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Characterization of Fayalite from Copper Slags

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 I. Mihailova,
Journal of the University of Chemical D. Mehandjiev
Technology and Metallurgy, 45, 3, 2010, 317-326

CHARACTERIZATION OF FAYALITE FROM COPPER SLAGS

I. Mihailova1, D. Mehandjiev2

1
University of Chemical Technology and Metallurgy Received 05 March 2010
8 Kl. Ohridski, Sofia 1756, Bulgaria Accepted 12 June 2010
E-mail: [email protected]
2
Institute of Catalysis, Bulgarian Academy of Sciences,
Acad. G. Bonchev St., Bldg. 11,Sofia 1113, Bulgaria

ABSTRACT

The aim of the present study was to characterize the fayalite crystal phases in two types of copper slag – flash
smelting furnace slag (FS) and converter (CS) slag, given their possible use in adsorption and catalytic processes. Two
typical slag compositions different in chemical composition and way of production were selected, in order to clarify how
these differences affect fayalite crystallization and composition. The main mineral phase found in copper slags is fayalite.
The samples of the slag were characterized using X-ray diffraction (XRD), Fourier transformation infrared spectroscopy
(FTIR), Light optical microscopy (LOM) in transmitted and reflected light.
Keywords: fayalite, copper slags, flash smelting furnace slag, converter slag.

INTRODUCTION is characterized by phases of the melilite group -

gehlenite and akermanite. Some studies, however, have
The chemical, phase and granulometric compo- shown that these slags have adsorption properties for
sition of metallurgical slags has always attracted a great heavy metals, such as lead, copper, etc., and the increased
deal of interest in view of their reuse in the process of content of these phases enhance the slag adsorption prop-
production or use for other purposes, such as the ex- erties [1, 2]. In such cases, slag can be successfully used
traction of certain metals from them or for the produc- as an adsorbent in purification of water containing heavy
tion of construction materials. Being a waste product, metals [3]. It was also found that metals adsorbed on
the slag recovery or disposal in designated places is the slag surface, for example copper, make it catalyti-
closely related to the issue of environmental protec- cally active in processes of complete oxidation and cata-
tion. During the cooling of the slag, crystallisation pro- lytic removal of carbon monoxide and harmful organic
cesses occur in it and certain phases are formed. The substances [4]. The flash smelting furnace slag and con-
main phases formed during each crystallization process verter slags in copper production contain mainly fayalite
are known, and they depend on the cooling conditions due to the nature of the process of production.
of the metallurgical slag at certain stages in the produc- Fayalite is a common member of the olivine
tion process. Since slag-forming additives (fluxes) are group of minerals. Olivine is a name for a series of
based on silicon, aluminium, calcium and magnesium, silicate minerals with the formula M2SiO4, where M is
compounds of mineral analogues are formed, a process most commonly Fe or Mg. Fayalite (Fe 2SiO4) and
similar to the process of crystallization in natural sili- forsterite (Mg2SiO4) form a substitutional solid solu-
cate melts - volcanic lava or magma. For example, the tion where the iron and magnesium atoms can be sub-
slag from processing and production of ferrous metals stituted for each other without significantly changing

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 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

the crystal structure. The complete solid solution be- and astronomical geomaterials. Olivines are the major
tween these two elements is observed in olivine. Com- component of Earth’s mantle, they are common to many
positions in the Mg–Fe series commonly are identified types of meteorites, and have been identified on the sur-
by the molar percentages of forsterite (Fo) and fayalite faces of planetary bodies and in the spectra of astronomical
(Fa) (e.g., Fo90Fa10), or in shortened form, by just their targets. Olivine phases are indicators of low-silica envi-
forsterite number, where Fo# = Mg/(Mg+Fe)×100. ronments, they crystallize at high temperatures, and they
The crystal structure of Fe2SiO4 has been refined generally break down readily in the presence of weather-
using X-ray methods [5-7]. Olivine has an orthorhombic ing agents such as water. As such, their identification and
structure. The structure consists of isolated SiO44- tetra- characterization is a subject of considerable interest to a
hedra, which are held together by M cations occupying wide variety of researchers [10]. Olivines are, quite liter-
two types of octahedral site (M1 and M2). The isolated ally, universally relevant minerals.
tetrahedra point alternately up and down along rows par- On Earth, olivine compositions in the forsterite–
allel to the z-axis. The magnetic spin structure has been fayalite series are common in mafic to ultramafic rocks,
determined using powder neutron diffraction at 4 and 58 in which their compositions typically range from about
K by Santoro et al., who have also measured the powder Fo85–95. Compositions between Fo80 and Fo50 are typical
magnetic susceptibility between 4 and 300K [8]. of gabbroic rocks. Olivine group minerals can be formed
Olivine with up to one formula unit of calcium in natural and in technological processes - in certain
(CaMgSiO4) is referred to as monticellite. The iron ana- mineral aggregates (rocks), in slags of the Blast furnace
logue, kirschsteinite (CaFeSiO4), is rare in nature. There and agglomerates [11]. Fayalite also has considerable
also is a manganese end member, tephroite (Mn2SiO4). technological importance in copper metallurgical slags.
The metal cations occupy two positions in the crystal Ivanov et al. carried out interesting research on
structure, M1 and M2, which are defined by their sym- phase composition and structure of copper slag from
metry; commonly, Fe2+ displays a preference for the Bulgarian plants [12-16].
M1 site. The members of the olivine group are pre- Our previous research [17, 18] on the phase com-
sented in Table 1. M. W. Schaefer has reported large position and structure of flash smelting furnace slag and
amounts of Fe3+ ions in fayalites (members of the olivine converter slag from copper production found that the
group) from various localities. Such data are contrary to chemical compositions of fayalite included Al, Mg, Zn,
the generally held belief that fayalite is incapable of ac- Cu, Al, Ca and other elements as isomorphic impuri-
commodating much Fe3+ ions in its crystal structure [9]. ties. The phases in the samples were characterized by a
Members of the olivine group (olivines) are im- variable and non-stoichiometric composition. However,
portant rock-forming minerals in terrestrial, planetary, the preference of the various elements contained in the
slag to the different crystalline or amorphous phases
Table 1. Olivine End-Members. was clearly manifested.
Mineral names Chemical The aim of the present study was to characterize
the fayalite crystal phases in two types of copper slag –
composition
flash smelting furnace slag and converter slag, given their
Forsterite Mg2SiO4 possible use in adsorption and catalytic processes. Two
Fayalite Fe2SiO4 typical slag compositions different in chemical compo-
Tephroite Mn2SiO4 sition and way of production were selected, in order to
Liebenbergite Ni2SiO4 clarify how these differences affect fayalite crystalliza-
tion and composition.
Co-olivine Co2SiO4
Ca-olivine Ca2SiO4 EXPERIMENTAL
Monticellite CaMgSiO4
Kirschsteinite CaFeSiO4 Two kinds of copper slags were examined – slag
from flash-smelting furnace process and converter slag.
Glaucochroite CaMnSiO4
Samples were taken from the slag fields used for crys-

318
 I. Mihailova, D. Mehandjiev

tallization of the liquid slag by spraying with water. The between different samples, light optical microscopy in
samples of copper flash smelting furnace slag and con- transmitted and reflected light was used. In this study
verter slag are labeled as FS and CS respectively. The we have used polarizing microscopes Laboval – pol – u
samples of the slag were characterized using X-ray dif- “Carl Zeiss” Jena.
fraction (XRD), Fourier transformation infrared spec-
troscopy (FTIR), Light optical microscopy (LOM) in RESULTS AND DISCUSSION
transmitted and reflected light. Quantitative determi-
nation of elements in the samples was carried out by Chemical composition results
Gravimetric analysis, Complexonometry, Atomic ab- Table 2 shows the chemical composition of
sorption spectrometry (AAS) and Inductively coupled samples of slag.
plasma (ICP-OES). The XRD characterization of the
different samples of slag was conducted using a DRON X-ray diffraction
3M X-ray diffractometer with a CoKá radiation (40 Fig. 1 shows X-Ray diffraction data for samples
kV, 25 mA) as an X-ray source (λ = 0.17903 nm). The of slag.
samples were continuously scanned over an angular Fayalite (Fe2SiO4) and magnetite (Fe3O4) are two
range of 2è 8 – 90° using a step size of 0.05°. PowderCell dominant phases in the samples. The two presented X-
2.4 software [19] was used to determine the unit cell ray diffraction patterns show amorphous halo at lower
parameters on the basis of experimental X-ray data. values of 2è, associated with the presence of amorphous
FTIR spectroscopy has been applied. Infrared transmit- phase. The converter slag sample contains larger amount
tance spectra were recorded by using pressed pellet tech- of magnetite in comparison with the sample of flash
nique in KBr. The measurements were made with a FTIR smelting furnace slag. Divergence between experimen-
spectrophotometer Bruker EQUINOX 55 in the fre- tal data and reference pattern data for the intensity of
quency range from 4000 to 400 cm-1. In order to have a diffraction peaks may be observed. The reflections of
good evaluation about the structures and textures in- the fayalite phase with the indices (120) (240) (020)
cluded of each sample as well as to make a comparison (130) have a higher intensity than expected. This is due

Fig. 1. XRD patterns of samples of copper slags

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 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

Table 2. Chemical composition of slag samples. ing furnace slag sample and 31.0 ° 2è (d = 3.34) in the
Elements/ Content, %mass XRD pattern of converter slag sample are an exception.
Oxides Flash Converter Their presence is likely due to copper sulphide phases.
smelting Slag (CS) The cell parameters of fayalite and magnetite
furnace found in slag were calculated using the program Pow-
slag (FS) der Cell 2.4. They are given in Table 3.
SiO2 25.56 22.45
As seen in Table 3, the values of the unit cell
CaO 5.94 1.52
parameters of fayalite and magnetite in copper slags are
MgO 1.59 0.48
K2O 0.78 0.44 very close to literature values for pure phases.
Na2O 0.76 0.62
Fe 46.63 47.71 FTIR analysis
Cu 1.14 5.07 Fayalite is an especially important phase for dif-
Pb 0.06 0.66 ferent types of spectroscopy because, by definition, it
Zn 0.33 1.05 contains an equal distri­bution of Fe2+ cations between
Ni 0.017 0.036 the M1 and M2 octahedral sites. Thus, features associ-
Co 0.043 0.160
ated with each of the two sites must represent equal
As 0.02 0.02
numbers of Fe2+ cations, removing the uncertainties
Sb 0.021 0.064
Bi 0.020 0.007 associated with assumptions about order/disorder of Fe2+
Cd 0.016 0.002 and other cations [24].
Cr 0.004 0.043 Thermal infrared band assignments for Mg–Fe
S 0.18 0.74 olivines were determined early on [25-26] from trans-
Ó 83.111 81.072 mission spectra and many studies have resulted in re-
fined and extended assignments. Symmetry analysis in-
to textures in the samples related to fayalite crystals dicates that there are a total of 84 normal modes of
morphology. The presence of additional crystalline vibration [27], 35 of which are infrared active (but which
phases could not be ascertained from the presented XRD may not be individually observable in unpolarized spec-
patterns. Peaks with negligible intensity remain after tra, or may be too weak to be observed). These modes
juxtaposing diffraction maxima with the reference pat- represent internal stretching and bending modes as well
terns for fayalite and magnetite. Diffraction maxima at as lattice modes (cation translations and rigid rotation–
34.8 ° 2è (d = 3.00) in the XRD pattern of flash smelt- translation) of the SiO4 tetrahedra. In spectra of ran-

Table 3. Cell parameters of the crystalline phases in the slags. Comparison with literary data.

Sample Cell parameter of Cell parameters of fayalite (orthorhombic)

magnetite (cubic)
= = > ?
Flash smelting 8.385 4.824 10.477 6.089
furnace slag (FS)
Converter slag 8.412 4.825 10.502 6.120
(CS)
Magnetite 8.3958
[20]
Magnetite 8.3965
[21]
Magnetite 8.3970
[22]
Fayalite 4.818 10.471 6.086
[5]
Fayalite 4.818 10.470 6.086
[23]

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 I. Mihailova, D. Mehandjiev

Fig. 2. FTIR spectra of the samples of copper slags

domly oriented samples, the three principal bands be- tional translational modes and combinations of SiO4
tween : 1000 and 850 cm-1 are the result of splitting of and cation translations are observed [10].
degenerate Si–O asymmetric stretching vibrations of the Fig. 2 shows FTIR spectra of samples.
í3 mode in SiO4. A feature near 825 cm-1 results from As can be seen the presented spectra are mainly
the í1 mode (symmetric stretch), and three or four fea- due to the fayalite phase in the samples.
tures in the 610–460 cm-1 region can be attributed to split- The vibrational modes in olivine series minerals
ting of the degenerate í4 asymmetric bending vibration. vary slightly as a function of solid solution composi-
Features in the 500–200 cm-1 region are attributable to tion, leading to shifts in band position and changes in
the í2 symmetric bending mode, rotations and translation band strength, including the presence or absence of some
of the SiO4 tetrahedron, and translations of one of the features. Regardless of whether the measured olivines
divalent cations. In the far infrared (200–85 cm-1), addi- are natural or synthetic, their infrared spectra exhibit a

Table 4. Olivine transmittance band positions, cm-1.

Sample / Fo# Band Band Band Band Band Band Band Band
1 2 3 4 5 6 7 8
FS (this study) 948 914 874 826 562 502 472 425
CS (this study) 947 911 873 826 564 504 475 413
Fo31 956 927 883 833 582 516 482 (417)
Fo29 955 926 878 831 573 513 482 411
Fo18 951 918 874 829 567 511 480 411
Fo14 950 920 883 831 570 506 479 (407)
Fo11 947 920 874 829 563 507 476 409
Fo9 949 920 876 831 570 506 478 (413)
Fo1 945 916 874 828 563 505 475 (419)
Fo0 945 917 875 830 566 507 478 –
Fo0 946 917 879 830 569 505 479 (418)

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 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

generally linear decrease in the wavenumber position the forsterite number Fo# was calculated, assuming that
of each band as the molar proportion of Fe increases, all magnesium and iron participate in the fayalite phase
and this trend is attributed to the increasing radius and formation in both slags. The calculated values are as fol-
mass of the cation linking the SiO4 tetrahedra. The lin- lows: Fo# = 4.5 (FS) and Fo# = 1.4 (CS). The forsterite
earity of band positions as a function of composition in number value of fayalite in flash smelting furnace slag is
the forsterite – fayalite series indicates a nearly random higher than that in converter slag, which should be ex-
distribution of Mg2+ and Fe2+ in the M1 and M2 sites pected given the higher content of magnesium in the phase.
and that any significant deviation from linearity would Experimental values for the forsterite number of
indicate ordering of the Mg2+ and Fe2+ ions [10]. fayalite phases may also be calculated using the linear
In Table 4, experimental data for fayalite in cop- relationship between the band position and the forsterite
per slag is compared to literature data [10] for olivines number. In Fig. 3 is shown the dependence of position
with a forsterite number (Fo#) in the range of 31-0. of the band 1 at : 950 cm-1 on the forsterite number,
There is a good correspondence between experimental according to literature data [28, 29].
data and literature data for olivines with Fo# below 11. In Fig. 3 with straight horizontal lines are also
Due to the low content of magnesium in slag, the given the values derived by us for the same band of the
forsterite number of the fayalite phase formed in slag fayalite phase in both slags. The intersection points of
should be small. It is interesting to make a theoretical these lines with the straight line give the forsterite num-
estimate of the expected forsterite number on the basis ber value. Thus the calculated value for FS sample is 8.3,
of the available data for the content of the main com-
ponents involved in fayalite structure formation. Mag-
nesium, iron and silicon content in FS and CS samples
are given in Table 1.
On the basis of these data using the formula
Fo# = a.100/a + 0,435.b, where a and b denote respec-
tively the percentage content of magnesium and iron,

956

954

952
-1
Band cm

950

948 FS
CS
946

944
0 5 10 15 20 25 30 35

Fo#
Fig. 3. The dependence of position of the band 1 at ~ 950 Fig. 4. Microstructure of sample of flash smelting furnace
cm-1 on the forsterite number (The equation of the straight slag. Elongate aggregates of fayalite and black magnetite
line is: Y= 945.088 + 0.34776 X. Then Fo# = 8.3 for the sample crystals in a groundmass of glass. 120x optical magnification.
of flash smelting furnace slag (FS) and Fo# = 5.5 for the Plane polarized (a) and cross polarized (b) transmitted light
sample of converter slag (CS). photomicrographs.

322
 I. Mihailova, D. Mehandjiev

Fig. 5. Typical morphology of fayalite crystals in the sample Fig. 6. Inclusions of magnetite and silicate glass in the
of flash smelting furnace slag. 120x optical magnification. fayalite crystals from flash smelting furnace slag. 120x optical
Plane polarized (a) and cross polarized (b) transmitted light magnification. Plane polarized (a) and cross polarized (b)
transmitted light photomicrographs.

and that for CS sample is 5.5. There are certain differ- observed. Since magnetite is clearly distinguished under
ences between calculated and found values of the forsterite X-rays as a separate phase, it appears that there is less
number, though the theoretical estimate suggesting a iron participating in the fayalite phase. At the same time
higher forsterite number of flash smelting furnace slag silicon-containing phases are additionally found that could
compared to that of converter slag was confirmed. increase the value of the forsterite number, which was
However, it should be kept in mind that silicon actually observed. Some deviations from data for the iso-
also plays a determining role. Calculations based on its morphic series forsterite - fayalite are inevitable and may
content show that fayalite formation phase, in which all be also due to possible inclusion in the olivine crystal
magnesium and iron participate can not be expected. structure of other cations present in the slag.
Taking into consideration the above limitation in the
calculation of the forsterite number, forsterite number Light optical microscopy
values obtained are 4.7 for flash smelting furnace slag Olivine group minerals crystallize in the same
and 1.6 for converter slag. The calculation assumes that system, both in rocks and in slags, but their morpholo-
all the magnesium participates as well as some iron, gies are different. The most frequently occurring forms
inasmuch as allowed by the presence of silicon. From of olivine in rocks have been analyzed by optical mi-
this follows that the excess iron should form a new phase croscopy. These forms are crystal and rounded. Olivine
and presence of magnetite in both slags was actually group minerals from slags show skeletoidal or crystal

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 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

Fig. 7. Allotriomorphic fayalite crystal in the converter slag. 120x optical magnification. lane polarized (a) and cross polarized
(b) transmitted light photomicrographs

Fig. 8. Fayalite displaying skeletal crystal form in the converter slag. 120x optical magnification. Plane polarized (a) and cross
polarized (b) transmitted light photomicrographs

Fig. 9. Typical morphology of fayalite crystals in the sample of converter slag. 120x optical magnification. Plane polarized (a) and
cross polarized (b) transmitted light photomicrographs.

324
 I. Mihailova, D. Mehandjiev

Fayalite crystals occurring in experimentally ob-

tained copper converter slags with variable SiO2 con-
tents are described [15]. The crystals differ in the de-
gree of skeletal growth which is explained in terms of
hindrances in heat transfer brought about by the in-
creasing viscosity of the melt upon increase of the SiO2
content. The formation of tubular inclusions in crystals
elongated along the b-axis is related to the influence of
sulphide droplets at the surface of the crystals [15].
In Figs. 4-10 are given the typical structural re-
lationships between phases present in the examined
samples of slag. It was confirmed that fayalite is the
dominant crystal phase, followed by magnetite and cop-
per sulphide inclusions, with the glass phase present
as a main mass. Fayalite crystals when viewed in trans-
mitted light were pleochroit with shades ranging from
green to pink. For FS sample were typical dendritic
growth and subparallel orientation in space as well as
not fully formed skeletal crystals. The relations be-
tween fayalite and the magnetite phase in the samples
differed. In fayalite crystals themselves there were small
grains of magnetite inclusions. In some cases the lat-
ter formed elongated zones in skeletal fayalite crystals
and showed simultaneous crystallization of both phases.
Heterogeneous xenomorphic crystals were typical
for CS sample. They included many impurities of crys-
talline phases and glass within their boundaries (Fig. 9).
Specific skeletal forms were also observed. The magne-
tite content was definitely higher compared to that in
FS sample and the amorphous phase was more hetero-
geneous.

CONCLUSIONS

From the present study of fayalite crystal phases

in two types of copper slag - flash smelting furnace slag
and converter slag the following conclusions can be
drawn:
Fig. 10. Fayalite (1), magnetite (2), sulphide inclusions (3) • Despite the complex composition of metallur-
and copper (4) in silicate glass a) and b) – sample of flash gical slag and the possibility of inclusion of other ele-
smelting furnace slag; c) – sample of converter slag. 120x ments as isomorphic impurities in the fayalite phase
optical magnification. Reflected light photomicrographs.
Fe2SiO4, the latter’s crystal lattice was not substantially
altered, according to XRD data. The values of the unit
form under microscope. Morphology of olivine crystal cell parameters of fayalite and magnetite in copper slags
forms in slags differs from those in natural aggregates were very close to literature values for pure phases. This
(rocks) [11]. may have been due to isomorphic substitutions of Fe2+,

325
 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

both by cations with smaller ionic radii, such as Mg2+, metalurgia, 3, 1966, 11–16, (in Bulgarian).
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morphology of fayalite in the examined samples of cop- 73-78.
per slag. Fayalite crystals included many impurities of 18. I. Mihailova, Ann. MGU, 52, Part 1 – Geol, 2009,
crystalline phases and glass within their boundaries. Spe- 78-84.
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• On the base of presented data the copper slags stitute for Materials Research and Testing Rudower
may be used as adsorbents and support for catalysts. Chaussee 512485 Berlin, Germany.
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