Journal of Environmental Chemical Engineering 2 (2014) 100–104

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Journal of Environmental Chemical Engineering

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

In(III) hydrometallurgical recovery from secondary materials

by solvent extraction
C. Lupi, D. Pilone *
Dipartimento ICMA, Sapienza Università di Roma, Via Eudossiana 18, 00184 Roma, Italy

A R T I C L E I N F O A B S T R A C T

Article history: Indium can be recovered from the residues of zinc and lead refineries and from electronic scrap. In the
Received 21 September 2013 hydrometallurgical processes the main problem is separating In(III) from Fe(III) that are both present in
Accepted 1 December 2013 the leaching solutions. In this work the extraction of In(III) from HCl, H2SO4, and HNO3 media using
D2EHPA, LIX 984, CYANEX 272 and IONQUEST 801 solutions in kerosene is investigated. In(III) is
Keywords: quantitatively extracted from every considered acidic solution by means of IONQUEST 801 even at quite
Indium recovery low pH.
Solvent extraction
D2EHPA allows to obtain extraction yields very similar to those obtainable by means of IONQUEST
D2EHPA
IONQUEST 801
801 except in the extraction tests from HCl solutions. The extraction behavior of some commonly
Reductive stripping associated metal ions such as Fe(III), Cu(II) and Zn(II), has also been investigated with the aim of attaining
high extraction selectivity. The results highlighted that both D2EHPA and IONQUEST 801 do not allow a
complete Fe(III)–In(III) separation, while In(III) can be effectively separated from Cu(II) and Zn(II). The
results highlighted that an effective Fe(III)–In(III) separation can be performed in the stripping stage.
ß 2013 Elsevier Ltd. All rights reserved.

Introduction The adsorption behavior of nanometer TiO2 for indium ions

Indium consumption grew at an ever-increasing rate up to now,
mainly due to indium applications in indium tin oxide (ITO) for
LCD’s high definition television as well as screens for cell phones,
tablet computers and other portable electronic devices. Other
applications for indium are semiconductor materials and low
melting point alloys for electronic and military devices.
Indium is mainly recovered from the residues of zinc and lead
refineries. Indium is generally found in low concentrations in some
sulphide ores of zinc, copper and lead, from which it is obtained as
a by-product. Since the use of these metals is likely to increase in
the near future, sincere efforts are being made to recover indium
from leaner sources, namely ores and wastes.
The most widely used techniques for the separation and pre-
concentration of trace indium include ion exchange [1], solid–
liquid separation [2] and liquid–liquid extraction [3].
The separation of In(III), Ga(III) and Zn(II) from sulphate
solutions has been studied using P507 extraction resin. The results
show that P507 extraction resin gave a theoretical separation of
In(III), Ga(III), and Zn(II) from dilute solutions by controlling pH
and using different concentrations of HCl eluent [4].
* Corresponding author. Tel.: +39 0644585879.
E-mail addresses: carla.lupi@uniroma1.it (C. Lupi), daniela.pilone@uniroma1.it
(D. Pilone).
was investigated. It was found that the adsorption percentage of
indium ions was more than 96% in the pH range 3.5–4.0, and the
desorption percentage of In(III) ions was more than 99% at
pH  1.5 [5].
In view of the complexity of materials that have to be processed
and of the desired purity of metals, solvent extraction offers an
effective technology for recovering metals. By using liquid–liquid
extraction operations the separation and recovery of gallium and
indium from zinc refinery residue has been carried out. Major
metal components other than zinc can be removed from leach
liquor by extraction with TBP. The remaining liquor then contains
rare metals, gallium, indium and zinc. Extraction equilibrium
formulations for the three metals in the ternary system with
D2EHPA in kerosene were determined [6].
The extraction behavior of indium and gallium from mixed
sulphuric acid solutions using D2EHPA has also been investigat-
ed. The distribution coefficients of indium and gallium increased
with pH while the separation factors decreased with pH due to
the difference in the complex formation behavior of both metal
ions and sulphate ions. Research carried out in this field
highlighted that distribution coefficients of indium and gallium
increased with the concentration of D2EHPA and that kerosene
was superior to benzene as diluent during extraction and
separation operations [7].
In literature the extraction of In(III) from HCl, H2SO4, and HNO3
media using Cyanex 923 solution in toluene has also been

2213-3437/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.12.004
 C. Lupi, D. Pilone / Journal of Environmental Chemical Engineering 2 (2014) 100–104 101

investigated. In(III) is quantitatively extracted over a fairly wide

range of HCl molarity, while from H2SO4 and HNO3 media the
extraction is quantitative at low acid concentration [8]. Solvent
extraction of indium from sulphate, nitrate and chloride solutions
by IONQUEST 801 has been also studied. The results showed that
indium can be selectively separated with high extraction yields
from sulphate solutions containing iron, zinc and copper [9].
The use of Cyanex 272 for the extraction and recovery of In(III)
and Ga(III) from various aqueous-phase and organic-phase
variables has been investigated [10]. LIX 984[11] in n-heptane
was used to extract Cu(II), Fe(III), Ga(III), Ni(II), In(III), Co(II), Zn(II)
and Pb(II). The observed extraction order was similar to that of LIX
84 [12]. However, some previous experiments carried out by the
same authors with Cu(II) showed that the extraction equilibrium
was reached in less time.
In this paper three different exchange extractants (organopho- Fig. 1. The effect of equilibrium pH on the extraction of In(III) from nitric solutions.
sphinic, organophosphonic and organophosphoric acids) and a In the organic phase the extractant concentration is 3 vol.% in kerosene.
chelating extractant (oxime) were tested. Aim of this work is to
identify the best extracting agent among CYANEX 272, IONQUEST
801, D2EHPA and LIX 984 and to optimize indium selective IONQUEST 801, D2EHPA and CYANEX 272 that are cation exchange
extraction from synthetic impure solutions simulating the extractants exchange metal for hydrogen:
composition of leach liquors coming from zinc and/or ‘‘old scrap’’
leaching. Process parameters used in the extraction and stripping Mnþ þ nRH $ MRn þ nHþ (1)
stages are studied in order to perform a selective In(III) recovery
and an effective In(III)–Fe(III) separation. In this case metal extraction power generally decreases with
increasing branching of the alkyl chain, moreover it is well known
Materials and methods that the acidities of the alkylphosphorus compounds show the
order phosphoric > phosphonic > phosphinic, and thus their
In(III), Fe(III), Zn(II) and Cu(II) solutions were prepared by extractions abilities to cations give the same order. These
dissolving analytical grade reagents (Fluka metal oxides) in observation could explain why CYANEX 272 has a lower extraction
sulphuric, hydrochloric and nitric acid solutions, respectively. power and extracts at higher pH [13].
The synthetic solution had the following composition: 1.3 g/L In, LIX1 984 is a chelating extractant that forms a specific
3.2 g/L Fe, 5.3 g/L Zn and 1.1 g/L Cu. The selected acid and sodium complex with the metal ion with a reaction that is similar, but
hydroxide solutions were used in order to change the initial chemically different, to cation exchange extractant [14]. The
solution pH. Organic reagents such as D2EHPA (bis-(2-ethylhexyl) formation of the different complexes of the metals with
phosphoric acid), Cyanex 272 (bis-2,4,4-trimethylpentyl phosphi- hydroxyoxime molecules, including the solvates, in general
nic acid), LIX1 984 (mixture of 5dodecylsalicylaldoxime and 2- depends both upon the acidity of the aqueous phase and the
hydroxy-5-nonyl-acetophenone oxime), IONQUEST 801 (2-ethyl- molar ratio of the metal to hydroxyoxime [11]. In our particular
hexyl phosphonic acid mono-2-ethylhexyl ester) were employed extraction system probably LIX1 984 could allow high In(III)
for extraction without further purification. Commercial grade extraction yield at pH higher than 4.
kerosene was used as diluent for organic extractant. Fig. 2 shows the effectiveness of several extractants during
Equal volumes (50 ml) of the two phases were put in a In(III) extraction from sulphate solutions at different pHs. This
separatory funnel and shaken at room temperature for a time figure highlights that both IONQUEST 801 and D2EHPA are the
interval determined on the ground of kinetic tests. The two phases most effective extractants. In particular at pH lower than 0.7
were separated after the mixture was settled. IONQUEST 801 seems to be slightly more effective than D2EHPA,
The aqueous phase pH was measured by an Amel 334-B pH- while the two extractants show the same behavior for higher pH.
meter. The concentrations of metal ions in the aqueous raffinate The curve obtained by using CYANEX 272 is characterized by a
were measured by A.A.S. (atomic absorption spectroscopy), while milder slope and an acceptable extraction yield can be reached
those in the organic phase were deduced from the difference
between the initial concentration of the considered metal ion in
the aqueous phase and that in the raffinate. The A.A.S. sensitivity is
0.18 mg/ml for In(III), 0.04 mg/ml for Fe(III), 0.008 mg/ml for Zn and
0.03 mg/ml for Cu.

Results and discussion

Tests have been performed in order to choose the extractant

that allows to reach the highest In(III) extraction yields from
different acidic solutions. On the ground of a previous research [9]
kerosene was selected as diluent used with every tested
extractant.
Fig. 1 shows the extraction yields obtained for nitric solutions. It
can be highlighted that while the curves obtained with IONQUEST
801 and D2EHPA are very close, the one obtained with CYANEX 272
reaches extraction yields close to 90% only for pH higher than 3. LIX Fig. 2. The effect of equilibrium pH on the extraction of In(III) from sulphate
984 seems to be uneffective independently of the selected pH. solutions. In the organic phase the extractant concentration is 3 vol.% in kerosene.
102 C. Lupi, D. Pilone / Journal of Environmental Chemical Engineering 2 (2014) 100–104
Fig. 3. The effect of equilibrium pH on the extraction of In(III) from chloride
solutions. In the organic phase the extractant concentration is 3 vol.% in kerosene.
only at pH higher than 2. LIX1 984 allows to obtain a curve very
similar to the one obtained by CYANEX 272, but it is shifted toward
a higher pH range. The same considerations made for Fig. 1 apply to
Fig. 2. It can also be noted that the extraction efficiency suddenly
decreases at pH higher than 2.2. This is due to precipitation
phenomena and demixing problems.
When In(III) is extracted from chloride solutions (Fig. 3) the best
results are attained by means of IONQUEST 801 that allows to
extract 100% of indium in one stage at pH higher than 1. D2EHPA
and CYANEX 272 could be interesting as potential extractants
although they allow to reach extraction efficiencies equal to 60%
(pH 1.5) and 70% (pH 3.4), respectively. LIX, once again, seems to be
the less effective. By comparing Figs. 1–3 it can be gathered that the
chelating extractant does not extract In(III) from any of the
considered solutions at least in the considered pH range. Moreover
the lower In(III) extraction yield obtained with D2EHPA in chloride
solution could be explained considering that in sulphate and
nitrate media the extraction mechanism is purely ion exchange,
while in chloride media the corresponding reaction is:
mInCl2þ ðaqÞ þ ðm þ 1Þ ðHRÞ2ðorgÞ ! Inm Clm R2ðm þ 1Þ H2ðorgÞ þ 2mHþ ðaqÞ
(2)
Moreover in high hydrochloric acid concentrations (>1 M)
solvation mechanism also occurs:
InCl3ðaqÞ þ ðHRÞ2ðorgÞ ! InCl3 2HRðorgÞ (3)
Thus by comparing the results in Figs. 1–3 it can be inferred,
according with others authors, that the extraction of indium was in
the order HNO3 > H2SO4 > HCl at least for acid concentrations
below 2 M [15–17].
On the ground of those results it is evident that IONQUEST 801
and D2EHPA show good In(III) extraction efficiency at least in tests
carried out with sulphuric and nitric solutions. For that reason
further extraction tests were carried out by using those extractants
and sulphate aqueous solutions. In fact sulphuric solutions are
preferable in comparison with nitric solutions that cause demixing
problems.
Preliminary kinetic tests showed that In(III) extraction is very
fast and that equilibrium conditions are already reached after
1 min. This very fast reaction, together with the fast demixing
process, would produce high productivity during continuous pilot
plant extraction tests.
Effective leach solution purification requires the selection of an
extractant that allows to obtain high extraction yields as well as
high selectivity. The solvent choice has to be performed on the
basis of its selectivity. To this end solvent extraction tests were
Table 1
Effect of D2EHPA concentration on In(III), Fe(III), Zn(II) and Cu(II) extraction yields
(%).
In Fe Zn Cu
D2EHPA 3% 98.3 54.1 3.2 9.4
D2EHPA 8% 99.6 65.9 – 1.2
D2EHPA 15% 100 97 – 1.3
carried out in order to evaluate if indium can be selectively
extracted from aqueous solutions containing 1.3 g/L In, 3.2 g/L Fe,
5.3 g/L Zn and 1.1 g/L Cu.
Extraction tests performed by using different D2EHPA con-
centrations in kerosene show that In(III) extraction yield is always
very high, Zn(II) and Cu(II) extraction yields are negligible while
Fe(III) extraction increases with increasing the extractant concen-
tration (Table 1).
Further extraction tests were performed by using D2EHPA
3 vol.% in kerosene. In fact being In(III) characterized by a very high
affinity for D2EHPA and by a very fast extraction kinetic, it should
be preferentially extracted, leaving only a limited quantity of
extractant available for extracting other metal ions. The results
reported in Fig. 4 show that In(III) extraction efficiency increases
with increasing pH up to 1, in fact it increases from 72% at pH 0.1 to
96% at pH 1 and afterward it remains almost constant.
This figure highlights also that Cu(II) and Zn(II) extraction is
quite low independently of the selected pH, while Fe(III) extraction
yield passes from 32% at pH 0.1 to 54% at pH 2.2. These results
suggest that the most suitable pH range is 0.8–1.2, although this
solution would require a subsequent stripping operation able to
separate Fe(III) from In(III).
Among the tested extractants IONQUEST 801 was the most
effective. For that reason its selectivity was evaluated for different
extractant concentrations. As it can be observed in Fig. 5, at pH 1.8
Cu(II) remains in the aqueous raffinate, while Zn(II) extraction,
which is almost 0% for an IONQUEST 801 concentration equal to
3 vol.%, increases up to 38% when 30 vol.% IONQUEST 801 is used.
Both In(III) and Fe(III) are extracted with high efficiency, although
In (III) seems to have higher affinity for IONQUEST 801. This is
particularly evident at low extractant concentrations.
Solvent extraction tests at different pH were then carried out by
means of an organic phase containing 8 vol.% of IONQUEST 801.
This concentration would allow to extract more than 90% of In(III)
limiting Fe(III) and Zn(II) extraction to 55% and 10%, respectively,
and leaving Cu(II) in the aqueous raffinate.
The results reported in Fig. 6 point out that In(III) extraction
yield is always higher than 90%, Fe(III) extraction yield increases
Fig. 4. Extraction yields of In(III), Cu(II), Fe(III) and Zn(II) by using as extractant
D2EHPA (3 vol.% in kerosene).
 C. Lupi, D. Pilone / Journal of Environmental Chemical Engineering 2 (2014) 100–104 103

Fig. 5. Extraction yields at pH 1.8 of In(III), Cu(II), Fe(III) and Zn(II) by using as
Fig. 7. Separation factors [In(III)/Fe(III)] as a function of the equilibrium pH.
extractant IONQUEST 801 in kerosene.

these extractants are highlighted in Fig. 7 that shows the

Fig. 6. Extraction yields of In(III), Cu(II), Fe(III) and Zn(II) by using as extractant
IONQUEST 801 (8 vol.% in kerosene).
from 29% at pH 0.1 to 60% at pH 1.8, while a low percentage of
Zn(II) and Cu(II) are extracted. Similarly to D2EHPA, IONQUEST 801
does not allow Fe(III)–In(III) separation, but looking at the
experimental curves it is evident that Fe(III) extraction is strongly
affected by solution pH while In extraction remains almost
constant. This could suggest that by using a lower extractant
concentration (Fig. 5) and a pH equal to 0.5 a better In(III)–Fe(III)
separation could be achieved. But, considering that Fe(III)
concentration in the aqueous phase is always higher than that
of In(III), the complete Fe(III)–In(III) separation cannot be obtained
in the extraction stage. In order to have an overview of D2EHPA and
IONQUEST 801 extraction capabilities distribution coefficients of
different metal ions are reported in Table 2, while the conditions
that allow to obtain the best In(III)/Fe(III) separation by means of
separation factor versus the equilibrium pH. By observing this
figure it can be pointed out that D2EHPA allows to obtain the
higher separation factor and that the maximum value of this
parameter is reached with D2EHPA at a pH that is higher than the
one characterizing the maximum of the curve obtained with
IONQUEST 801.
Both D2EHPA and IONQUEST 801 have proven to be In(III)
excellent extractants, however they extract with very high
efficiency also Fe(III) ions. Considering that Fe(III) is always
present in the solutions that have to be purified whatever their
source (zinc extraction process, electronic scrap processing, etc.), it
is necessary to perform a selective separation of indium from iron
during the stripping stage.
Preliminary Fe(III) stripping tests from D2EHPA were per-
formed by using aqueous solutions having different concentrations
of both H2SO4 and HCl. The obtained results show that acid
concentration up to 1 N does not allow stripping of Fe(III). By
increasing acid concentration the stripping yield increases more
pronounced when using HCl. Particularly stripping yield reaches
100% using 6 N HCl, while by using 6 N H2SO4 the stripping yield
does not exceed 30%.
Preliminary Fe(III) and In(III) stripping tests from loaded
D2EHPA and IONQUEST 801 have been performed using as
stripping reactant HCl aqueous solutions at different concentra-
tions. The two organics containing 1 g/L of both Fe(III) and In(III)
were mixed for 15 min with the aqueous phases by using an O/A
ratio equal to 1. The results reported in Fig. 8a andb show that the
stripping behavior of the two systems does not allow to reach a
good separation between Fe(III) and In(III). By observing Fig. 8 it
can be seen that in the case of stripping from D2EHPA the
separation of In(III) from Fe(III) is possible for HCl concentration
between 0.5 and 1 N where no Fe(III) is stripped, but In(III)
stripping is lower than 5% for a single contact.

Table 2
Distribution coefficient of different metal ions for IONQUEST 801 (8 vol.% in kerosene) and D2EHPA (3 vol.% in kerosene).

pH IONQUEST 801 D2EHPA

DIn DFe DCu DZn DIn DFe DCu DZn

0.1 10.90 0.41 0.01 0.03 2.64 0.47 0.09 0.00

0.6 23.39 0.47 0.01 0.05 10.76 0.75 0.11 0.00
1.0 33.48 1.33 0.02 0.04 30.25 0.49 0.05 0.04
1.3 42.48 1.86 0.005 0.07 – – – –
1.8 29.30 1.38 0.02 0.09 – – – –
2.2 – – – – 57.82 1.18 0.10 0.03
2.5 – – – – 49.00 0.04 0.03
104 C. Lupi, D. Pilone / Journal of Environmental Chemical Engineering 2 (2014) 100–104
Fig. 8. Iron and Indium stripping yield from IONQUEST 801 (a) and D2EHPA (b) vs. acidity of stripping solution.
Fig. 9. Block flow diagram of the proposed process.
Those results suggest that iron stripping need to be performed
in a different way. A possible method to achieve In(III)/Fe(III)
separation is to perform a reductive stripping of Fe(III) from
D2EHPA [18]. With this method the ferric ion stripping is achieved
in vacuum by galvanic stripping using zinc powder as the reducing
agent. The redox reaction in the organic phase and the stripping are
simultaneously performed. The results showed that a contact time
of 60 min is required to reach the maximum yield, that a zinc
excess of 300% compared with the stoichiometric quantity gives
satisfactory results and that a stripping yield greater than 89% in
only one stage can be achieved, depending on A/O ratio, at 80 kPa of
pressure. Unfortunately metallic Zn added to reduce Fe(III) is
partially dissolved in the organic phase and thus the proposed
process has to include a Zn(II) stripping stage.
Fig. 9 highlights that in order to achieve In(III)/Fe(III) separation
in the stripping stage firstly iron can be easily stripped, while
indium remains in the organic phase. In fact preliminary tests
carried out by using as a reducing agent both zinc and manganese
highlighted that the reductive stripping is not effective for
removing In(III) from the organic phase. Zn(II) stripping must be
performed in a subsequent stage by using 0.1 N H2SO4: this low
H2SO4 concentration does not allow In(III) stripping. The last
stripping stage is In(III) stripping that can be easily performed by
means of 2 N HCl solution.
Conclusions
Solvent extraction tests carried out on synthetic solutions by
using different extractants showed that IONQUEST 801 and
D2EHPA allow to obtain the highest In(III) extraction yield even
at low equilibrium pH and low extractant concentration. Both
D2EHPA and IONQUEST 801 have proven to be In(III) excellent
extractants, but they extract with very high efficiency Fe(III) ions
too. The results highlighted that an effective In(III)–Fe(III)
separation from D2EHPA can be achieved in the stripping stage
by coupling Fe(III) reductive stripping with conventional stripping
of In(III) and Zn(II).
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