Minerals Engineering xxx (2015) xxx–xxx

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

a ? c ? b-phase transformation of spodumene with hybrid microwave

and conventional furnaces
Olli Peltosaari ⇑, Pekka Tanskanen, Eetu-Pekka Heikkinen, Timo Fabritius
Process Metallurgy Research Group, University of Oulu, P.O. Box 4300, 90014 Oulu, Finland

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

Article history: Spodumene is the most important lithium containing hard rock mineral. In order to extract lithium from
Received 23 December 2014 spodumene concentrate by leaching, the crystal structure of spodumene must be converted from the nat-
Revised 14 April 2015 ural monoclinic a-form to the tetragonal b-form. The technical possibilities to generate the heat to the
Accepted 17 April 2015
conversion process of spodumene concentrate via microwaves were studied. The heat treatment exper-
Available online xxxx
iments were carried out with a domestic microwave furnace (700 W) with silicon carbide susceptor and
with the conventional resistance heated furnace as a reference. In the microwave furnace the phase
Keywords:
transformation of spodumene began after 110 s of heating and samples were converted almost com-
Roasting
Extractive metallurgy
pletely to b-spodumene after 170 s. Partial melting of gangue minerals was observed in samples after
Mineral processing 170 s of heating. Heating in microwave furnace for 170 s corresponded with the heating of approximately
480–600 s at temperature of 1100 °C in the conventional furnace. In addition to a- and b-forms an inter-
mediate phase, hexagonal c-spodumene, was identified from samples heated with both furnaces. The
conversion of spodumene samples was verified with X-ray diffraction (XRD) and with field emission
scanning electron microscope (FESEM).
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction low-temperature a-spodumene (C2/c). The tetragonal high-temper-

Lithium is the lightest metal and it has a high electrochemical
reactivity. Because of its properties, lithium is a desired raw material
of growing battery industry. Principally lithium is traded in the form
of lithium carbonate or lithium hydroxide. Mainly due to the growth
of the battery industry, the demand of lithium chemicals has
increased worldwide in recent years. There are few commercially
exploitable lithium minerals occurring in pegmatites. Spodumene
(LiAlSi2O6), petalite (LiAlSi4O10) and lepidolite (K(Li,Al,Rb)3
(Al,Si)4O10 (F,OH)2) are lithium containing hard rock minerals which
are mined for their lithium content. The most important of these is
spodumene which is used as a raw material in the lithium
extraction.
Spodumene is a single-chain silicate and belongs to pyroxene
group. Pure spodumene has the stoichiometric chemical composi-
tion of 8.0 wt.% Li2O, 27.4 wt.% Al2O3 and 64.6 wt.% SiO2.
Pegmatitic spodumene ore contains typically quartz, albite, micro-
cline and muscovite as gangue minerals. Spodumene has three
polymorphic forms. The form occurring in nature is monoclinic
⇑ Corresponding author.
E-mail address: olli.peltosaari@oulu.fi (O. Peltosaari).
ature form is called b-spodumene (or LiAlSi2O6 II) (P43212) which is
stuffed derivative of the keatite structure (Li and Peacor, 1968). The
third hexagonal high-temperature form which is stuffed derivative
of the high-quartz is known as c-spodumene (or LiAlSi2O6 III or vir-
gilite) (P6222) (Li, 1968).
The most commonly lithium is processed to form of lithium car-
bonate. The production chain of lithium carbonate from spo-
dumene ore comprises four main steps: mining, beneficiation,
heat treatment and lithium extraction. Spodumene can be concen-
trated with flotation or heavy liquid separation that produce con-
centrates with spodumene content at least of 75 wt.%. The
chemical extraction of lithium from spodumene concentrate
requires the phase transformation from a-form to b-form. This is
because a-spodumene is a relatively compact mineral and it has
a low reactivity whereas the b-spodumene as a porous material
has a larger surface area and a much higher reactivity. It has been
long known from atmospheric studies that this change of crystal
lattice takes place at elevated temperatures (Munoz, 1969). The
required temperature for the phase transformation is 1000–
1100 °C. The indirect fired rotary kiln in which the tube is heated
from outside with burners or heating elements is a commonly used
method for heat treatment of spodumene concentrate (Garrett,

http://dx.doi.org/10.1016/j.mineng.2015.04.012
0892-6875/Ó 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Peltosaari, O., et al. a ? c ? b-phase transformation of spodumene with hybrid microwave and conventional furnaces.
Miner. Eng. (2015), http://dx.doi.org/10.1016/j.mineng.2015.04.012
2 O. Peltosaari et al. / Minerals Engineering xxx (2015) xxx–xxx

2004). Large gas flow rates during the conversion process of spo- 2. Experimental
dumene concentrate are not desirable because of the fragility of
the formed b-spodumene. b-spodumene can easily break down to 2.1. Materials
fine grained material on the effect of mechanical abrasion and drift
with the gas flow to the gas filters. Due to this predisposition the The material used in experiments of this study was pegmatitic
indirect heating in which heat is generated indirectly without spodumene ore from Ullava in Central Ostrobothnia (Finland)
any gas flows inside the kiln might be the more appropriate (Kuusela et al., 2011). The ore was crushed and then sieved into
solution for heat treatment. The lithium can be recovered as a car- six different particle sizes. Fractions under 2 mm were concen-
bonate from the converted spodumene concentrate with sulfuric trated with heavy liquid separation (Na6O39W12
H2O (aq),
acid process (Garrett, 2004) or with sodium carbonate autoclave q = 2.89 g/cm3). Spodumene pieces in the larger fractions were vis-
process (Chen et al., 2011; Olivier and Nenniger, 1979). ibly recognizable from gangue minerals and therefore the separa-
Microwave energy has been found to have potential for wide tion was carried out by hand-picking. The particle sizes that
range of applications in mineral treatment and metal recovery pro- were used in experiments with microwave and conventional fur-
cesses such as heating, roasting and smelting (Haque, 1999; naces are specified in Table 1. Despite of careful separation the spo-
Pickles, 2009). However, there has been only a little research con- dumene concentrates contained some quartz, microcline and albite
cerning the theoretical aspects of microwave treatment of minerals as gangue minerals.
of two areas: prediction of mineral heating rate in an applied
dielectric field and the modeling of thermal stresses within irradi-
2.2. Methods
ated mineral matrices (Kingman and Rowson, 1998). Microwave
heating offers many advantages compared to conventional heating
2.2.1. Hybrid microwave heating and conventional heating
processes such as non-contact heating, energy transfer without
The microwave furnace used in this study was a normal domes-
heat transfer, rapid heating, selective heating, quick start-up and
tic microwave oven. The microwave furnace consisted of a
stopping, heating starting from interior of material body as well
2.45 GHz magnetron with a 700 W power output and a rectangular
as higher level of safety and automation (Haque, 1999). Effective
multimode cavity. SiC was used as a susceptor material because of
microwave heating could possibly reduce the treatment time and
its high dielectric loss factor and good refractory properties (Zhao
required energy consumption of many applications in mineral
et al., 2000). Cylindrical SiC tube with a height of 45 mm, an outer
treatment processes.
diameter of 18 mm and a wall thickness of 2.75 mm was sur-
Based on their ability to absorb microwaves materials can be
rounded by porous alumina sheet and quartz glass as thermal insu-
classified as transparent materials, conductors or absorbers. The
lations. The sample was situated inside the SiC tube. Due to
primary parameter that illustrates this ability is the dielectric loss
inhomogeneity of electric field inside the microwave cavity, the
factor. Chen et al. (1984) exposed 40 minerals individually to
hottest spot of cavity needed to be determined, into which the
microwave radiation and found out that most silicates are trans-
whole configuration was situated. The arrangement of the sample,
parent to microwaves. Silicates have a low dielectric loss factor,
the SiC susceptor and the thermal insulation of the microwave cav-
so they do not absorb the microwave radiation nor transform it
ity are shown in Fig. 1. Thermocouple was used for measuring the
into heat at room temperature. Generally the dielectric loss factor
temperature of the samples. Due to interaction between thermo-
increases exponentially with temperature (Zhao et al., 2000).
couple and microwaves during the microwave heating, tempera-
Hence, the heating of silicates could be possible in high tempera-
ture was measured directly from the sample inside the SiC tube,
tures with microwaves. Materials which are excellent absorbers
immediately after the heating was ended. The selected heating
can be used as a microwave heating assistant (susceptor) when
times were based on the glow of the SiC tube meaning the moment
installed together with transparent material. The susceptor is
when the color of the tube changes from black to pale red. The
heated up by microwaves and simultaneously the transparent
glow was achieved after 90–100 s of heating. Because of this, the
material is heated up via conduction and radiation by the suscep-
heating times of 110–170 s with 10 s second-steps were chosen
tor. When the microwave coupling temperature of transparent
to be used in the experiments. Spodumene samples were partly
material is achieved the rapid microwave heating of materials
melted after 170 s of heating. After heating the samples were left
can occur. The microwave heating technique using a susceptor as
to cool in air inside the SiC tube. Heating power was 700 W in each
a heating assistance is called hybrid microwave heating due to
experiment. Due to strong volume increase during the phase trans-
the fact that it is a combination of conventional heating and micro-
formation, the sample size was kept small (2 g) for preventing
wave heating (Zhao et al., 2000).
sample packing inside the tube.
The aim of this study was to explore tentatively the technical
The reference experiments were carried out in a conventional
possibilities to generate the heat to the conversion process of spo-
resistance heated furnace. The purpose was to determine the tem-
dumene concentrate with microwaves. The objective was to exam-
perature and time in which spodumene sample is completely con-
ine the technical potential of microwaves for heat treatment of
verted into b-spodumene and compare the results with the results
spodumene concentrate, not so much to evaluate the energy con-
gained from the microwave experiments. The furnace was heated
sumption of different heating methods. In the preliminary studies
up to the required temperature. A 2 g spodumene sample situated
was observed the same fact which literature had revealed before,
in a platinum crucible was put into the hot furnace. The first exper-
of spodumene being a transparent material and not heating up
iments were performed with two hours heating time at
directly with microwaves at room temperature. Therefore the
hybrid microwave heating with silicon carbide tube (SiC) susceptor
was used in microwave experiments. Experiments with a conven- Table 1
tional furnace were carried out as a reference. The phases of sam- Particle sizes used in experiments.
ples were identified and relations of spodumene polymorphs were Particle size (mm)
determined with X-ray diffraction (XRD) and field emission scan-
0.5–0.85 1.0–2.0 2.0–4.0 4.0–6.0
ning electron microscope (FESEM). Different particle sizes, heating
times and temperatures were used in experiments. The results of Microwave furnace x x x x
Conventional furnace x
different heating methods were compared.

Please cite this article in press as: Peltosaari, O., et al. a ? c ? b-phase transformation of spodumene with hybrid microwave and conventional furnaces.
Miner. Eng. (2015), http://dx.doi.org/10.1016/j.mineng.2015.04.012
 O. Peltosaari et al. / Minerals Engineering xxx (2015) xxx–xxx 3

Table 2
The relative fractions of spodumene polymorphs in samples heated with microwave
furnace and temperatures of the 2.0–4.0 mm samples measured immediately after
hybrid microwave heating.

t (s) 0.5–0.85 mm 1.0–2.0 mm

a (%) b (%) c (%) a (%) b (%) c (%)
110 79 6 15 99 0 1
120 33 32 35 77 6 17
130 26 34 39 71 9 20
140 19 45 36 30 30 40
150 14 50 36 9 61 30
160 11 71 18 10 65 25
170 2 94 4 6 80 14
T (°C) 2.0–4.0 mm 4.0–6.0 mm
a (%) b (%) c (%) a (%) b (%) c (%)
110 910 95 1 5 96 0 4
120 970 85 3 12 86 3 11
130 1022 35 21 44 42 22 36
140 1066 25 29 46 19 37 44
150 1107 13 49 38 13 45 42
Fig. 1. Schematic diagram of sample, susceptor and thermal insulation in 160 1154 5 82 13 2 65 33
microwave cavity. 170 1197 2 91 7 6 90 5

temperatures of 800, 900, 1000, 1050 and 1100 °C. Based on the
results of these experiments, the next experiments were carried
out with heating times of 2, 4, 6, 8, 10 and 15 min in 1100 °C.
After the heating period the samples were removed from furnace
and cooled in air at room temperature. All experiments on both
furnaces were performed in atmospheric pressure.

2.2.2. Sample characterization

The samples from both the microwave and conventional exper-
iments were analyzed using X-ray diffraction (XRD) method
(Siemens 5000) using a Cu tube as a radiation source. Samples were
ground to fine powder with an agate mortar. Measurements were
performed using diffraction angle range of 10–50° and scanning rate
of 0.02°/s. The main phases were identified from obtained diffrac-
tion patterns by Diffracplus Basic Evaluation Package EVA 12 soft-
ware. The mass proportions of each phase were determined using
a Rietveld method on Diffracplus TOPAS R version 3.0 software.
Required crystal structures were downloaded from the Fig. 2. X-ray diffraction patterns of 2–4 mm spodumene samples converted with
Crystallography Open Database (Gražulis et al., 2012; Grazulis et microwave furnace. Spodumene polymorphs are labeled as a, b and c. Peaks of
al., 2009; Downs and Hall-Wallace, 2003). Only the fractions of a-, gangue minerals are neglected for clarity.

b- and c-structures in the samples were calculated from the results

obtained from TOPAS whereas the fractions of gangue minerals
were ignored. Results from XRD were verified with field emission
scanning microscope (FESEM) and with energy-dispersive X-ray
spectroscopy (EDS) for which was prepared the polished section
from one sample.
3. Results
3.1. Phase transformation with hybrid microwave heating
SiC tube heated up very rapidly leading to rapid conversion of
all the spodumene samples. The calculated relative fractions of
spodumene polymorphs and temperatures of 2.0–4.0 mm spo-
dumene samples after hybrid microwave heating with different
heating times are presented in Table 2. Temperature of sample
was 910 °C after 110 s and increased up to 1197 °C after 170 s of
heating. The X-ray diffraction patterns of 2.0–4.0 mm spodumene
samples converted using microwave hybrid heating are shown in
Fig. 2. a-, b- and c-spodumene as well as some gangue minerals
such as quartz, albite and microcline were identified from the sam-
ples. Some c-spodumene was already formed after first 110 s of
heating. However, the conversion into b-spodumene had not begun
after first 110 s with the exception of the finest 0.5–0.85 mm frac-
tion in which a small amount of b-spodumene had been formed.
Most XRD-peaks of c-spodumene are overlapping with peaks of
b-spodumene. The main peak of both b- and c-phases is located
at the same position at approximately 25.5° in 2h-scale. The most
obvious evidence of formation of c-spodumene is the peak located
at 19.5° in 2h-scale after 130 s of heating in Fig 2. It is the strongest
peak of c-spodumene which is not overlapping with peaks of other
phases. The intensity of the peak reached the maximum point after
140 s heating and after that decreased due to conversion of c-form
into b-form. According to calculated relative fractions of spo-
dumene polymorphs in Table 2, the phase transformation began
approximately at 110 s and almost all of the spodumene was trans-
formed into b-form after 170 s of heating. c-spodumene occurred
as the intermediate phase during the transformation.
The hexagonal b-quartz solid solution Li2Al2Si3O10 and c-spo-
dumene have very similar XRD-patterns, so FESEM with EDS was
used in order to confirm that these phases had not been misinter-
preted as each other. The polished section was prepared from
2.0–4.0 mm sample heated 140 s with microwave furnace. 44 point
analysis were taken from the various parts of the specimen by EDS.
Lithium cannot be determined in the EDS spectrum because of its

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low atomic number, so the Si/Al-ratios of the analysis were com-

pared. All analysis had the Si/Al-ratio near 2:1 which corresponded
with the Si/Al-ratio of spodumene. Li2Al2Si3O10 has a Si/Al-ratio of
3:2 which was not observed in the analyses. Additionally Li (1970)
has stated that the high-quartz solid solution (Li2O
Al2O3
nSiO2)
transforms into the keatite solid solution (b-spodumene) at ele-
vated temperature, which was observed at present study, only
when n is greater than or equal to 3.5. Spodumene has n of 4
and Li2Al2Si3O10 has n of 3. Different spodumene polymorphs could
not be distinguished from each other with EDS analyses because of
the same chemical composition.

3.2. Phase transformation with conventional heating

The X-ray diffraction patterns of the first experiments with con-

ventional furnace are represented in Fig. 3. The samples were con-
verted for 2 h at temperatures ranging from 800 °C to 1100 °C. A
Fig. 4. X-ray diffraction patterns of 2.0–4.0 mm spodumene samples converted
small amount of c-spodumene and some b-spodumene was formed
with conventional furnace at temperature of 1100 °C. Spodumene polymorphs are
at temperature of 800 °C. Strong conversion into b-spodumene labeled as a, b and c. Peaks of gangue minerals are neglected for clarity.
began at temperatures over 900 °C. a-spodumene disappeared
and the maximum amount of c-spodumene was reached at temper-
ature of 1000 °C. The whole sample was converted into b-form at
temperature of 1100 °C. The second set of experiments was per- Table 3
The relative fractions of spodumene polymorphs in samples heated with conventional
formed with different heating times at 1100 °C. That was the tem- furnace.
perature where all of the c-form had disappeared in the first set of
experiments. The X-ray diffraction patterns obtained from the 2nd T (°C) 2.0–4.0 mm (t = 120 min) t (s) 2.0–4.0 mm (T = 1100 °C)

set of experiments at 1100 °C are presented in Fig. 4. All of a (%) b (%) c (%) a (%) b (%) c (%)
a-spodumene was disappeared and the maximum amount of 800 91 2 7 0 100 0 0
c-spodumene was formed after 120 s. Most of the c-spodumene 900 71 9 20 120 0 55 45
was converted into b-form after 480 s although whole conversion 1000 0 59 41 240 0 77 23
1050 0 88 12 360 0 82 18
took 900 s. The calculated fractions of different spodumene poly-
1100 0 100 0 480 0 92 8
morphs from every experiment are presented in Table 3. 600 0 93 7
900 0 100 0

4. Discussion

4.1. Conversion of spodumene in microwave furnace
Changes in the relative fractions of the three spodumene poly-
morphs as a function of microwave heating time is presented in
Fig. 5. The phase transformation from a-form to c- and b-forms
slowed down when the content of a-form in the sample was
decreased to approximately 20–30%. Heat transfer slowed down
due to poor thermal conductivity of b- and c-spodumenes in com-
parison to a-spodumene (Hofmeister and Pertermann, 2008) due
Fig. 3. X-ray diffraction patterns of 2.0–4.0 mm spodumene samples converted at
2 h with conventional furnace. Spodumene polymorphs are labeled as a, b and c.
Peaks of gangue minerals are neglected for clarity.
to which they began to isolate the relict of the a-phase. a-spo-
dumene was almost disappeared after 170 s of heating in which
point the reached temperature of the sample was 1197 °C and
heating was suspended due to partial melting of the concentrate.
The melting point of spodumene is relatively high (1420 °C), which
means that partial melting was caused by the gangue minerals. The
graphs presented in Fig. 5 show that c-spodumene is obviously the
intermediate form during the phase transformation from a-form to
b-form. The small amount of c-spodumene was already formed
after 110 s in which point temperature of the sample was 910 °C.
The highest content at approximately 40% of c-spodumene was
reached after 140 s of heating when temperature was risen up to
1066 °C. The higher than 46% content of c-spodumene was not
observed in any of the experiments. The portion of b-spodumene
increased almost linearly throughout the whole time range that
was being considered. Almost all of a- and c-forms were converted
to b-form after 170 s of heating. Based on the experiments it can be
concluded that heat treatment of spodumene can be realized with
microwave hybrid heating with SiC susceptor with right heating
power and time.
The cylindrical SiC tube was chosen as a susceptor because of its
good dielectric and refractory properties. Additionally, the SiC had
been used as a susceptor in many hybrid microwave sintering
studies where room-temperature-transparent materials were suc-
cessfully heated (Zhao et al., 2000; Huang et al., 2009; Brandão et
al., 2012). Tubular susceptor had probably correcting effect to the
inhomogeneous electromagnetic field, so that the sample was
heated more uniformly without hot spots which could cause par-
tial melting of samples in early stage. The SiC tube heated the sam-
ples effectively in the experiments, but the effect of microwave

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 O. Peltosaari et al. / Minerals Engineering xxx (2015) xxx–xxx 5

As seen from Fig 5, there were no significant differences

Relative fraction of α-s podumene [%]

100 between the conversion rates of different particle sizes. The micro-
90 wave furnace unit was not accurate enough to find clearly observ-
80 able differences in such a small sample size that was used in the
70 experiments. The finest 0.5–0.85 mm fraction was converted
60 slightly faster than coarser fractions and 1.0–2.0 mm fraction
50
slightly more slowly than other fractions during the first 140 s
but there was no difference at the end of the heating. Because
40
the direct influence of microwaves to the samples was presumably
30
only minor or insignificant, it can be expected that the phase trans-
20 formation of spodumene is likely to occur faster in fine particle
10 sizes, as the heat is conducted faster from the surfaces to the inte-
0 rior of the particles. The greater heating rates of coarser fractions
110 120 130 140 150 160 170
than 1.0–2.0 mm fraction at the beginning of the heating was likely
Heating time [s] caused by the narrowness of the SiC tube. The particles of the frac-
0,5-0,85 mm 1,0-2,0 mm 2,0-4,0 mm 4,0-6,0 mm tions over 2 mm were large enough to have a direct contact with
hot walls of the SiC tube and the main conduction heat transfer
Relative fraction of γ-s podumene [%]

100 occurred directly from the hot wall, whereas the main conduction
90 heat transfer occurred by from particle to particle in 1.0–2.0 mm
80 fraction. Additionally air between the particles slowed the heat
70 transfer compared to finest 0.5–0.85 mm fraction. However, the
60 conversion occurred very rapidly in each case.
50
4.2. Conversion of spodumene in conventional furnace
40
30
Changes in the relative fractions of three spodumene poly-
20 morphs as a function of heating temperature and heating time
10 are presented in Fig. 6(A) and (B), respectively. It can be seen that
0 complete phase transformation from a-form to b-form requires
110 120 130 140 150 160 170 temperatures over 1050 °C for a heating time of 2 h. At tempera-
Heating time [s] ture of 1100 °C the phase transformation from a-form to other
0,5-0,85 mm 1,0-2,0 mm 2,0-4,0 mm 4,0-6,0 mm forms occurs rapidly but transformation from c-form to b-form
takes more than 600 s. It is obvious that the increase of
Relative fraction of β-s podumene [%]

100
90
80 A 100
70 90
Relative fraction [%]

60 80
70
50
60
40
50
30 40
20 30
10 20
0 10
110 120 130 140 150 160 170 0
800 900 1000 1050 1100
Heating time [s]
Temperature [°C]
0,5-0,85 mm 1,0-2,0 mm 2,0-4,0 mm 4,0-6,0 mm
α β γ
Fig. 5. Relative fractions of a-, c- and b-spodumenes in the samples converted with
microwave furnace. B 100
90
Relative fraction [%]

80
radiation was unclear. Because the samples were surrounded by 70
the SiC tube with high loss factor, it is possible that the tube 60
absorbed all of the microwave radiation and acted as a shield 50
40
between radiation and the samples. In that case, the sample was
30
only conventionally heated by the susceptor. Zhao et al. (2000) sta-
20
ted that microwaves can penetrate the wall of the SiC susceptor, if
10
the wall is thin enough. They used a wall thickness of 2 mm which
0
is slightly thinner than the one used in present work, so it is prob- 0 120 240 360 480 600 900
able that a small portion of radiation interacted with samples. It is Heating time [s]
not clear whether the heating process was hybrid microwave heat-
α β γ
ing or purely indirect conventional heating process. The primary
heating of samples was obviously caused by SiC tube and direct Fig. 6. Relative fractions of samples converted in conventional furnace (A) for 2 h
influence of microwaves remained unclear. heating time (B) at temperature of 1100 °C.

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6 O. Peltosaari et al. / Minerals Engineering xxx (2015) xxx–xxx
temperature or heating time favors the progression of phase trans-
formations. In order to avoid the occurrence of c-spodumene relics
in industrial applications, it is recommended to perform the heat
treatment in temperatures over 1050 °C.
4.3. Comparison of heating methods
According to X-ray patterns and Rietveld analysis 170 s heating
with microwaves corresponds to a heating of approximately
480–600 s at 1100 °C in the conventional furnace. After 170 s of
heating the temperature of sample was 1197 °C in hybrid micro-
wave heating experiments which explains the high rate of phase
transformation. On both methods c-spodumene was formed in
these conditions. The highest mass proportion of c-spodumene
reached with both methods was approximately 45%. The tempera-
tures measured after microwave experiments were consistent with
temperatures used in the conventional furnace in the terms of the
formation of different spodumene polymorphs. The conversion of
a-spodumene into c-spodumene began at 800–900 °C and conver-
sion of c-form into b-form at 900–950 °C. There was probably
some post-heating with the microwave experiments due to the
cooling method. The sample was cooled with the hot tube so the
heating continued a few tens of seconds after the microwave
heating had ended. The advantage of microwave heating compared
to conventional heating was rapid heating in the experimental
conditions used in present study.
4.4. Phase transformation via c-spodumene
Tetragonal b-spodumene has been prepared from natural mon-
oclinic a-spodumene in many 1-atm studies in which lithium was
extracted from b-spodumene with different methods (Olivier and
Nenniger, 1979; Gabra et al., 1975; Chen et al., 2011; Rosales et
al., 2014). Complete conversion of a-spodumene into b-spo-
dumene was achieved after heat treatment at temperature ranging
between 1000–1100 °C depending on the study. None of those
1-atm studies reported the formation of c-spodumene in any stage
of phase transformation. However, Munoz (1969) found that
b-spodumene transforms into c-spodumene at elevated pressures.
Monoclinic a-spodumene can be converted to hexagonal
c-spodumene via amorphization of the structure. It is widely known
that while heating a glass with a spodumene composition the first
crystallizing phase is c-spodumene which in elevated temperatures
transforms into b-spodumene. Preparing of c-spodumene in this
way is very common (Wu et al., 2004; Guo et al., 2006; Nordmann
and Cheng, 1997). Two ways to prepare c-spodumene from natural
a-spodumene has been introduced in literature and both of them
require the amorphization of the structure of a-spodumene.
Amorphization is performed via melting with alloying elements
(Nordmann and Cheng, 1997) or via mechanical treatment
(Kotsupalo et al., 2010; Gasalla et al., 1987). After heating the
amorphous spodumene metastable c-form appears approximately
at 800 °C which is subsequently converted into b-spodumene at
higher temperatures between 900 and 1080 °C depending on the
experimental conditions (Nordmann and Cheng, 1997; Guo et al.,
2006; Kotsupalo et al., 2010; Gasalla et al., 1987).
Ferro et al. (2004) observed that a rare Li zeolite bikitaite
[Li2(Al2Si4O12)
2H2O, P1] transforms to c-spodumene at tempera-
ture of 800 °C and Hurlbut (1957) found the transformation of bik-
itaite to b-spodumene upon heating to 900 °C. It is suspected that
phase transformation of spodumene from a-form into b-form
happens via c-form under controlled heating (Li, 1968). These sus-
picions were based on the density changes during the phase trans-
formation and the transformation between c- and b-form. Densities
of a-, c- and b-spodumenes are 3.16, 2.395 and 2.365 g/cm3,
respectively. Density of spodumene consequently decreases during
Please cite this article in press as: Peltosaari, O., et al. a ? c ? b-phase transformation of spodumene with hybrid microwave and conventional furnaces.
Miner. Eng. (2015), http://dx.doi.org/10.1016/j.mineng.2015.04.012
the whole a ? c ? b-transformation. London (1984) did not
encounter two phase field b-spodumene and c-spodumene in his
study but he stated that extremely small Gibbs free energy change
associated with transformation reaction between b-spodumene
and c-spodumene could cause metastable persistence of one phase
or other in experimental runs.
In this work c-spodumene appeared as an intermediate phase
in a phase transformation of a-spodumene into b-spodumene after
2 h heat treatment of spodumene concentrate at temperature of
800 °C and transformed into b-spodumene at 900–1100 °C. The
forming temperatures of c- and b-forms corresponded with the
temperatures reported in the amorphous phase heat treatment
studies above, although the heated spodumene was in crystalline
a-form in the present study (according to X-ray diffraction).
The results were similar also with the temperatures reported with
bikitaite above. However, there have been no previous reports of
c-spodumene formation as an intermediate phase in the
transformation between crystalline natural a-spodumene and
b-spodumene under such experimental conditions as was in
present study.
4.5. Practical meaning of results
Spodumene is normally extracted by leaching process from
tetragonal b-spodumene. The formation of c-spodumene should
be monitored in industrial applications. If pure b-spodumene with-
out a- and c-residuals is the desired outcome, the heating time of
spodumene should be adequate. If the heating time is too short,
residuals can exist in the conversion product and complicate the
following leaching process. This could cause losses in the yield of
lithium. The high temperature and long heating time favor the pro-
gression of phase transformation. On the other hand, the excessive
heating will cause the partial melting and agglomeration of con-
centrate resulting in losses in the recovery of lithium. The partial
melting of concentrate can begin at multiphase grain junctions
already below the temperature of 1000 °C. Since there are no stud-
ies on the extraction of lithium from hexagonal c-spodumene, the
effect of c-spodumene to the leaching process is unclear. In the
case that c-spodumene has some negative effects to the leaching
process and the concentrate must be converted at temperature of
1100 °C, beneficiation process is required to produce higher grade
concentrates in order to avoid the agglomeration of concentrate. In
the economic point of view the higher required heat treatment
temperature and higher required grade of concentrate will increase
the costs of production process of lithium carbonate.
The SiC could be viable tube material for the indirect fired
rotary kiln when converting spodumene concentrate. The rela-
tively high conversion temperature of spodumene is above usable
limits of ordinary metals such as carbon steel or stainless steel
whereas SiC has a high mechanical strength and high thermal con-
ductivity at high temperatures. The indirect fired rotary kiln with
microwave heated SiC tube could be viable industrial application
for the technique used in present study. Tsurunaga (2006) intro-
duced the semi-industrialized indirect fired rotary kiln with SiC
tube for the calcination of limestone. The tube was heated with
regenerative burners and kerosene was used as a fuel on that appli-
cation. Based on present study the heat could be alternatively gen-
erated with microwaves in this type of applications. The energy
consumptions of different heating methods for the tube of indirect
fired rotary kiln is difficult to assess. Principally the energy con-
sumption of microwave process depends on the insulation of the
tube and the energy efficiency of the magnetrons to convert elec-
tricity to microwaves. However, this study was not intended to
answer all issues considering the microwave heat treatment of
spodumene. One issue that remained unanswered was the nature
of direct interaction between spodumene and microwaves at the
 O. Peltosaari et al. / Minerals Engineering xxx (2015) xxx–xxx
high temperatures. It would be one factor favoring the microwave
heating solution if the spodumene could be directly heated with
microwaves at elevated temperatures. In that case the silicon car-
bide at the lower and hottest part of the tube could be substituted
for some microwave transparent material and the end of the heat-
ing could be performed directly with microwaves.
5. Conclusions
The present study shows that phase transformation of spo-
dumene from a- to b-form can be performed by hybrid microwave
technique with SiC susceptor. Conversion of spodumene samples
occurred very rapidly when concentrate was heated with SiC tube
in the microwave furnace. Samples were converted almost
completely to b-spodumene after 170 s of heating when the final
temperature of the samples were 1197 °C. Particle size did not affect
significantly the conversion rate of spodumene in such a small sam-
ple size that was used in this study. It is possible that microwaves did
not heat the samples directly and heating occurred only via conduc-
tion and radiation by hot SiC tube. The 170 s heating with microwave
furnace corresponded with 480–600 s heating with conventional
furnace at temperature of 1100 °C. c-spodumene occurred as an
intermediate phase in phase transformation between a- and
b-spodumene, which has not been previously reported. Small
amount of c-spodumene formed in hybrid microwave experiments
after 110 s of heating when reached temperature was 910 °C. In con-
ventional furnace experiments, c-spodumene appeared at 800 °C
and transformed completely to b-spodumene after 900 s of heating
at 1100 °C. Results were based on XRD and FESEM analysis.
Acknowledgements
This research was a part of the Compact, Combined and Co-
working Pretreatments for Mining Industry (CCCP) research project
in Green Mining Programme. The Finnish Funding Agency for
Technology and Innovation (TEKES) and other companies which
have been funding this work are acknowledged. Center of micro-
scopy and nanotechnology (CMNT) is acknowledged for its analysis
services. Mr. Tommi Kokkonen and Mr. Riku Mattila are thanked
for their technical support.
References
Brandão, A.D., Antunes, I., Frade, J.R., Torre, J., Mikhalev, S.M., Fagg, D.P., 2012.
Mechanochemical preparation, sintering aids and hybrid microwave sintering
in the proton conductor Sr0.02La0.98Nb1 xVxO4 d, x = 0, 0.15. Int. J. Hydrogen
Energy 37 (8), 7252–7261.
Chen, T.T., Dutrizac, J.E., Haque, K.E., Wyslouzil, W., Kashyap, S., 1984. The relative
transparency of minerals to microwave radiation. Can. Metall. Quat. 23 (3),
349–351.
Chen, Y., Tian, Q., Chen, B., Shi, X., Liao, T., 2011. Preparation of lithium carbonate
from spodumene by a sodium carbonate autoclave process. Hydrometallurgy
109 (1), 43–46.
Downs, R.T., Hall-Wallace, M., 2003. The American mineralogist crystal structure
database. Am. Mineral. 88 (1), 247–250.
Please cite this article in press as: Peltosaari, O., et al. a ? c ? b-phase transformation of spodumene with hybrid microwave and conventional furnaces.
Miner. Eng. (2015), http://dx.doi.org/10.1016/j.mineng.2015.04.012
7
Ferro, O., Quartieri, S., Vezzalini, G., Ceriani, C., Fois, E., Gamba, A., Cruciani, G., 2004.
Dehydration dynamics of bikitaite: Part I. In situ synchrotron powder X-ray
diffraction study. Am. Mineral. 89 (1), 94–101.
Gabra, G.G., Torma, A.E., Olivier, C.A., 1975. Pressure leaching of beta-spodumene by
sodium chloride. Can. Metall. Quat. 14 (4), 355–359.
Garrett, D.E., 2004. Handbook of Lithium and Natural Calcium Chloride: Their
Deposits, Processing, Uses and Properties. Academic Press.
Gasalla, H.J., Aglietti, E.F., Lopez, J.M., Pereira, E., 1987. Changes in physicochemical
properties of a-spodumene by mechanochemical treatment. Mater. Chem.
Phys. 17 (4), 379–389.
Grazulis, S., Chateigner, D., Downs, R.T., Yokochi, A.T., Quiros, M., Lutterotti, L.,
Manakova, E., Butkus, J., Moeck, P., Le Bail, A., 2009. Crystallography open
database – an open-access collection of crystal structures. J. Appl. Crystallogr.
42 (4), 726–729.
Gražulis, S., Daškevič, A., Merkys, A., Chateigner, D., Lutterotti, L., Quirós, M.,
Serebryanaya, N.R., Moeck, P., Downs, R.T., LeBail, A., 2012. Crystallography
open database (COD): an open-access collection of crystal structures and
platform for world-wide collaboration. Nucl. Acids Res. 40 (D1), D420–D427.
Guo, X.Z., Cao, M., Han, C., Song, F.F., 2006. Crystallinity and crystallization
mechanism of lithium aluminosilicate glass by X-ray diffractometry. Trans.
Nonferr. Metals Soc. China 16 (3), 593–597.
Haque, K.E., 1999. Microwave energy for mineral treatment processes – a brief
review. Int. J. Miner. Process. 57 (1), 1–24.
Hofmeister, A.M., Pertermann, M., 2008. Thermal diffusivity of clinopyroxenes at
elevated temperature. Eur. J. Mineral. 20 (4), 537–549.
Huang, Z., Gotoh, M., Hirose, Y., 2009. Improving sinterability of ceramics using
hybrid microwave heating. J. Mater. Process. Technol. 209 (5), 2446–2452.
Hurlbut, C.S., 1957. Bikitaite, a new mineral from Southern Rhodesia. Am. Mineral.
42 (11–2), 792–797.
Kingman, S.W., Rowson, N.A., 1998. Microwave treatment of minerals – a review.
Miner. Eng. 11 (11), 1081–1087.
Kotsupalo, N.P., Menzheres, L.T., Ryabtsev, A.D., Boldyrev, V.V., 2010. Mechanical
activation of a-spodumene for further processing into lithium compounds.
Theor. Found. Chem. Eng. 44 (4), 503–507.
Kuusela, J., Ahtola, T., Koistinen, E., Seppänen, H., Hatakka, T., Lohva, T., 2011. Report
of investigations on the Rapasaaret lithium pegmatite deposit in Kaustinen-
Kokkola, Western Finland. Geol. Surv. Finland (Report: 42/2011).
Li, C.T., 1968. The crystal structure of LiAlSi2O6 III (high-quartz solid solution).
Zeitschrift Kristallogr.– Cryst. Mater. 127 (1-6), 327–348.
Li, C.T., 1970. The crystal structure of Li2Al2Si3O10 (high-quartz solid solution).
Zeitschrift Kristallogr.– Cryst. Mater. 132 (1-6), 118–128.
Li, C.T., Peacor, D.R., 1968. The crystal structure of LiAlSi2O6-II (‘‘b spodumene’’).
Zeitschrift Kristallogr.– Cryst. Mater. 126 (1-6), 46–65.
London, D., 1984. Experimental phase equilibria in the system LiAlSiO4–SiO2–H2O: a
petrogenetic grid for lithium-rich pegmatites. Am. Mineral. 69 (11–12), 995–
1004.
Munoz, J.L., 1969. Stability relations of LiAlSi2O6 at high pressures. Mineral. Soc. Am.
Spec. Pap. 2, 203–209.
Nordmann, A., Cheng, Y.B., 1997. Crystallization behaviour and microstructural
evolution of a Li2O–Al2O3–SiO2 glass derived from spodumene mineral. J. Mater.
Sci. 32 (1), 83–89.
Olivier, C.A., Nenniger, E.H., 1979. Continuous process for the production of lithium
carbonate. CIM Bull. 72 (807), 131–136.
Pickles, C.A., 2009. Microwaves in extractive metallurgy: part 1 – review of
fundamentals. Miner. Eng. 22 (13), 1102–1111.
Rosales, G.D., Ruiz, M.D.C., Rodriguez, M.H., 2014. Novel process for the extraction of
lithium from b-spodumene by leaching with HF. Hydrometallurgy 147–148, 1–
6.
Tsurunaga, K., 2006. Progress in development of a new indirect fired lime kiln. In:
11th ILA-Congress, Prague, May pp. 16–19.
Wu, S., Liu, Y., He, L., Wang, F., 2004. Preparation of b-spodumene-based glass–
ceramic powders by polyacrylamide gel process. Mater. Lett. 58 (22), 2772–
2775.
Zhao, C., Vleugels, J., Groffils, C., Luypaert, P.J., Van der Biest, O., 2000. Hybrid
sintering with a tubular susceptor in a cylindrical single-mode microwave
furnace. Acta Mater. 48 (14), 3795–3801.