round shape acted as the seed crystal. The particles accumulated around the titanium seeds of part A and thus
the size increased. At the same time, the size of titanium

Fig. 9 Micro-morphology and EDS results ((a) the upper spot, (b) the lower one) of the titanium (white raised) of part B in gadolinium

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JOURNAL OF RARE EARTHS, Vol. 32, No. 11, Nov. 2014

Fig. 10 Micro-morphology (a) and electronic diffraction pattern


(b) of gadolinium substrate of part B

had low efficiency of space filling. It was because of this


lower efficiency that led to the faster transport and thus
led to the better purity.
As for substrates, impurity particles as solutes existed in the gadolinium solvent before SSE and in part
A after SSE. It was totally different in part B, the surface became smoother and had not many pits inside.
This phenomenon resulted from SSE. It meant that
the sample in part B had been purified by SSE processing.
According to the SSE process, a crude model was established as shown in Fig. 11. The size of inclusion became bigger after transportation. At the same time, impurities in anode may be less and less until a steady-state
distribution realized after enough time[11,33]. On the contrary, impurities in cathode may be more and more. This
was a very easy model. And the fact should be far more
complicated than this.
In brief, SSE is a complicated and interesting process
worthy of our intensive study to give some helpful guidance to the whole metal preparation field to thoroughly
uncover its mysterious veil.

decreased greatly. It is implied that titanium transport


from anode to cathode during SSE.
The morphology and the electron diffraction pattern of
gadolinium substrate are shown in Fig. 10. In Fig. 10, the
structure of the substrate is smooth. There were less and
tinier dots inside. EDS results show that the content of
gadolinium was more than 95%, the rest was copper.
These copper particles may be introduced by sample
preparation. The diffraction pattern showed that the
structure was b.c.c. As mentioned above, this structure

Fig. 11 Schematic diagram of the transportation of titanium during SSE

3 Conclusions
Rare earth metal gadolinium was prepared by fluorination, reduction and distillation in this work. After that,
the metal was processed into rods to carry out solid state
electrotransport. The results showed that the part with the
highest temperature had the minimal impurities. The
comparison of contents for different parts of the rod gave
lights upon the realization of the important effect of the
electronegativity on migration of impurity particles during SSE processing. HRTEM results demonstrated that
impurities especially titanium migrated from anode to
cathode during SSE.

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