Minerals Engineering 99 (2016) 123–132

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

The flotation of aluminosilicate polymorphic minerals with anionic and

cationic collectors q
Junxun Jin a, Huimin Gao a,⇑, Xumeng Chen b, Yongjun Peng b, Fanfei Min c
a
School of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, China
b
School of Chemical Engineering, The University of Queensland, St Lucia 4072, Australia
c
School of Materials Science and Engineering, Anhui University of Science and Technology, Anhui 232001, China

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

Article history: Andalusite, sillimanite, and kyanite are three polymorphic minerals with the same formula of Al2SiO5 but
Received 30 December 2015 different crystal structures. Despite their high economic values, selectively recovering them by flotation
Revised 5 June 2016 is a challenge. In this study, the flotation behavior of the three minerals with two types of widely used
Accepted 2 August 2016
collectors, anionic sodium hexadecanesulfonate (SHS) and cationic octadecylamine (OA) were examined
Available online 6 August 2016
at acidic pH. It was found that the flotation behavior of the three polymorphic minerals was different
under the same flotation condition. In the presence of collector OA, the order of the flotation recovery
Keywords:
of the three minerals was kyanite > sillimanite > andalusite, and the recovery increased with slurry pH.
Andalusite
Sillimanite
However, in the presence of collector SHS, the trend of the flotation recovery of the three minerals
Kyanite was completely opposite. X-ray photoelectron spectroscopy (XPS) was applied to quantitatively measure
Flotation the collector adsorption and the surface active sites. The interaction between collectors and minerals was
XPS also studied by zeta potential measurements and calculating the adsorption energy using molecular
Molecular dynamics simulation dynamics (MD) simulation. It was found that the adsorption of collector OA was through the interaction
of amine cations with O atoms by electrostatic attraction and hydrogen bonding. The highest flotation
recovery of kyanite among the three minerals was related to the closest packing arrangement of oxygen
atoms which leads to the highest electronegativity and therefore the lowest adsorption energy of OA. In
comparison, the adsorption of collector SHS was mainly through the chemical interaction of sulfonate
anions with Al atoms. The adsorption energy of SHS on andalusite surface was the lowest, which resulted
from the lowest electronegativity of andalusite surface.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction addition, Al2SiO5 minerals are used to produce high performance

Andalusite, sillimanite, and kyanite are three polymorphic min-
erals with the same chemical formula of Al2SiO5 which contains
62.92% Al2O3 and 37.08% SiO2 (Comodi et al., 1997; Harben,
1995). However, the crystal structures of the three minerals are
different. Andalusite and sillimanite crystallize in the orthorhom-
bic system while kyanite crystallizes in the triclinic system
(Aryal et al., 2008).
Al2SiO5 minerals are important raw materials for producing
high alumina refractory materials. After calcination at tempera-
tures higher than 1000 °C, they can be transformed to mullite
(3Al2O3
2SiO2) which is a high-grade refractory material with
excellent heat and thermal shock resistance and particularly good
creep resistance (McMichael, 1990; Winter and Ghose, 1979). In
q
Presented at Flotation ’15
⇑ Corresponding author at: 122 Luoshi Road, Hongshan, Wuhan 430070, China.
E-mail address: gaohuimin1958@126.com (H. Gao).
lightweight aluminum-silicon alloys, and fabricate metallic fibers
and the leading edge of supersonic aircrafts and spaceships
(Schneider et al., 2008; Skoog and Moore, 1988).
The Al2SiO5 minerals are composed of regionally metamor-
phosed rocks differing mainly in the degree of metamorphism,
and the formation process is controlled by temperature and pres-
sure (Donna, 2002; Klein et al., 1993). Kyanite, andalusite and sil-
limanite are formed in the metamorphic area of high or medium
pressure and low temperature, low pressure and low temperature,
and medium or low pressure and low temperature, respectively
(Kerrick, 1990). The entropy and Gibbs free energy of the three Al2-
SiO5 minerals are very similar, so they can be stably formed at the
transition temperature (Kerrick, 1990). The ore deposit where two
or even three of the Al2SiO5 minerals are associated is not rare
(Chinner, 1966; Hietanen, 1956; Pitcher, 1965; White et al.,
1967). The different formation conditions lead to different crystal
structures of the three Al2SiO5 minerals. Fig. 1 shows the unit cell
models of the three minerals. They have one common feature

http://dx.doi.org/10.1016/j.mineng.2016.08.005
0892-6875/Ó 2016 Elsevier Ltd. All rights reserved.
124 J. Jin et al. / Minerals Engineering 99 (2016) 123–132
Fig. 1. The unit cell model of kyanite (a), andalusite (b), and sillimanite (c).
which is that half of the Al atoms occur in six-fold coordination
forming chains of edge-shared AlO6 octahedra parallel to the crys-
tallographic c-axis (Ohuchi et al., 2006). The differences in their
stability depend on the chemical bonding of the remaining Al
atoms in each polymorph: Al is in four-fold (tetrahedral) coordina-
tion in sillimanite (Burnham, 1963; Padlewski et al., 1992; Yang
et al., 1997b), five-fold coordination (trigonal bipyramidal) in
andalusite (Burnham and Buerger, 1961; Finger and Prince, 1972;
Ralph et al., 1984), and six-fold coordination (octahedral) in kyan-
ite (Ohuchi et al., 2006; Yang et al., 1997a). The Si atom is in four-
fold (tetrahedral) coordination in all three polymorphs.
A concentration process is necessary in order to produce Al2SiO5
mineral products from ores to meet industrial needs (Guo et al.,
2015; Xu et al., 2015; Zhang et al., 2016). The traditional concen-
tration methods are magnetic separation and gravity separation.
However, flotation is becoming the dominant concentration
method due to the decreasing ore grade and the growing industrial
demand for higher product grades (Brandao and Mendes, 1998; Lin
et al., 2011). Both cationic collectors such as amine types and anio-
nic collectors such as sulfonate types have been applied in the
flotation of andalusite, sillimanite, and kyanite at acidic pH
(Bulut and Yurtsever, 2004; Prabhakar et al., 2006; Zhou and
Zhang, 2011). The selection of collectors is usually based on min-
eral surface properties which are highly dependent on slurry pH.
In general, a higher dissolution rate of both Al3+ and Si4+ occurs
at acidic conditions than at alkaline conditions and the release of
Al3+ and Si4+ is not in accordance with the stoichiometric ratio of
atoms in the mineral. More Al3+ than Si4+ is leached from mineral
surfaces, resulting in more positively charged mineral surfaces
which can benefit the adsorption of anionic collectors (Sun and
Yin, 2001). Under neutral pH conditions, the surfaces of Al2SiO5
minerals are negatively charged (Bulut and Yurtsever, 2004; Sun
and Yin, 2001; Zhou and Zhang, 2011), and therefore the cationic
collectors can be applied to float these minerals.
The surface properties of Al2SiO5 minerals are highly dependent
on their crystal structures. Smolik et al. (1966) found that the zero
point of charge of the three Al2SiO5 minerals were different and
related to the ratio of AlAO bonds to SiAO bonds on the cleavage
surface. It is anticipated that the flotation behaviors of the three
Al2SiO5 minerals by using anionic collectors and cationic collectors
are different due to the different mineral surface properties. Smolik
et al. (1966) also studied the dissolution rate of kyanite and anda-
lusite leached at pH 2.7 and pH 11.1 for 60 min and found that the
dissolution rate of Si4+ and Al3+ from these minerals was very low.
Therefore, in the flotation of Al2SiO5 minerals the concentration of
dissolved Si4+ and Al3+ in the slurry may be too low to affect the
behavior of collectors. The different response of cationic or anionic
collectors to the three Al2SiO5 minerals has not been studied. Such
a study is important especially when the selective separation of
two or even three of the Al2SiO5 minerals is required.
Molecular dynamics (MD) simulation is a useful tool to investi-
gate the interactions of reagents with mineral surfaces and the
effect of mineral crystal structures (Du and Miller, 2007; Marzari
et al., 1997; Rai et al., 2011; Segall et al., 2002; Wang et al.,
2008). Rai et al. (2011) demonstrated that MD simulations were
able to describe the structure specificity of oleate molecules and
their interactions with different crystallographic planes of silicate
minerals. It is anticipated that this method can be used to investi-
gate the interaction of cationic and anionic collectors with the
three Al2SiO5 minerals at a molecular scale.
Sodium hexadecanesulfonate (SHS) and Octadecylamine (OA)
have been widely used as collectors in the flotation of oxide and
silicate minerals including Al2SiO5 minerals at acidic pH
(Fuerstenau, 1976; Sun and Yin, 2001). In this study, these two
collectors were examined in the flotation of the three Al2SiO5
minerals. Zeta potential measurements, X-ray photoelectron
spectroscopy analyses and MD simulations were used to study
the interaction between Al2SiO5 minerals and the two collectors.
2. Experimental
2.1. Materials and reagents
Kyanite, andalusite and sillimanite single minerals were sup-
plied from a kyanite mine in Nanyang, Henan, China, an andalusite
mine in Henan, China, and a sillimanite mine in Hebei, China,
respectively. High grade minerals were handpicked, crushed in a
roll crusher, dry ground in a porcelain mill and then screened to
collect 0.10 mm + 0.074 mm particle size fractions. Table 1 shows
the chemical composition of the mineral samples analyzed by XRF.
The content of alumina of the samples was 62.76 wt.%, 61.77 wt.%
and 60.56 wt.%, respectively. X-ray diffraction analysis of the sam-
ples revealed the purity of the minerals to be more than 95 wt.%.
Sodium hexadecanesulfonate (SHS) and octadecylamine (OA)
with 99% purity were obtained from Sinopharm Chemical Reagent
Co., Ltd. OA was prepared by mixing equimolar amounts of octade-
cylamine and hydrochloric acid. SHS and OA were used in the form
of 0.5 wt.% solution. 1.0 wt.% HCl or NaOH solution was used to
adjust the slurry pH. De-ionized (DI) water was used in all exper-
iments. All chemical solutions were made fresh daily.
2.2. Flotation tests
An XFG laboratory mechanical flotation cell with a volume of
35 ml was used in this study. 2.0 g single mineral was firstly mixed
with 35 ml DI water in the flotation cell for 1 min with an impeller
speed of 2000 rpm. 1.0 wt.% HCl or NaOH solution was then added
Table 1
Chemical components of kyanite, andalusite and sillimanite (%).
Al2O3 SiO2 Fe2O3 TiO2 K2O Na2O CaO Ignition
loss
Kyanite 62.76 35.65 0.15 – 0.02 – 0.08 1.04
Andalusite 61.77 37.28 0.55 0.06 0.03 0.17 – 0.14
Sillimanite 60.56 38.22 0.41 0.12 0.02 – 0.43 0.24

to adjust the pulp pH. Collector was then added and conditioned
for 3 min. Flotation was conducted at an air rate of 20 mL min1.
The total flotation time was 3 min and the concentrates were col-
lected by manually scraping. Both the concentrates collected and
the tailings remained in the cell were dried and weighed for calcu-
lating flotation recoveries.
2.3. Zeta potential measurements
Zeta potentials measurements were carried out by ZetaPlus
Zeta Potential Analyzer (Brookhaven Instruments Corporation,
USA). The measurements were performed at 25 °C. 20.0 mg sample
was placed in a 150 ml beaker with 100 ml DI water containing
103 M KCl as a supporting electrolyte. The pH value was then
adjusted using HCl or NaOH solutions and the sample was condi-
tioned for 6 min. Some suspension was sampled for the Zeta poten-
tial measurements. Each sample was measured three times and the
average zeta potential with standard deviation was reported.
2.4. X-ray photoelectron spectroscopy (XPS) analyses
XPS measurements were carried out by the Thermo Electron
Corporation VG Multilab 2000 with a monochromatic Al X-ray
source operating at 300 W. The samples were analyzed at a pres-
sure of 108 Torr at room temperature. Each analysis started with
a survey scan from 0 to 1100 eV using a pass energy of 100 eV at
steps of 1.0 eV with 1 sweep. High resolution spectra of Al2p,
Si2p, O1s, N1s, S2p and C1s were collected at 25 eV pass energy
at steps of 100 meV with 2 sweeps. The measurements were per-
formed at a take-off angle of 45°. The depth of analysis was approx-
imately between 2 and 5 nm. The samples in the absence and
presence of SHS and OA for XPS analyses (about 10 ml of slurry)
were collected from flotation slurry. The slurry samples were
washed with DI water to remove any soluble species and then
introduced into the fore-vacuum of the spectrometer as concen-
trated slurries. The samples were firstly examined in the survey
mode to identify all elements present on the surface, and then var-
ious elemental regions were scanned in order to extract informa-
tion on chemical bonding and elemental valence. Binding
energies were charge-corrected by referencing to adventitious car-
bon at 284.6 eV (Metson, 1999).
2.5. Molecular dynamics (MD) simulations
2.5.1. Force field calculations
The MD simulations were conducted in a Forcite module of
Material Studio 6.0 based on the COMPASS force field method.
The functional forms used in this force field as shown in Eq. (1)
are the same as those used in CFF-type force fields (Hwang et al.,
1994; Rigby, 2004; Sun, 1998).
X 2 3 4
Etotal ¼ ½k2 ðb  b0 Þ þ k3 ðb  b0 Þ þ k4 ðb  b0 Þ 
b
X 2.5.4. Mineral-reagent complexes
þ ½k2 ðh  h0 Þ2 þ k3 ðh  h0 Þ3 þ k4 ðh  h0 Þ4 
X
h surface. The initial geometry of mineral-reagent complex was gen-
þ ½k1 ð1  cos /Þ þ k2 ð1  cos 2/Þ þ k3 ð1  cos 3/Þ
/
X X
0 0
þ k2 v2 þ kðb  b0 Þðb  b0 Þ
v b;b0
X X
þ kðb  b0 Þðh  h0 Þ þ ðb  b0 Þ½k1 cos / þ k2 cos 2/ þ k3 cos3/
b;h b;/
X X 0
þ ðh  h0 Þ½k1 cos/ þ k2 cos2/ þ k3 cos 3/ þ kðh  h00 Þðh  h0 Þ
h;/
X X qi qj
þ kðh  h0 Þðh 0
 h00 Þ cos/ þ
0
b;h ;/ i;j
r ij
J. Jin et al. / Minerals Engineering 99 (2016) 123–132 125
where b, h, /, and v denote bond lengths, valence angles, dihedral
angles, and Wilson out-of-plane displacements, respectively, and
the subscript zero is used to denote the reference unperturbed val-
ues, with the remaining force field parameters denoted by ki. The
functions are divided into two categories or valence terms, diagonal
and off-diagonal cross-coupling terms and nonbond interaction
terms. The nonbonded interactions including a Lennard-Jones9-6
(LJ-9-6) function (Halgren, 1992) for the van der Waals term and
a Coulombic function for an electrostatic interaction are described
by the last two terms, in which rij denotes the inter-atom distance,
qi and qj denote the atom charges, and rij0 and eij denote the LJ-9-6
parameters. The LJ-9-6 parameters (e and r0) are given for like atom
pairs. For unlike atom pairs, a sixth-power mean rule (Waldman
and Hagler, 1993) is used to calculate the off-diagonal parameters:
6 6 !1=6
ðr 0ii Þ þ ðr 0jj Þ
r0ij ¼ ð2Þ
2
0 1
3 3
pffiffiffiffiffiffiffi ðr 0i Þ ðr 0j Þ
eij ¼ 2 ei ej @ 6 6
A ð3Þ
ðr 0i Þ þ ðr0j Þ
The electrostatic interaction is represented by the partial atomic
charge model. To make the charge parameters transferable, bond-
increments dij which represents the charge separation between
two valence-bonded atoms i and j are used in the force field as
parameters (Sun and Rigby, 1997). The net charge of atom i is a
summation of all bond-increments related to this atom:
X
qi ¼ dij ð4Þ
j
where j represents all atoms that are valence-bonded to atom i.
2.5.2. Reagent molecules
OA and SHS molecules with a three-dimensional model were
optimized using the DMol3 module at the level of local density
approximation (LDA) using Perdew-Wang (PWC) function. The
optimization quality was medium and a symmetry calculated
was opened. The optimized atomic structure with partial charges
on the constituent atoms is shown in Fig. 2.
2.5.3. Mineral surfaces
A 2D periodic surface cell was created from the unit cell of the
mineral at the cleavage plane of Al2SiO5 minerals. Based on the
data in literature, the complete cleavage planes of kyanite, andalu-
site and sillimanite are (1 0 0), (1 1 0) and (0 1 0), respectively (Lin
et al., 2011; Wang et al., 2003). As a result, the (1 0 0) plane of
kyanite, the (1 1 0) plane of andalusite and the (0 1 0) plane of sil-
limanite were optimized in this study. The surface energy was then
calculated for these optimized mineral surfaces.
The optimized reagent molecule was docked on the mineral
erated physically on the screen using the molecular graphics
method and the possible interactions of reagent functional groups
with the atoms of mineral surface were considered. The reagent
molecule was then allowed to relax completely on the mineral sur-
face. Several initial conformations were assessed to locate the min-
imum energy conformation of reagent molecules at mineral
surfaces.
b;h
2 !9 !6 3
X r 0ij r 0ij 2.5.5. Computation of interaction energies
þ eij 42 3 5
MD simulation was applied to simulate the reagent-mineral
ij
r ij r ij
surface interaction. Because MD simulation uses the force field
ð1Þ parameters from experimental results or calculations and is based
126 J. Jin et al. / Minerals Engineering 99 (2016) 123–132

Fig. 2. The optimized model of octadecylamine (a) and hexadecyl sulfonate (b).

on the Newtonian motion equations, it requires less calculation

and is more suitable for larger systems compared to the simulation
based on quantum mechanics method (Brown and Julian, 1991;
Jeffrey and Fox, 1984).
In this study, MD simulations were conducted using a
Canonical ensemble (NVT) method at 298 K with a time step
of 0.75 fs, and a total simulation time length of 150.0 ps which
was sufficient for equilibration based on the energy change in
the molecular simulation process of OA and SHS on Al2SiO5
minerals. The non-bonded interaction energies including van
der Waals and Coulomb were calculated by Ewald summation
method. In order to simplify the simulation and reduce the
calculation time, the simulation was conducted in an ideal
vacuum environment. After completing the calculation, 200
reagent-mineral interaction patterns were generated. The
configuration with the lowest energy was selected as the
optimum configuration. The interaction energy was calculated Fig. 3. Flotation recovery of kyanite, sillimanite and andalusite as a function of OA
using the following formula (Rai, 2002): concentration at pH 6.5.

DE ¼ Ecomplex  ðEsurface þ Ereagent Þ ð5Þ

where Ecomplex is the total energy of the optimized mineral-reagent
complex, Esurface and Ereagent represent the total energy of mineral
surface and reagent molecule, respectively. A negative interaction
energy (DE) indicates the stable interaction between the reagent
and the mineral surface. A more negative value of DE indicates a
more favorable interaction. If DE is zero or positive, the adsorption
of reagent on mineral surface would be difficult to occur.
3. Results and discussion
3.1. Flotation
3.1.1. Flotation using octadecylamine (OA)
The flotation behavior of the three Al2SiO5 minerals using OA as
the collector was studied firstly. Fig. 3 shows the flotation recovery
of kyanite, sillimanite and andalusite as a function of OA concen-
tration at pH 6.5. The flotation recovery of all the three minerals
increased with the OA concentration. The maximum recovery
was achieved at an OA concentration of 4  104 mol L1 and fur-
ther increasing the OA concentration had little effect on mineral
recovery. In general, at the same OA concentration, kyanite pre-
sented the highest flotation recovery and andalusite presented
the lowest flotation recovery.
Fig.4 shows the flotation recovery of the three minerals as a
function of pH at an OA concentration of 4  104 mol L1. All
the three minerals showed a poor floatability when pH was below
2.5. However, the flotation recovery increased significantly after
increasing the slurry pH from 2.5 to 3.5. A further increase of pH
could still slightly improve the flotation. The recovery of kyanite,
andalusite and sillimanite at pH 6.5 was 90.21%, 69.62% and
83.64%, respectively. In general, pH played an important role in
the flotation of Al2SiO5 minerals with cationic collector OA. At
the same pH, kyanite always presented the highest flotation recov-
ery while andalusite always presented the lowest flotation
recovery.
 J. Jin et al. / Minerals Engineering 99 (2016) 123–132
Fig. 4. Flotation recovery of kyanite, sillimanite and andalusite as a function of
slurry pH at an OA concentration of 4  104 mol L1.
3.1.2. Flotation using sodium hexadecanesulfonate (SHS)
Fig. 5 shows the flotation recovery of the three minerals as a
function of SHS concentration at pH = 3.0. The flotation recovery
of all the three minerals gradually increased with SHS concentra-
tion until the recovery reached a maximum at an SHS concentra-
tion of 7.5  104 mol L1. The highest recovery of kyanite,
andalusite and sillimanite was 69.47%, 83.37% and 75.05%, respec-
tively. Under the same flotation condition, andalusite presented
the highest flotation recovery while kyanite presented the lowest
flotation recovery.
Fig. 6 shows the flotation recovery of andalusite, sillimanite and
kyanite as a function of slurry pH at an SHS concentration of
7.5  104 mol L1. The recovery of all the three minerals
decreased with pH. At pH 1.5, the recovery of andalusite, silliman-
ite and kyanite was 87.85%, 84.41% and 78.36% respectively. After
increasing pH to 7.0, the recovery of all the three minerals dropped
below 20%.
3.2. Zeta potential measurements
The electrostatic interaction plays an important role in collector
adsorption on mineral surface. It has been reported that all the
three Al2SiO5 minerals contain SiO4 tetrahedra and AlO6 octahedra
in their crystal structures and SiAO has a higher bonding strength
than AlAO (Hu et al., 2003; Sun and Yin, 2001). Therefore, the
cleavage of Al2SiO5 minerals usually occurs along planes connected
by AlAO bonds, producing valence-unsaturated AlAO bonds and
Fig. 5. Flotation recovery of kyanite, sillimanite and andalusite as a function of SHS
concentration at pH 3.0.
127
Fig. 6. Flotation recovery of kyanite, sillimanite and andalusite as a function of
slurry pH at an SHS concentration of 7.5  104 mol L1.
SiAO bonds which dictate the surface electrical properties of Al2-
SiO5 minerals. SiO4 tetrahedra interacts with water molecules
and the surfaces are covered with OH which can be dissociated
or adsorb H atoms. AlO6 octahedra produces various AlAOH ions
with different degrees of hydration and the change of pH may
influence the density of AlAOH ions (Sun and Yin, 2001; Yoon
et al., 1979).
The zeta potentials of kyanite, andalusite and sillimanite as a
function of pH were measured and the results are shown in
Fig. 7. Kyanite, andalusite and sillimanite exhibited an iso-
electric point (IEP) at pH 6.6, pH 6.0 and pH 5.5, respectively. They
were positively charged at pH smaller than their IEP values, but
negatively charged at pH greater than their IEP values. With an
increase in pH, they became more negatively charged. At acidic
conditions from pH 1.5–6.5, the collector OA is present in the form
of cations (Cao et al., 2010, 2011; Wang et al., 2014b), while SHS
with the pK of sulfonic acid being about 1.5 is present in the form
of anions (Somasundaran and Fuerstenau, 1966). The increased
flotation recovery in the presence of OA and the decreased flotation
in the presence of SHS with pH suggest that electrostatic interac-
tions may play a role in the adsorption of OA and SHS on Al2SiO5
mineral surfaces. However, the sign and magnitude of the surface
charge did not exactly correlate with the flotation results. Fig. 7
shows that sillimanite was the most negatively charged among
the three Al2SiO5 minerals, but its recovery in flotation in the
presence of OA or SHS was between kyanite recovery and
andalusite recovery as shown in Figs. 4 and 6. It is clear that other
Fig. 7. Zeta potentials of the three Al2SiO5 minerals as a function of pH: error bars
represent mean values of three tests ± standard deviation.
128 J. Jin et al. / Minerals Engineering 99 (2016) 123–132

mechanisms may also be responsible for the adsorption of OA and andalusite, and six-fold coordination forming AlO6 octahedra in
SHS on Al2SiO5 mineral surfaces. In this study, XPS analyses and the kyanite. The AlAO bond distance of AlO4 tetrahedra and AlO6
computation of interaction energies by MD simulation were con- octahedra is 0.17 nm and 0.19 nm, respectively, and the AlAO bond
ducted to further understand the adsorption of collectors on min- distance of AlO5 hexahedra is between AlO6 octahedra and AlO4
eral surfaces. tetrahedra (Aryal et al., 2008; Sun and Yin, 2001). There is a general
trend between bond length and bond strength. Usually, the shorter
3.3. XPS analyses the bond, the stronger the bond (Price and Ross, 1992). As a
result, the AlAO bond of AlO4 tetrahedra is the most difficult to
The three Al2SiO5 minerals share the same chemical composi- break, while the AlAO bond of AlO6 octahedra is the most easily
tion but have different crystal structures. Crystal structures of sil- to break. Consequently, the concentration of Al on kyanite surface
icate minerals not only have a direct effect on the properties of is higher than that on the sillimanite surface due to a larger
the cleaved surfaces but also influence the interaction with collec- number of AlAO bond cleavages.
tors and therefore play an important role in mineral flotation. XPS The change of slurry pH had a slight influence on the composi-
is a surface sensitive technique and has been widely used to ana- tion of surface species. As shown in Table 2, the concentration of O
lyze the mineral surface properties (Chen et al., 2014; Peng et al., increased slightly with the increase of the slurry pH, while the sur-
2012; Wang et al., 2014a). In this study, XPS was used to investi- face concentrations of Al and Si decreased with the increase of the
gate the surface species on the three Al2SiO5 minerals and also slurry pH. In addition, the Al-to-Si ratio on the surfaces of all the
the interaction of mineral surfaces with collectors. three minerals was slightly higher at pH 1.5 than at pH 6.5, which
indicates that more Al than Si was leached from mineral surfaces at
3.3.1. Surface species of the three Al2SiO5 minerals the acidic condition. Since more Al3+ are exposed on mineral sur-
Mineral samples after conditioning at different pH values in the faces at more acidic pH, mineral surfaces become more positively
flotation cell were taken and then subjected to XPS measurements. charged, which can benefit the adsorption of anionic collectors,
Table 2 shows the atomic concentration of O, Si and Al on the sur- but is unfavorable for the adsorption of cationic collectors.
faces of three Al2SiO5 minerals at pH 1.5 and 6.5. The XPS-
measured atomic concentration was normalized to oxygen, alu-
minum and silicon. The component removed from the elemental 3.3.2. Collector adsorption on mineral surfaces
accounting by this normalization process was C in the form of 3.3.2.1. Adsorption of octadecylamine (OA). The adsorption of OA on
adventitious hydrocarbons. Table 3 shows the Al-to-Si ratio at Al2SiO5 minerals has not been reported in literature. However, a
the surface of the three Al2SiO5 minerals at pH 1.5 and 6.5. similar system was studied by Xia et al. (2009) who investigated
As shown in Table 2, among the three minerals, Al concentra- the adsorption of dodecylamine on kaolinite and found that dode-
tion was the highest on kyanite surface while the lowest on silli- cylamine was difficult to adsorb onto kaolinite through chemical
manite surface. This should be related to the different stability of bonding with Al atoms. Although the carbon chain length of dode-
their surface bonds due to different crystal structures. In general, cylamine and OA is different, their properties and adsorption
the crystal structures of the three Al2SiO5 minerals have a common mechanisms should be similar due to the presence of the same
feature that half of the Al atoms occur in six-fold coordination polar group. It is anticipated that OA should be difficult to adsorb
forming AlO6 octahedra. The differences in their stability depend onto the three Al2SiO5 minerals with Al atoms through chemical
on the chemical bonding of the remaining Al atoms in each adsorption but most likely with O atoms by physical adsorption
polymorph: Al is in four-fold coordination forming AlO4 tetrahedra as a result of electrostatic interactions and hydrogen bonding. As
in sillimanite, five-fold coordination forming AlO5 hexahedra in shown in Table 2, among the three minerals, sillimanite has the
highest oxygen concentration on the surface. At the same OA con-
centration, sillimanite should present the highest floatability since
Table 2
it has the highest oxygen concentration on the surface to interact
XPS derived surface concentrations (atomic % normalized to Al, O and Si) of the three
Al2SiO5 polymorphic minerals at pH 1.5 and 6.5. with OA. However, this prediction does not correlate well with
the flotation results in Fig. 4 which shows that kyanite rather than
Sample Element Concentration (at.%)
sillimanite presented the highest flotation recovery. This indicates
pH = 1.5 pH = 6.5 that the flotation behavior of these Al2SiO5 minerals did not
Kyanite O 60.05 60.47 entirely depend on the amount of surface oxygen available for col-
Si 17.88 17.87 lector interaction but was more related to the affinity of OA to the
Al 22.07 21.66 surface of each mineral. Therefore, the interaction of OA with the
Andalusite O 59.71 60.63 three Al2SiO5 minerals was investigated by XPS measurements.
Si 19.09 18.95 XPS survey scan was conducted to measure the surface ele-
Al 21.20 20.42
ments on the three Al2SiO5 minerals in the absence and presence
Sillimanite O 61.31 61.85 of collector OA. Table 4 summarizes the binding energy of each
Si 19.57 19.49
Al 19.12 18.66
detected element and the atomic concentrations which were nor-
malized to oxygen, aluminum, silicon, carbon and nitrogen. In
the absence of OA, the element of C1s originated from environmen-
tal contamination, but in the presence of OA, it originated from
Table 3
both environmental contamination and adsorbed OA. N1s signal
Al-to-Si ratio at the surface of the three Al2SiO5 polymorphic minerals at pH = 1.5 and was detected on the surfaces after being treated with collector
pH = 6.5. OA, and was from the amino group of the collector. The results sug-
Sample Al-to-Si ratio
gest that OA adsorbed on the three Al2SiO5 minerals. In addition,
the surface concentrations of Si and Al decreased slightly while
pH = 1.5 pH = 6.5
the surface concentration of O decreased substantially after OA
Kyanite 1.23 1.21 addition. It is clear that OA adsorbed onto the three Al2SiO5
Andalusite 1.11 1.08
minerals by the interaction of amine cations with O atoms rather
Sillimanite 0.98 0.96
than Al atoms.
 J. Jin et al. / Minerals Engineering 99 (2016) 123–132 129

Table 4 Table 5
XPS derived surface binding energy and concentrations (atomic % normalized to Al, O, XPS derived surface binding energy and concentrations (atomic % normalized to Al, O,
Si, N and C) on the three Al2SiO5 polymorphic minerals at pH 6.5 in the absence and Si, S and C) on the three Al2SiO5 polymorphic minerals at pH 1.5 in the absence and
presence of OA (4  104 mol L1), BE – binding energy, C – concentration. presence of SHS (7.5  104 mol L1), BE – binding energy, C – concentration.

Sample Element The absence of OA The presence of OA Sample Element The absence of SHS The presence of SHS
BE (eV) C (at.%) BE (eV) C (at.%) BE (eV) C (at.%) BE (eV) C (at.%)
Kyanite C1s 284.60 15.21 284.60 27.98 Kyanite C1s 284.60 15.16 284.60 26.83
O1s 531.53 51.27 531.41 39.50 O1s 531.56 50.95 531.39 41.89
Si2p 102.41 15.15 102.30 13.81 Si2p 102.38 15.17 102.31 14.06
Al2p 74.76 18.37 74.58 17.08 Al2p 74.74 18.72 74.17 16.16
N1s 401.07 1.63 S2p 168.32 1.06
Andalusite C1s 284.60 15.15 284.60 26.17 Andalusite C1s 284.60 15.20 284.60 46.02
O1s 531.64 51.44 531.54 41.00 O1s 531.59 50.63 531.51 33.40
Si2p 102.53 16.08 102.44 14.37 Si2p 102.52 16.19 102.42 10.32
Al2p 74.78 17.33 74.62 17.20 Al2p 74.70 17.98 73.85 7.10
N1s 400.50 1.26 S2p 168.74 3.16
Sillimanite C1s 284.60 15.22 284.60 27.25 Sillimanite C1s 284.60 15.22 284.60 36.50
O1s 531.90 52.44 531.80 41.39 O1s 531.80 51.98 531.78 36.41
Si2p 102.71 16.52 102.64 14.81 Si2p 102.63 16.59 102.61 15.16
Al2p 74.85 15.82 74.68 15.13 Al2p 74.83 16.21 74.08 9.29
N1s 401.13 1.42 S2p 168.53 2.64

Table 4 also shows that the nitrogen concentration on the sur-
faces of kyanite, andalusite and sillimanite in the presence of col-
lector OA was 1.63%, 1.26% and 1.42%, respectively. A higher
nitrogen concentration indicates the presence of a higher amount
of collector on the surface. Therefore, the highest adsorption of
OA occurred on kyanite surface while the lowest OA adsorption
occurred on andalusite surface.
well with the lowest flotation recovery under the same flotation
condition. In addition, aluminum concentration on mineral surface
also decreased significantly after being treated with SHS. The high-
est decrease occurred on andalusite surface, which is consistent
with the highest flotation recovery as well.

3.4. Computation of interaction energies by MD simulations

3.3.2.2. Adsorption of sodium hexadecanesulfonate (SHS). Wei and
Wei (1991) studied the adsorption of petroleum sulfonate on kyan-
ite surface by zeta potential and infrared spectroscopy and found
that the adsorption occurred mainly through chemical bonding. A
later study by Zhou and Zhang (2011) also showed that petroleum
sulfonate adsorbed onto andalusite surface through chemical
adsorption. The collector SHS used in this study has a similar struc-
ture as petroleum sulfonate. Therefore, SHS may adsorb onto the
three Al2SiO5 minerals through a chemical interaction. In this
study, XPS measurements were applied to investigate the interac-
tion of SHS with the three Al2SiO5 minerals.
XPS survey scan was conducted to measure the surface ele-
ments on the three Al2SiO5 minerals in the absence and presence
of collector SHS. Table 5 summarizes the binding energy of each
detected element and the atomic concentrations which were nor-
malized to oxygen, aluminum, silicon, carbon and sulfur. Again,
in the absence of SHS, the element of C1s originated from environ-
mental contamination, but in the presence of SHS, it originated
from both environmental contamination and adsorbed SHS. S2p
signals of the sulfonate group were detected on the surface of all
the three minerals in the presence of SHS, which indicates that
SHS adsorbed on the mineral surfaces. In addition, a clear shift of
the Al2p binding energy was observed after SHS addition and the
shifts on kyanite, andalusite and sillimanite were 0.57 eV, 0.85 eV
and 0.75 eV, respectively. The chemical shifts of other elements
were less than 0.2 eV. The higher chemical shifts of the Al2p indi-
cate that SHS adsorbed onto the three Al2SiO5 minerals by the
interaction of sulfonate anions with Al atoms.
Although the three Al2SiO5 minerals were conditioned with the
same dosage of SHS, the changes of surface element concentrations
were different. Sulfur concentrations on the surfaces of kyanite,
andalusite and sillimanite were 1.06%, 3.16% and 2.64%, respec-
tively. The highest sulfur concentration on andalusite surface sug-
gests the highest collector adsorption, which is consistent with the
highest flotation recovery shown in Fig. 6. In contrast, the sulfur
concentration on kyanite surface was the lowest, which correlates
MD simulation is a powerful tool to investigate the solid-liquid
interface properties and is able to provide the adsorption structure
and dynamics in a molecular scale which cannot be easily studied
in the laboratory (Leermakers et al., 2006; Reimer et al., 2005;
Tarek et al., 1998). This study applied the Forcite module in Mate-
rial Studio 6.0 to conduct the MD simulation of collectors and min-
eral surfaces. The energy was calculated during the simulation and
the adsorption strength of the mineral surface by collectors was
analyzed by the adsorption energy.
The MD simulation was conducted on the complete cleavage
plane of each mineral which is (1 0 0) plane of kyanite, (1 1 0)
plane of andalusite and (0 1 0) plane of sillimanite. Prior to simula-
tion, the optimized unit cell was firstly imported and build-
surfaces-cleave surface function was applied to obtain the cleavage
plane of each mineral. Subsequently, supercells were created based
on the cleavage planes to expand the surfaces for the interaction of
collectors with minerals. Fig. 8 shows the created supercell sur-
faces of kyanite, andalusite and sillimanite.
According to XPS analyses, OA adsorbs on the Al2SiO5 mineral
surfaces mainly through the reaction with surface O atoms,
whereas the adsorption of SHS relies on the interaction with sur-
face Al atoms. Therefore, after placing the collector on crystal sur-
faces during simulation, priority was given to the interaction of OA
with surface O atoms and the interaction of SHS with surface Al
atoms. The adsorption status of OA with mineral surfaces was
determined by the initial distance between the H atom of the head
group and the surface O atoms, while the adsorption status of SHS
with mineral surfaces was determined by the initial distance
between the O atom of the head group and the surface Al atoms.
The adsorption status of OA and SHS on each mineral surface at
the lowest simulation energy was shown in Figs. 9 and 10,
respectively.
The adsorption energy of OA and SHS on mineral surfaces was
calculated to investigate the interaction between collectors and
minerals. When collector interacts with mineral surface, a lower
130 J. Jin et al. / Minerals Engineering 99 (2016) 123–132

Fig. 8. Supercell surfaces of kyanite (1 0 0) plane (a), andalusite (1 1 0) plane (b) and sillimanite (0 1 0) plane (c).

Fig. 9. The adsorption configuration of OA with kyanite (a), andalusite (b) and sillimanite (c).

Fig. 10. The adsorption configuration of SHS with kyanite (a), andalusite (b) and sillimanite (c).

adsorption energy indicates a more stable interaction and there- of OA on mineral surfaces. The lowest DE was found in the kyanite
fore a better flotation performance. system and the highest DE was in the andalusite system. Therefore,
As shown in Table 6, the interaction energy (DE) of OA with the OA has the highest affinity to kyanite surface but the lowest affin-
three Al2SiO5 minerals is negative, indicating the stable adsorption ity to andalusite surface.
 J. Jin et al. / Minerals Engineering 99 (2016) 123–132
Table 6
A comparison of the interaction energy of OA and water on the three Al2SiO5 minerals
(kJ mol1).
Mineral OA
Kyanite 1278.29
Andalusite 1059.24
Sillimanite 1100.72
Table 7
A comparison of the interaction energy of SHS and water on the three Al2SiO5
minerals (kJ mol1).
Mineral SHS
Kyanite 2063.68
Andalusite 5696.25
Sillimanite 5122.47
Kyanite has the closest packing arrangement of oxygen atoms
while andalusite has the loosest packing arrangement of oxygen
atoms (Smolik et al., 1966). Since the adsorption of collector OA
on Al2SiO5 minerals is through the interaction between amine
cations and oxygen atoms, the different packing arrangement of
oxygen atoms may determine the affinity of OA. The electronega-
tivity of the mineral surface is related to the packing arrangement
of surface atoms. The electronegativity is higher when the packing
arrangement of oxygen atoms is closer. Therefore, kyanite has the
highest electronegativity while andalusite has the lowest elec-
tronegativity. OA which is a cationic collector should be easier to
adsorb onto the surface with a higher electronegativity. As a result,
the adsorption of collector OA is the easiest on kyanite surface
while the most difficult on andalusite surface.
Table 7 shows the interaction energy of SHS with the three
Al2SiO5 minerals. In all the three systems, the total energy
decreased after the mineral surfaces interacting with collector
SHS, resulting in negative DE. The most negative DE was found
in the andalusite-SHS system, which indicates that andalusite has
the strongest interaction with SHS. The results match well with
the flotation results and the XPS analyses. The different interaction
between sulfonate anions and aluminum ions of the three Al2SiO5
minerals is also attributed to the different packing arrangement of
oxygen ion and the electronegativity on the crystal surfaces. Since
SHS is an anionic collector, it should be more difficult to adsorb
onto the surface which has a higher electronegativity. Therefore
SHS is the most difficult to adsorb onto kyanite surface which
has the highest electronegativity among the three minerals while
the easiest to adsorb onto andalusite surface which has the lowest
electronegativity.
In the computations, it was difficult to include water molecules
as indicated in other studies (Rath et al., 2014; Yu et al., 2015).
However, it was possible to compute interaction energy for water
adsorption on the three Al2SiO5 minerals. As showed in Tables 6
and 7, in all cases, the interaction energy for OA or SHS adsorption
was lower than that for water adsorption suggesting that OA or
SHS would replace water on Al2SiO5 minerals.
The computations reported in this study did not take into
account the effect of pH. More sophisticated and more computer
intensive computations would be needed for studying the effect
of pH on the interactions of surfactants with the mineral surface.
Despite this, the close match observed between the flotation of
these Al2SiO5 minerals using these surfactants and molecular mod-
eling computations which model the crystal structure specific
interactions demonstrate the power of such computations in being
able to capture the essential differences in mineral-surfactant
interactions.
131
4. Conclusions
The three Al2SiO5 polymorphic minerals, andalusite, sillimanite,
Water and kyanite, showed different flotation behavior due to their
501.08 different crystal structures. When using OA as the collector, the
802.48 order of the floatability was kyanite > sillimanite > andalusite and
637.11
the flotation recovery of all the three minerals increased with
pH. In contrast, when using SHS as the collector, the order of the
floatability was andalusite > sillimanite > kyanite and the recovery
of all the three minerals decreased with pH.
The surface species of the three Al2SiO5 minerals were different
due to the different crystal structures and were affected by slurry
pH. The collector OA adsorbed onto Al2SiO5 mineral surfaces by
Water
the interaction of amine cations with O atoms. Kyanite surface
501.08
had the highest adsorption of collector OA while andalusite surface
802.48
637.11 had the lowest OA adsorption. Different from collector OA, collec-
tor SHS adsorbed onto the three minerals by the interaction of
sulfonate anions with Al atoms rather with O atoms. The adsorp-
tion of SHS was the highest on andalusite surface and the lowest
on kyanite surface.
The interaction energy was negative in all the mineral-collector
systems. In the presence of collector OA, the lowest DE was found
in the kyanite system while the highest DE was in the andalusite
system, which indicates that the adsorption of OA on kyanite sur-
face was the easiest while the adsorption on andalusite surface was
the most difficult. In the presence of the collector SHS, the lowest
DE was found in the andalusite system and the highest DE was
in the kyanite system, which suggests the highest adsorption on
andalusite surface and the lowest adsorption on kyanite surface.
The different collector adsorption behavior was mainly caused
by the different interaction mechanisms. The adsorption of collec-
tor OA was through the interaction of amine cations with O atoms
by electrostatic attraction and hydrogen bonding. The highest
kyanite flotation recovery among the three minerals was related
to the closest packing arrangement of oxygen atoms which leads
to the highest electronegativity and therefore the lowest adsorp-
tion energy of cationic OA. Andalusite showed the best floatability
in the presence of collector SHS due to the strongest interaction of
sulfonate anions with Al atoms.
Acknowledgements
The authors gratefully acknowledge the financial support of this
study from Wuhan University of Technology. Nanyang Kyanite
Mining Limited is thanked for the supply of the mineral samples.
The first author also thanks the scholarship provided by Wuhan
University of Technology.
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