ISIJ International, Vol.

58 (2018),
ISIJ International,
No. 3 Vol. 58 (2018), No. 3, pp. 379–400

Review

Measurement for Contact Angle of Iron Ore Particles and Water

Kai TANG,1) Xuewei LV,1,2)* Shanshan WU,1) Senwei XUAN,1) Xiaobo HUANG3) and Chenguang BAI1)

1) School of Materials Science and Engineering, Chongqing University, No. 174 Shazheng Street, Shapingba District,
Chongqing, 400044 China. 2) The State Key Laboratory of Mechanical Transmissions, Chongqing University, No. 174
Shazheng Street, Shapingba District, Chongqing, 400044 China. 3) Technique Center, Handan Iron and Steel Com-
pany, Hebei Iron and Steel Group, at No. 232 Fuxing Road, Handan, Hebei, 056000 China.
(Received on July 21, 2017; accepted on November 10, 2017)

Contact angle, as a key index for the wettability of iron ore particles by water, is of very important for
the iron ore processing like beneficiation, sintering and pelletizing.
Methods developed for measuring the contact angles generally can be divided into direct and indirect
methods, which were summarized in present study and their advantages and disadvantages are all com-
pared. Capillary rise method may be the most applicative approach for porous particles.
Most of the contact angles between iron ore particles with water reported in the literatures were col-
lected and the influence of the physical and chemical properties of iron ore particles were analyzed. The
result shows that iron ore particles are hydrophilic and its water contact angles are influenced by the
complicate interaction of chemical compositions, especially the content of oxy-hydroxides and the surface
morphology. Generally, the water contact angle of goethite is the smallest. Complicate surface morphology
suggest a better wettability. Furthermore, the penetration behavior of natural iron ore particles and syn-
thetic iron ore particles are obviously different during the contact angle measurement. Compared with
sessile drop method, capillary rise methods are more suitable for the measurement of natural iron oxides.
Some empirical equations to predict the contact angle were collected and compared. The wettability can
be improved by increasing the surface morphology of particles, coating of iron ore particles, and high-
temperature treatment.

KEY WORDS: wettability; contact angle; chemical composition; surface morphology; iron ore particles.

(solid, liquid and gas) and was further studied by many

1. Introduction
Granulation1–4) process is a typical method getting iron
ore particles together to form pellets/granules using water
as the binder in steel making industry. A good granulation
result can make a better permeability of the bed of granules
in the sintering strand.5,6) With the decreasing of high grade
iron ore, sinter preparation in the iron ore industry is rou-
tinely performed using a blend of different ores with low
total Fe content which usually called low grade iron ores.
However, there is little regard for how this may be affect-
ing the granulation performance. Maeda et al.7) discovered
that the use of some low grade iron ores in granulation
may cause the fracture of sintered ores, which suggests the
sintered ore has a low strength. Due to the above uncertain
situation, this is particularly important for iron ore samples
where significant differences in surface chemistry may be
expected to be altered substantially granulation process. It
is believed that the granule strength is largely determined by
the wettability of iron ore particles, the surface characteris-
tics and properties of binders.8)
Wettability9) is always characterized by contact angle
which is first expressed by Young10) as a three phases angle
* Corresponding author: E-mail: lvxuewei@163.com
DOI: http://dx.doi.org/10.2355/isijinternational.ISIJINT-2017-424
authors. Not only in granulation process, but also in mineral
processing fields such as wet grinding, flotation, etc.,11–17)
contact angles of iron ore particles and water, as a classical
parameter, is widely studied.
Generally, it is believed that smaller contact angle sug-
gests better wettability and easier to agglomerate. The
reason is that water droplet spread smoothly on mate-
rial surface with good wettability, and moderate water in
granulation can increase the strength of the liquid bridges
between particles.18–20) Agglomeration21–23) is a process of
wetting particles and making them coalesced together. As
the schematic illustration of agglomerate during granulation
process shown in Fig. 1, first, water droplet is dripped on the
surface of powder bed and begin to disperse. At the same
time, penetration occurs and water contact inner particles
through void of inter-particle. According to the distribu-
tion situations of water, it can be classified into pendular,
funicular, capillary and droplet.24,25) When penetration time
increases, water gradually filled into the space of inter-
particles, while the states are transferred from pendular to
droplet. Rumpf26) and Kapur et al.24) found that the strength
of granules depends on the porosity of particles and connect-
ing forces between particles. Among these forces, capillary
force is conservative that act to pull particles together.27)
Willet et al.28) numerically solved the full Laplace–Young

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 ISIJ International, Vol. 58 (2018), No. 3
equation and then fitted empirical expressions to the results,
as Eq. (1) shows.
2 a LV cos 
F= 1
 h2 a  2  h2 a  ............... (1)
1.0  2.1    10.0   and the indirect one. The direct measurement can be easily
 V   V 
Where γLV is the liquid surface tension, a is the radius of
particle, h is the half distance between two vertical slices of
particle surface, V is the bridge volume, θ is contact angle
and r is the curvature of the bridge surface, which can be
calculated from the two principal radii of curvature of the
surface, as shown in Fig. 2. It can be seen that the force
turns out to be directly proportional to the contact angle
of the system.29) Through this equation, the effect of water
contact angle on granulation can be indirectly characterized.
However, for porous particles like natural iron ore par-
ticles, the liquid soaked into intra-granular pores influences
its amount used in granulation process. It is helpful to
improve granulation by optimizing proportioning of iron
ore under the guidance of contact angle. Therefore, it is a
Fig. 1. Schematic illustration of agglomerate during granulation
process.
Fig. 2. Schematic of a liquid bridge between spheres.
Fig. 3. Categories of contact angle measurement methods.
© 2018 ISIJ
vital issue that how to obtain accurate contact angle of iron
ore particle.
According to various determinations for the contact
angle of particles, the measurement methods for contact
angle can be divided into two categories: the direct method
used for the contact angle of solid, but with a requirement
of a rigid homogeneous smooth surface.30) And compared
with the direct measurements, the latter methods are more
generally used in contact angle measurements for particles,
due to the great small size of particles cannot be convenient
to measure with the direct one. As shown in Fig. 3, there
are many measurement methods that have been developed
for particles: sessile drop method,31–37) captive bubble tech-
nique,38–40) Wilhelmy plate,41) capillary rise method,42,43) and
some other new measurements,44–47) all of the above are
briefly described below.
Many previous works have been done to determine the
contact angle of particles or powders, but there still has
relatively few studies on the contact angle of iron ore par-
ticles. Most papers are based on synthetic iron ore particles
and did not go deep into the relation between contact angles
and properties of iron ore particles. Iveson et al.48,49) have
done a series work on the contact angle of iron ore fines,
include measure the value of advancing contact angle of 17
different iron ores. Huang et al.50) tested contact angles of 7
kinds of iron ore particles with water and proposed a new
model for contact angle.
Results of contact angles of natural porous iron ore
particles and water is more significant to be evaluated for
wettability of most iron ore particles and understanding
granulation process. It should be understood that strict sci-
entific contact angle is not suitable to get the overall knowl-
edge of wettability for natural iron ore particles because
some vital messages are not include, such as porosity, sur-
face roughness and heterogeneity. In capillary rise methods,
particle groups used are always porous and without uniform
size, which properties is familiar with the materials used in
granulators. Therefore, contact angles measured with these
methods contain some surface properties of particles and
can be used to improve granulation. In the paper of Mao et
al.,51) they have proved contact angles obtained by capillary
rise methods are appropriate to evaluate granulation results
and gave a binary linear regression equation.
The present review covers the various measurements of
contact angle for particles, and some important basic theories
were explained in detail. Materials and results of contact
angle measurement for iron ore particles and water were col-
lected and summarized. Also, influencing factors were dis-
cussed carefully and some useful suggestions were proposed.
380
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2. Contact Angle
2.1. Equilibrium Contact Angle
Contact angles can be defined as equilibrium and dynamic
contact angle.
Droplet is always spherical as it is free from the effect
of force field and only forced by the surface tension. But
when it contacts with solid surface, the final shape of the
droplet depends on the cohesion inside and the adhesive
force between solid and liquid. In addition, droplet can
spread out on solid surface and form an angle on the contact
line between three phases: solid, liquid and gas, which is
defined as the equilibrium contact angle. As shown in Fig.
4, the droplet on solid surface bears three forces, and an
equilibrium contact angle emerged when the forces balance.
In 1805, Young10) proposed the famous equation to
describe this situation, which is known as the Young’s
equation:
 LG  cos Y   SG   LS ........................ (2)
Where γSG (N/m) is the solid-gas interfacial energy, γLG
(N/m) is the liquid-gas interfacial energy, and γLS (N/m) is
the liquid-solid interfacial energy, where interfacial energy
has unit mJ m − 2. But this equation is valid only when the
solid surface is an ideal one which is rigid smooth, homog-
enous, inert, planar and non-deformable.52)
2.2. Dynamic Contact Angle
The surface of real solid is not as smooth and uniform as
the ideal, so the interfacial energy of the surface in different
position is inconstant. Hence, the contact angle isn’t a set-
tled value suggest by the Young’s equation, but is a dynamic
value between two relatively stable angles, which is called
the contact angle hysteresis. The contact angle hysteresis
is the embodiment of surface roughness and heterogeneity.
As shown in Fig. 5, the advancing contact angle is a special
angle formed when the gas-solid interface is replaced by
the liquid-solid interface as the droplet is going to run at a
gradient plate. While, on the other side of the droplet, the
liquid-solid interface is replaced by the gas-solid interface.
And the angle formed on the gas-liquid-solid contact line is
the receding contact angle. The contact angle hysteresis can
be calculated by the following equation:
   A   R ............................... (3)
Where Δθ (degree) is the contact angle hysteresis, θA
Fig. 4. Forces involved on a droplet placed on a solid surface.
Fig. 5. Advancing contact angle and receding contact angle.
381
(degree) is the advancing contact angle and θR (degree) is
the receding contact angle.
It is reported that the advancing contact angle is always
larger than the receding contact angle. The swelling behav-
ior and surface roughness make contribution to this phe-
nomenon.53)
3. Contact Angle Measurement Methods for Particles
Contact angle measurement methods can be divided into
two categories according to various methods proposed by
literatures. One is called the direct methods and the other is
the indirect methods.33)
3.1. Direct Methods
Generally, sessile drop method,36,54,55) captive bubble
method,38,56,57) environmental scanning electron microscopy
(ESEM) method44,52,58,59) and gel trapping method45,47) are
direct methods. These methods obtain contact angles by
observing the forming angles directly based on the theory of
Young. The use of high speed CCD camera, scanning elec-
tron microscope (SEM), or Environment Scanning Electron
Microscope (ESEM) makes it possible to observe contact
angles from macroscopic to microscopic. Obviously, the
direct methods have advantages of convenient operation and
apparent results compared to indirect methods.
Sessile drop method is one of the most widely used
direct techniques to measure the contact angle. Usually, the
surface of materials is highly required smooth planar and
non-porous so that it can obtain reliable results. For solid
particles, the sessile drop method still can be applied when
particles are compressed into compacts or tablets to form
flat surface. In this way a high speed CCD camera is used
to capture pictures of the compressed particle substrate and
droplet on the compact/table. The schematic of the apparatus
is shown in Fig. 6. The dynamic contact angle is produced
by increasing/decreasing the volume of droplet by using a
syringe. Pictures of equilibrium states or dynamic states
are analyzed by image analysis software and then the static
contact angle is obtained. There are some drawbacks exist
in the traditional sessile drop method, and some measures
have been proposed to improve this method,33–35,53,60–63) also,
it was modified for finely particles.32,44)
3.2. Indirect Methods
For indirect methods, the core theories are the famous
Washburn equation or some other mechanical equilibrium
formulas (such as Wihelmy plate method41)), and contact
Fig. 6. Left: The schematic diagram of apparatus using sessile
drop method: 1- high speed CCD camera, 2- light source,
3- sample rig. Right: Drop of water on the modified flat
surface.62)
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 ISIJ International, Vol. 58 (2018), No. 3
angles can be obtained by calculating these equations. Com-
pared with direct methods, indirect methods seem to more
popular in contact angle measurements for particles.
Among these indirect methods, capillary rise methods
are broadly used for contact angle measurement of particles
due to its appropriate for porous particles. The classical
capillary rise method is the Washburn method64) first pro-
posed by Washburn in 1921. Based on the traditional one,
varieties of alternative capillary rise methods have been
developed to apply in particle contact angle measurements.
Wei et al.65) have classified the capillary rise method as
the height method, the pressure,66,67) mass method,41,68) and
other methods such as thin-layer wicking method34,69–71)
and equilibrium height method.72,73) To apply the Washburn
equation, the properties of liquid and flow are restricted as
follows:41,74)
(1) Newtonian fluid (i.e., constant viscosity) acting as
a continuum, (2) incompressible (i.e., constant density)
laminar flow, (3) steady-flow situation (4) fully developed
flow, and (5) no-slip (i.e., zero velocity of fluid at the fluid/
capillary wall interface). (6) no external pressure and (7)
negligible gravitational
As the Washburn equation shows:
 LV reff cos 
h2  t ........................... (4)
2 4.
Where h (m) is the height of liquid front, t (s) is the pen-
etrating time, γLV (N/m) is the surface tension of penetrat-
ing liquid, reff42,66,74–78) (m) is the effective capillary radius,
η (Pa.s) is the viscosity of the wetting liquid. The contact
angle can be calculated by curves of square of penetration
height h2 verses time t.
As it’s shown in Fig. 7, the test particles are compressed
in a tube which bottom is always covered by a film to bare
the particles and allow the liquid penetrate. The liquid
start penetrating when the tube bottom contacts liquid. The
Fig. 7. Left: The schematic diagram of Washburn method. Right:
A typical curve of h 2 versus time.79)
Fig. 8. Research overview of the development time of measurement methods for contact angle.
© 2018 ISIJ
height of the liquid front is recorded and the relation of the
square height and time obtained to calculate the contact
angle using Eq. (4).
3.3. Summary of the Various Methods
Contact angle measurement methods were proposed
and modified by many authors. In chronological order,
Wilhelmy plate method80) appeared to be the earliest way
to measure contact angle among these methods. The famous
Washburn64) method was developed in 1921 for contact
angle measurement of powders, and after that the pressure
method was delivered.67) Both sessile drop method and cap-
tive bubble method were developed in 1930s, and extended
by Zisman and co-workers81) in 1946. Diggins66) , Delker72)
and Lago73) modified capillary rise methods based on
equilibrium capillary height. Moreover, thin layer wicking
method,70) the ESEM method,82) weight method78) and gel
trapping technique47) were developed in recent years. The
overview of the development time of each measurement
method is shown in Fig. 8.
The advantages and disadvantages of these methods were
summarized from literature and were shown in Table 1,
including some modified ways.
Measurements of Contact Angle for Iron Ore
Particles
Iron ore particles are natural particles that most are
irregular and porous. It may be difficult to determine contact
angles of natural iron ore particles due to the complicated
surface morphology and pores inside particles. Various
methods were used to determine contact angles between iron
ore particles and some common reagents, but among these
methods, capillary rise method and sessile drop method are
widely used methods.
4.1. Sessile Drop Method
4.1.1. Materials
In this method, the test iron ore particles are most man-
made in laboratory and some come from industrial raw
materials. The main physical properties of iron ore particles
that authors used are listed in Table 2.
Magnetite nanoparticles were synthesized by co-precipi-
tation of Fe(II) and Fe(III).83) Hematite particles obtained by
the mixture of FeCl3 solution and NaOH solution are mono-
sized cuboid,84) and Plaza R C et al.85) synthesized hema-
tite particles by hydrolysis of Fe(III)-chloride solutions.
Goethite and hematite that J Shang experimented were got
following the way Schwertmann and Cornell proposed;53,86)
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Table 1. Advantages and disadvantages of methods commonly used in particles.

Method Sample Advantages Disadvantages Modified ways

Influenced by liquid diffu- Use adhesive to
compact/tablet Easy to conduct, apparent
sion, compacting ways prepare sample
Sessile drop
Not suitable for porous
Single particle Precise for finely particles –
non-spherical particles
Not suitable for water Accurately
Substrate made
Direct Captive bubble Convenient, and apparent swelling particles, and adjust the bubble
of particles
methods influenced by distortion size by pressure
No damage to materials and
Not suitable for low contact
ESEM Single particle can be used in established –
angle and water wettability
temperature or humidity
Not suitable for porous
Gel trapping Single particle apparent –
non-spherical particles
Not suitable for water
Use adhesive to
Wilhelmy plate Plate a wide range of wettability swelling particles, influenced
prepare sample
by compacting ways
The true liquid front is
Washburn method reproducible
uncertain
Use laboratory
Indirect Weight method centrifuge to
Column
methods Equilibrium height reproducible and good prepare particle
Capillary Influenced by packing ways bed
method sensitivity
rise method
Pressure method
can be used for non spheri- The true liquid front is uncer-
Wicking method Thin layer cal particles, and avoids the tain and not usable for –
packing influence contact angles larger than 90°

Table 2. Main physical properties of particles.

Author Particles Source Particle shape Size

Potapova79) Magnetite nanocrystals Synthetic Spherical 5–15 nm
Costanzo80) Monosized hematite Synthetic Cuboid About 2/3 in 1 μm
Plaza81) Hematite Synthetic Approximately spherical 60 ± 7; 520 ± 30 nm
Goethite Acicular 1 814 ± 38 nm
Shang51) Synthetic
Hematite Spherical 146 ± 1 nm
Fe1 – 42.24 μm
Susana L82) 2
Ores
Fe – 129.36 μm
Bare SPIONs – 10.9 ± 0.2 nm
Bare SPIONs (treated) – 12.5 ± 0.4 nm
Negatively charged SPIONs – 11.8 ± 0.3 nm
Javanbakht83) Synthetic
Negatively charged SPIONs (treated) – 12.3 ± 0.3 nm
Positively charged SPIONs – 12.2 ± 0.2 nm
Positively charged SPIONs (treated) – 13.6 ± 0.2 nm
Kulal84) Fe2O3 (thin film) Synthetic – ≤1.2 μm (thickness)
Hematite – –
Ratha85) Magnetite Ores – –
Goethite – –
S1
S2
86)
Neto S3 Synthetic Spherical 10.9 ± 3.5 nm
S4
S5
Reagent hematite – – –
A – –
5)
MAEDA B – –
Ores
F – –
K – –
1, 2: iron ores but they differ in terms of particle size distribution.

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 ISIJ International, Vol. 58 (2018), No. 3

besides, particles used in the experimental work of Susana
L are the raw materials used in the production of welding
wires,87) and handpicked hematite, magnetite, and goethite
samples used in the test of Ratha88) were obtained from dif-
ferent iron ore mines of Odisha, which iron oxide content
varies between 97.5 and 99%. Nanoparticles were obtained
by heating the mixture of FeCl2·4H2O and FeCl3·6H2O in
diethylene glycol. Among the process, negatively charged
SPIONs and positively charged SPIONs were obtained by a
series of treatments. The treated SPIONs were taken directly
from photo-initiated chemical vapor deposition (PICVD).89)
The Fe2O3 thin films were prepared by Kulal,90) which
were obtained by immersing a glass/stainless steel substrate
in a FeSO4 solution and a NaOH solution, in turn. In the
experiment of Neto,91) sample S1 is magnectic iron oxide,
S2 is magnetic iron oxide coated with PDMS at 250°C for
8 cycles in soxhlet, S3 is magnetic iron oxide coated with
PDMS at 250°C, 17 cycles in soxhlet, S4 is magnetic iron
oxide coated with PDMS at 50°C for 8 cycles in soxhlet, S5
is magnetic iron oxide coated with PDMS at 50°C 17 cycles
in soxhlet. Ores A, B and F are hematite iron ores, and ores
J and K are limonite iron ores.7)
Surface morphology of iron ore particles are shown in
Fig. 9, which were captured by SEM or TEM. It indicates
that the particles synthesized in laboratory were granular
and regular. The synthetic particles were always pre-
processed before contact angle measurements, since sessile
drop method required a continuous flat sample. The test
iron ore particles were made into suspension and the sus-
pension were withdrawn and equally distributed on a glass
microscope slides which were held strictly horizontal. The
slides covered with a suspension of particles were dry in air
or a vacuum. This preparation method is mentioned at the
second part, and it’s an alternative way to prepare samples
for no harm to samples and can make uniform plats. But
the natural ore particles used in the work of Susana L have
not undergone any preparation or surface cleaning and were
used ‘as received’.
4.1.2. Contact Angles
By use of a Gaertner (Chicago, IL) telemicroscope with
an eyepiece goniometer, the advancing contact angles of
monosized hematite were directly measured by Costanzo.84)
Due to the particles are cuboid, the film made of particles
are flat and shiny, as shown in Fig. 10. Contact angles were
read within only a second or so after depositing the drops,

(a) (b)

(c) (d)

(e) (f)

Fig. 9. Surface morphology of iron ore particles: (a). SEM micrograph of the synthetic monodisperse cuboid hematite
particles;84) (b). TEM micrographs of hematite particles of two size;85) (c). SEM micrographs of the film surfaces;
left: goethite and right: hematite.53) (d). HR-SEM images of synthetic magnetite particles on a ZnSe substrate;92)
(e). Reflected microphotographs of hematite, magnetite and goethite;88) (f). TEM Micrographs of the sample S2.91)

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 ISIJ International, Vol. 58 (2018), No. 3
and for a-bromonaphthalene, diiodomethane, water, glyc-
erol, formamide, ethylene glycol are 13.8 ± 0.4°, 19.4 ± 0.5°,
22.5 ± 0.5°, 26.4 ± 0.5°, 17.3 ± 0.5°, 14.0 ± 0.5°, respectively.
In the experiment of Shang,53) contact angles of goethite
with diiodomethane, water and formamide are 19.4 ± 0.4°,
22.8 ± 1.8° and 24.1 ± 1.0°, respectively; for goethite, they
are 25.0 ± 0.8°, 46.9 ± 2.3° and 18.5 ± 1.7°. As shown in Fig.
11, during the measurement, contact angles stay constant
for hematite sample, which indicates that hematite particles
formed a nonporous film with a periodical surface rough-
ness. The different behavior of typical slip/stick patterns of
the three liquid that in dynamic method can be explained
by their different Bond numbers. Based on the result, they
developed three types of mechanisms during contact angle
measurements, which are swelling, non-swelling and porous
and non-swelling, non-porous. Swelling films seal itself
when in contact with polar liquid, but acid–base interac-
tions can cause the drop shape to change with time. The
non-swelling, porous films, as goethite, both acid-base inter-
actions and imbibition can cause the drop shape changes.
The hematite sample is a non-swelling, non-porous film
(The hematite are non-porous because it was manmade),
so the drop shape remains stable during the measurement.
Potapova et al.83) found an interesting phenomenon that
contact angles are changed a lot after the treatment of
calcium ions and it seems that calcium ions have a great
influence on the contact angle of iron ore particles and
Fig. 10. Photograph of a microscope glass slide coated with a
layer of hematite (arrow).84)
Fig. 11. Contact angles and drop diameters of test liquids as a function of time. Left: static method; right: dynamic
method.53)
385
water. Contact angles of water with magnetite of different
treatments are slightly above 20. It is reported that calcium
ions can react with hydroxyls and release protons and add-
ing positive charge to the surface.93,94) Interactions of metal–
water are stronger than hydrogen bonding between the sur-
face hydroxyls and water.95) The Gibbs energy increased as
hydroxyl groups is substituted with calcium and the surface
hydrophilicity increased with the result of the decreasing of
contact angle. The silicate species could increase the amount
of hydroxyl groups which caused the decrease of contact
angle. The contact angle of water and the magnetite treated
with maleic acid ester reached 44 ± 3° may be due to the
formation of hemimicelles on the surface.96)
Javanbakht89) investigate the charge effect of bare, posi-
tively and negatively charged SPIONs (superparamagnetic
iron oxide nanoparticles) on surface functionalization of
the particles following treatment by PICVD (photo-initiated
chemical vapour deposition). Contatc angles of samples and
deionized water are obtained as shown in Table 3. It can
be concluded that both positively and negatively charged
SPIONs take on a hydrophobic behaviour post-treatment.
Kulal90) observed that the Fe2O3 thin films are superhy-
drophilic. Figure 12 shows contact angle measurement of
Fe2O3 thin films and the SEM micrographs of thin films,
and through SEM picture, smooth, irregular shaped particles
gather on the thin film surface can be observed. Results
show that water contact angle is less than 10°. This may be
due to the strong cohesive force between the water droplet
and hydroxide present in the iron oxide compound.
Contact angle of the three minerals with sodium oleate
solutions of different concentrations were measured by
Rath88) and are shown in Table 4. Contact angles of mag-
netite are larger than others at any concentrations of oleate
which indicates a worse wettability. According to their
results, contact angles increased by increasing the concen-
Table 3. Contact angle of deionized water and samples.
Samples Untreated Treated
Bare SPIONs 40° ± 9° 77° ± 14°
Positively charged SPIONs 58° ± 12° 100° ± 23°
Negatively charged SPIONs 47° ± 13° 97° ± 15°
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Fig. 13. Superficial wetness of samples S1 (A); S5 (B); S4 (C); S3

(D) and S2 (E).91)

Fig. 14. Relationship between contact angle at 0 min of retention

time and surface roughness of pure hematite.7)

Fig. 12. Water contact angle of Fe2O3 thin films and SEM micro-
graphs of Fe2O3 thin films at two different magnifications
(a) × 5 000 and (b) × 10 000.90)

Table 4. Contact angle of hematite, magnetite and goethite with

water.

Oleate concentration (g/t)

Sample
0 50 100 150 200 300
Hematite 32.67° 60.89° 70.79° 80.69° 83.66° 87.13°
Magnetite 34.16° 62.38° 75.74° 83.66° 90.10° 91.58°
Fig. 15. Relationship between contact angles at 0 min of retention
Goethite 19.31° 21.29° 27.72° 34.65° 37.62° 40.59°
time and surface roughness of iron ores.7)

tration of oleate. Table 5. Contact angle at 0 min of retention time for pure hema-
The particles of magnetic iron oxide were synthesized tite with different.
by the coprecipitation method.91) The functionalization of Surface roughness (μm)
the iron oxides was performed by coating surface with Porosity (%)
3.2–3.5 3.6–5.5 3.3–4.7 2.6–3.9 1.4–1.7
PDMS oil. S1 is magnetic iron oxide, S2 is magnetic iron
oxide coated with PDMS at 250°C for 8 cycles in soxhlet, 5 67.08° 74.58° 76.67° 72.92° 58.33°
S3 is magnetic iron oxide coated with PDMS at 250°C for 10 75.42° 83.75° 81.67° 80.42° 75.83°
17 cycles in soxhlet, S4 is magnetic iron oxide coated with 15 48.33° 71.25° 82.08° 68.75° 45.00°
PDMS at 50°C for 8 cycles in soxhlet and S5 is magnetic
20 35.42° 65.58° 60.42° 68.75° 33.75°
iron oxide coated with PDMS at 50°C 17 cycles in soxhlet.
Sample S1 showed hydrophilic behavior as the water droplet
on the surface of sample S1 spreaded completely. However, contact angle and surface roughness of pure hematite and
the samples coated with PDMS showed hydrophobic behav- iron oxides. Both the result shows that contact angle became
ior. Contact angles of each sample with water are measured large as the surface roughens became large.
by sessile drop method as shown in Fig. 13. Susana87) not only measured contact angles but also
MAEDA7) discussed the effect of porosity on iron ores obtained the experimental mean drop penetration time and
and concluded the relationship between surface roughness the standard error of the mean for each powder varying
and contact angle of iron ore in detail in their paper. Contact liquid binder. As shown in Fig. 16, 85.7 wt.% potassium
angle of pure hematite with different porosity and surface silicate solution penetrated in to particle bed. They think
roughness are shown in Table 5. The surface roughness of the infiltration of the fluids into powders interferes with
each sample was measured by the laser microscope. From the measurement of contact angle, because it is an unstable
the result, it indicates that the contact angles of the reagent condition and not meet the thermodynamic definition of
hematite samples become small in the order of samples with contact angle according to the theory of Young. There is
10%, 5%, 15% and 20% porosity. For the reason, they think not a general trend between the fluid rate penetration and
it due to that the sample surface becomes impossible to hold the contact angle values for the powder–liquid systems they
droplet on the sample surface as the porosity becomes over examined, but only for iron (Fe2), the larger the penetration
15%. Figures 14 and 15 show the relationships between velocity, the lower the contact angle.

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Fig. 16. Penetration of 85.7 wt.% potassium silicate solution on iron. The picture are taken at (a) after the impact on
powder compact, (b) 0.02 s, (c) 0.10 s, (b) 0.20 s and (d) 0.30 s after the impact.87)

Table 6. The test liquid, iron ore particles and contact angles (°).

Authors Materials A B C D E F G H
80)
Costanzo Hematite 13.8 ± 0.4 14.0 ± 0.5 19.4 ± 0.5 17.3 ± 0.5 – – 26.4 ± 0.5 22.5 ± 0.5
Magnetite1 – – – – – – – 22 ± 3
Magnetite2 – – – – – – – 19 ± 2
Potapova79)
Magnetite3 – – – – – – – ≤10
4
Magnetite – – – – – – – 44 ± 3
Plaza81) Hematite – – 17.1 ± 0.5 30.7 ± 1.0 – – – 21.5 ± 0.5
Fe5 – – – – 87.50 ± 0.77 83.00 ± 1.13 – –
Susana82)
Fe6 – – – – 85.15 ± 1.62 80.70 ± 2.89 – –
Goethite – – 19.4 ± 0.4 24.1 ± 1.0 – – – 22.8 ± 1.8
Shang51)
Hematite – – 25.0 ± 0.8 18.5 ± 1.7 – – – 46.9 ± 2.3
Bare SPIONs – – – – – – – 40 ± 9
Positively
– – – – – – – 58 ± 12
charged SPIONs
Negatively
– – – – – – – 47 ± 13
83)
charged SPIONs
Javanbakht *
Bare SPIONs – – – – – – – 77 ± 14
Positively
* – – – – – – – 100 ± 23
charged SPIONs
Negatively
* – – – – – – – 97 ± 15
charged SPIONs
Kulal84) Fe2O3 thin films – – – – – – – <10
Hematite – – – – – – – 32.67
Rath85) Magnetite – – – – – – – 34.16
Goethite – – – – – – – 19.31
S1 – – – – – – – 0
S2 – – – – – – – 120.4
Neto86) S3 – – – – – – – 107.9
S4 – – – – – – – 83.8
S5 – – – – – – – 45.9
Pure hematite – – – – – – – 33.75–83.75
A – – – – – – – 80–93.89
MAEDA5) B – – – – – – – 51.61–72.95
F – – – – – – – 61.35–71.30
K – – – – – – – 58.45–91.60
A: a-bromonaphthalene
B: ethylene glycol
C: diiodomethane
D: formamide
E: 85.7 wt.% sodium silicate
F: 85.7 wt.% potassium silicate
G: glycerol
H: water
1: synthetic magnetite
2: synthetic magnetite after consequent conditioning with 4 mM CaCl 2.
3: synthetic magnetite after consequent conditioning with 0.4 mM Na2SiO3.
4: synthetic magnetite after consequent conditioning with 25 mg L −1 maleic acid ester.
5: Iron ore powders with a size of 42.24 μm.
6: Iron ore powders with a size of 129.36 μm.
*: they are particles following treatment by PICVD

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Table 7. Values of surface tension (γL) and viscosity (η) of test 8. LIMS iron ore concentrates (FeCO3 and 2Fe2O3·3H2O)
liquids.70,79,87,97–99) were obtained from Jingtieshan Iron Mine of Jiuquan Steel
γL (mN/m) η (Pa.s) Company in Gansu Province of China.100) Magnetite pellet
concentrate after flotation and magnetic separation from the
a-bromonaphthalene 44.4 0.0489
pelletizing plant in Kiruna, Sweden was provided by LKAB
ethylene glycol 48.0 0.199 and was dried in an oven at 50°C before test.92) In the exper-
diiodomethane 50.8 0.028 iment of Iveson, ore compositions were determined using a
formamide 58.0 0.0455 manual point counting technique on a polished surface of
each ore.48) Both Iveson and Huang obtained the true density
85.7 wt.% sodium silicate 59.2 0.031
of samples by volumetric displacement of cyclohexane in a
85.7 wt.% potassium silicate 61.3 0.029 25 ml flask.48–50) SBET is the specific surface area represents
glycerol 64.0 14.90 the specific area of the internal and external surfaces was
water 72.8 0.010 measured by nitrogen adsorption method.50) The specific
surface area of goethite concentrate was determined based
on BET method.101)
Surface morphology of iron ore particles are also studied
by using SEM. Five typical images for five ores shown
in Fig. 18. Images (a) and (b) are SEM images of sample
S4 and S3, respectively; Images (c), (d) and (e) are SEM
images for sample A, B and C, respectively. All the SEM
pictures show that the natural particles were irregular and
angular in shape with a wide size range.
Reference liquid is important in capillary method. The
reference liquid authors used are summarized as shown in
Table 9. The assumed totally wetting liquids have a rather
small surface tension from Table 9.

4.2.2. Contact Angles

Fig. 17. Synthetic particles, ores and treated particles with con-
tact angles.
Contact angles of iron ore particles measured by sessile
drop method that above-mentioned are shown in Table 6,
and the properties of test liquids are given in Table 7.
Figure 17 shows contact angles of synthetic particles,
ores and treated particles. From Table 6 and Fig. 17 it can
be concluded that for a kind of iron ore particle the contact
angle is not a fix value but varies in some influencing factors.
Contact angles of synthetic hematite are less than 46.9°, and
for synthetic magnetite and synthetic goethite which are less
than 40° and about 22.8°. What’s more, there is not great
difference in contact angles between synthetic particles and
ore particles. But the contact angles of treated particles vary
in a large interval relates to the treated method.
4.2. Capillary Rise Methods
Capillary rise methods, including Washburn method, the
weight method, equilibrium height method, the pressure
method and thin-layer wicking method, are fully devel-
oped and commonly used in the contact angle determina-
tion of particles. But in contact angle measurements, only
Washburn method, the pressure method and thin-later wick-
ing method were used by some authors, wherein Iveson48,49)
and Huang50) studied contact angles of several natural iron
ore particles and obtained some significant laws.
4.2.1. Materials
Iron ore particles used in these methods are most come
from natural mines. The chemical composition and physi-
cal properties of used iron ore particles are shown in Table
Contact angles of the above-mentioned iron ore particles
were measured by capillary methods, and some significant
conclusions were obtained by authors.
In the study of Potapoya,92) for the natural magnetite
particles, the contact angle was estimated to be 50–60°.
Compared with the value of contact angle for synthetic
magnetite nanoparticles, they found that contact angles
of natural magnetite particles measured by the Washburn
method is normally reported to be higher, which may be
partly due to the measuring technique and physical proper-
ties of natural particles.
Adsorption of flotation reagents makes effect on the
wettability of magnetite concentrate. In their previous
research,103) it can be concluded that sodium metasilicate
could suppress the adsorption of the model collector on
magnetite with the absence of calcium ions. Table 10 shows
contact angle of magnetite concentrate upon modification
of the surface with 1 mg g − 1 water glass and Atrac 1 563
in 10 mM NaCl and 4 mM CaCl2 solution. It indicates that
calcium ions contribute to the increasing of contact angle of
magnetite concentrate by collector adsorption.
As Table 11 shows, water contact angle of the magnetite
concentrate after flotated is decreased by increasing the
concentration of water glass, and similar effect appeared
in the addition of sodium polyacrylate with the presence of
calcium, as shown in Table 12. But, the wettability didn’t
improved by increasing the concentration of sodium poly-
acrylate at a constant level of calcium. Wettability of the
flotated magnetite concentrate could be improved observ-
ably by prolonged treatment with water glass or rather short
conditioning with sodium polyacrylate.
Iveson et al.49) classified iron ores into two types which are
oxides and oxy-hydroxides. In a sense, hematite is oxide for

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Table 8. Chemical composition and physical properties of iron ore particles.

Chemical composition (mass%) SBET True density

Author Sample Size
TFe FeO CaO SiO2 Al2O3 MgO (103*m 2/kg) (103*kg/m3)
S1 61.53 0.29 0.02 3.05 2.06 0.16 9.098 4.32
S2 63.34 0.71 0.05 5.74 1.12 0.05 2.888 4.9
S3 64.51 0.45 0.02 4.3 0.68 0.05 1.602 4.96
Huang48) S4 58.27 0.22 0.04 5.55 1.37 0.08 ≤200 μm 24.544 3.93
S5 59.14 0.21 0.05 4.38 1.5 0.08 23.462 4.08
S6 61.26 0.32 0.03 3.69 2.25 0.06 7.788 4.58
S7 65.29 0.16 0.02 1.36 1.49 0.09 6.836 4.49
Qiu97) Magnetite 68.11 21.25 0.98 1.65 0.42 2.21 ≤74 μm 0.182 –
98)
Akdemir Hematite 67.82 – – – – – 10–38 μm – –
A – – – 3.2 – – – 3.57
B – – – 3.4 – – – 3.65
C – – – 0.6 – – – 4.49
D – – – 1.0 – – – 3.66
F – – – 0.2 – – – 4.00
G – – – 0.0 – – – 4.67
H – – – 1.4 – – – 4.25
Iveson47) I – – – 0.0 – – 53–150 μm – 4.95
J – – – 1.0 – – – 4.93
K – – – 0.0 – – – –
L – – – 5.0 – – – 4.61
M – – – 3.0 – – – 4.98
N – – – 4.4 – – – 4.85
O – – – 0.3 – – – 5.00
P – – – 0.6 – – – 4.58
Ea – – – – – – 134 μm – 4.06
Iveson46) Qa – – – 3.6 – – 77 μm – 4.58
a
R – – – 3.0 – – 87 μm – 5.29
Shang51) Goethite – – – – – – 1 814 ± 38 nm – –
Fe1 – – – – – – 42.24 μm – 7.684
Susana82)
Fe2 – – – – – – 129.36 μm – 7.812
A 58.27 0.22 0.04 5.55 1.37 0.08 – 3.93
B 59.14 0.21 0.05 4.38 1.50 0.08 – 4.08
C 61.53 0.29 0.02 3.05 2.06 0.16 – 4.32
D 60.91 0.29 0.02 4.07 2.54 0.05 – 4.51
E 61.26 0.32 0.03 3.69 2.25 0.06 – 4.60
Zhang99) 0.062–0.125 mm
F 65.29 0.16 0.02 1.36 1.49 0.09 – 4.49
G 62.24 0.23 0.04 4.40 2.31 0.08 – 4.63
H 63.34 0.71 0.05 5.74 1.12 0.05 – 4.90
I 62.84 0.35 0.02 4.49 2.46 0.02 – 5.10
J 65.72 0.34 0.09 3.37 1.27 0.02 – 5.18
100) Vanadium–Titanium
Long 53.97 20.89 1.13 3.38 4.18 2.73 ≤400 μm – –
magnetite concentrate
Potapoya88) Magnetite concentrate – – – – – – 0.5 –
96)
Liu LIMS iron ore concentrates 56.17 23.81 1.54 7.64 1.98 4.33 25–150 μm 8.12 –
Kirchberg67) Magnetite 71.04 – 0.3 0.6 0.1 0.4 ≤146 μm – –

its main composition is Fe2O3 and goethite oxy-hydroxide
for its primary is FeO(OH).104) Natural ores are consisted
of complex mixtures of those oxides and oxy-hydroxides.
Both Iveson49) and Zhang105) found there is a linear relation-
ship between the density and percent hematite, as Fig. 19
shows, the ore density increased with the increasing of the
content of hematite. The large uncertainties in their results
are to be expected the follows: (1) the materials are with
significant variation in both composition and morphology
between individual particles in the batch; (2) There is also
a difficulty in achieving uniform packing of the powders in
the columns. These uncertainties may cause the results not
accurate. But despite the large uncertainty in the contact
angle data, the content of oxides and oxy-hydroxides has a

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(f) (g)

(h) (i)

Fig. 18. The SEM images for the surface morphology of iron ore particles. (a): sample S3; (b): sample S4;50) (c): sample
A; (d): sample B; (e): sample C;48) (f): Ore A, Ore B, Ore C, Ore D;51) (g): SEM images of iron ores studied;102)
(h): magnetite;71) (i). natural magnetite particles on a carbon tape.92)

vital influence on contact angles which as Fig. 20 shows. of hematite.49)

Contact angles increased by increasing hematite content or
decreasing goethite content.48,49) They developed a fit func-
tion from the data:
  45 x  8 ................................. (5)
Where θ is the contact angle and x is the volume fraction
From the results they obtained, there has a strong corre-
lation between the hematite/goethite composition ratio and
the contact angle. They think particle porosity and surface
roughness are not the main strong influence on contact angle
measurement, but no powerful evidence was provided.
Zhang et al.105) obtained a liner relationship between LOI

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Table 9. Reference liquids used in literature.

Surface tension Viscosity

Author Liquid
(mN/m) (mPa.s)
Huang48)
Iveson46,47)
Zhang99) Cyclohexane 25.0 0.908
Long100)
Mao49)
Akdemir 98) Aerosol OT 75 26.0 200.000
Surfactant solutions 21.5 1.002
Susana82)
N–heptane 21.0 0.400 Fig. 20. Contact angle versus ore hematite content. Error bars
show 95% confidence intervals.49)
Susana82)
*
Water 72.1 1.002
Qiu97)
Shang51) Hexane 17.9 0.300
67)
Kirchberg n–Hexane 18.43 0.308
*: They determined the constant C used quartz powder and water for
which contact angle is 0.

Table 10. Water contact angle of magnetite concentrate upon

modification of the surface with 1 mg g −1 water glass
and Atrac 1 563 in 10 mM NaCl and 4 mM CaCl 2 solu-
tion at pH 9.

Collector concentration (mg g −1) 0 0.04 0.08

10 mM NaCl 34 ± 1° 28 ± 4° 32 ± 5°
4 mM CaCl2 40 ± 3° 44 ± 5° 58 ± 1°

Table 11. Water contact angle of the magnetite concentrate upon Fig. 21. Relationship between loss on ignition and weight loss
modification of the surface with water glass in 10 mM ratio.105)
NaCl at pH 9 for 9 h.

Water glass concentration (loss on ignition) and WLR (weight loss ratio), as Fig. 21
0 0.5 1 3
(mg g −1)
shows, the LOI increased with the increasing of WLR. They
Contact angle (°) 57 ± 5 41 ± 2 35 ± 1 28 ± 3 also gave a formula to describe the influences of hematite
content and LOI on contact angles, which is shown in Eq. (6).
Table 12. Water contact angle of the magnetite concentrate upon   0.24 x  1.9445 y  65.40 ................... (6)
modification of the surface with 0.04 mg g −1 sodium
polyacrylate at pH 9 for 1 h. Where x (vol.%) is the content of hematite and y is the
LOI (%) of iron ores.
CaCl2 concentration (mg g −1) 0 0.04 0.08
They also didn’t give a clear explanation of how surface
Contact angle (°) 55 ± 1 41 ± 8 25 ± 11 morphology influences the contact angle.
Huang et al.50) used the difference between the two sur-
face areas to describe the surface morphology index (SMI)
and defined SMI = SBET/SLPSA.106) SLPSA is the external surface
area from laser diffraction method.
They introduced LOI and gave formulas to calculate com-
positions of each oxide (Fe2O3.H2OG, Fe3O4M, Fe2O3T and
Fe2O3fH represents the mass fraction of goethite, magnetite,
total hematite and free hematite, respectively.):


Fe2O3  H 2OG  LOI  LOI 0 
177.72 ....... (7)

18.02
 LOI 0
 0.1 * LOI 
231.55
Fe3O4 M  FeO  ...................... (8)
71.85
Fig. 19. Ore density versus percent hematite. (Data come from
Zhang105) and Iveson49)).

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 ISIJ International, Vol. 58 (2018), No. 3
 167.55  159.70
Fe2O3T   TFe  FeO   ......... (9)
 71.85  111.70
159.70
Fe2O3 fH  Fe2O3T  Fe2O3  H 2OG  ..... (10)
177.72
With the calculated composition of each oxide, they also
found a relationship between measured density and calcu-
lated goethite content which is show in Fig. 22.
Then the volume% of goethite (φG) in an iron ore can be
calculated as:
Fe2O3  H 2OG
G   ore .................... (11)
3.83
Where, ρore is the true density of iron ore particles. Using
the Young-Dupre equation107) and similar to the calculation
of viscous Gibbs free energy for mixing, by using the rule
for average adhesion energy of heterogonous surfaces,108,109)
the adhesion energy between water and the iron ore surfaces
can be estimated as:
W  WO  (1  G )  WG  G ................. (12)
Where, WO represents all adhesion energy between water
and all non-hydroxide oxides (J/m2); WG is the adhesion
energy between water and goethite (J/m2).
Thus, a mathematical model for contact angle with the
volume% of goethite (φG) can be built as follows.
Fig. 22. Measured density as function of calculated goethite con-
tent.50)
Fig. 24. Influence of physical properties on relative contact angle (θRCA) of iron ores used.50)
© 2018 ISIJ
 l  v  (1  cos( ))  WO  (WG  WO )  G ....... (13)
Where, σl-v is the surface tension of water (0.072 J/m2).
Figure 23 is the relationship between adhesion energy and
the volume% of goethite, and it shows good agreement with
the experimental data (data of S7 was excluded). This model
can be explained by the report49) that any surface that has
a reduced ability of favorable H-bonding interactions with
water, would lead to the increase in contact angle of water
on the surface.
The results indicate that goethite content influenced
strongly on contact angles. But, opposite opinions hold on
the issue whether surface roughness and the particle porosity
between the samples can make strong influence on measured
2
contact angles. With a correlation coefficient Radj = 0.9 and
SMI ≥ 1, an equation was obtained to describe the influence
of physical properties on relative contact angles, shown as
Fig. 24.
 RCA  90 / SMI 0.1 .......................... (14)
By using multilinear regression method, the volume%
of goethite (φG) can be expressed as a function of SMI
and (pore volume) VPore with a regression correlation
2
Radj = 0.927.
G  0.266  SMI  0.769  Vpore ................ (15)
They also compare with the literature from Iveson.48,49)
The measured θRCA versus the calculated θcal based on
Fig. 23. Adhesion energy as function of volume% of goethite for
iron ores used.50)
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Fig. 26. Effects of binder dosage on the contact angle of the iron
concentrate.101)
Fig. 25. The measured θRCA versus the calculated θcal based on
Iveson’s data.50)

Table 13. Contact Angle for Different Grinding Times.102)

Grinding time (min) 0 3 6 9 12 30 60

Contact angle (°) 71 65 64 62 55 43 34

Table 14. Chemical compositions of Funa and Bentonite.101)

Binder Oorg SiO2 Al2O3 CaO MgO Fe2O3 P S CF

Funa 46.50 13.81 6.16 4.72 0.21 4.04 0.03 0.04 28.14
Bentonite 0 72.91 13.59 1.7 2.48 1.40 0.025 0.01 0

Fig. 27. Wetting heat of the iron concentrate affected by

Iveson’s data is shown in Fig. 25. It shows that the relative
contact angles have a linear relation with the calculated con-
tact angle with a fitting coefficient equals 0.515. But some
differences exist due to the error in measurements.
Long et al.102) have studied the influence of surface mor-
phology on contact angles of water and iron ore particles.
They controlled the size distribution by grinding particles,
surface roughness of particles after 60 min increased obvi-
ously and a relationship between contact angles and grind-
ing times was obtained as shown in Table 13.
From Table 13, we can see that contact angles decreased
with the increasing of grinding time. This may be due to
the surface roughness has changed after grinding, and they
thought this phenomenon agrees well with the finding that
the contact angle decreases when the roughness factor is
increased.110)
Qiu G101) concluded that the physical properties of bind-
ers influence the wettability of iron concentrate (magnetite).
Two binders were used in their experiment, and the chemi-
cal compositions were shown in Table 14.
Contact angle for magnetite is about 46° from Fig. 26,
and Funa has a stronger influence on the contact of iron
concentrate than betonite. The effects of binders on the wet-
ting heat of the concentrate were obtained and shown in Fig.
27. It can be seen that both Funa and bentonite can increase
the wetting heat of the concentrate. However, the increase
of the wetting heat caused by Funa is much greater than
that by bentonite. It suggests that Funa can greatly change
the wettability of the magnetite and make the surface much
more hydrophilic.
Shang53) has determined contact angles of three dif-
binders.101)
ferent liquids with goethite by using thin-layer wicking
method and Washburn method, which are shown in Figs.
28 and 29, respectively. Through the thin-layer wicking
method, contact angles for goethite with water, formamide,
diiodomethane are 34.1 ± 3.4°, 20.9 ± 1.8° and 46.7 ± 2.9°,
respectively. But for Washburn method, they didn’t calcu-
late contact angles because there distinct stage 2 of column
wicking wasn’t find. This may due to pore structure of the
packed soil colloids changed as the fluid was imbibed dur-
ing measurement. Surface tension and viscosity of the three
liquids can be seen in Table 9. They concluded that Thin-
layer wicking was better suited for contact angle measure-
ments because the colloids on the plates formed a more rigid
porous structure, and did not easily disperse.111)
Because tested liquid wets the powder bed better than
the reference liquids they choose, Susana L et al.87) try to
choose better reference liquid by employed the lipophilic to
hydrophilic ratio (LHR).112) But all these results suggest that
the LHR can give only limited information on the affinity of
the wetting medium with the powder and cannot be used as
a general guide for the selection of the proper wetting fluid,
which confirm that Washburn’s method is extremely sensi-
tive to the choice of the reference liquid used. They used
three surfactant solutions to be the reference liquids in the
Washburn method according to literature113) and obtained
curves of w2 versus time as shown in Fig. 30. Contact angles
of two iron ore particles can be calculate by using Washburn
equation.64) The result is bigger than the contact angle of
water and iron ore particles.

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Table 15. The advancing contact angle of iron ore concentrate

particles of different fractions by WCR (Washburn
Capillary Rise).

Particle size
25–45 45–62 62–96 96–150
(μm)
Contact angle
73.93 ± 7.26 69.35 ± 4.03 67.01 ± 3.48 64.92 ± 2.35
(°)

Table 16. Contact angle of LIMS iron ore concentrate particles

versus CTAB concentration.

Concentration of CTAB
0 40 80 120 160
solutions (mg/L)
Fig. 28. Wicking distance squared versus time for different test
liquids using thin-layer wicking.53) Contact angle (°) 69.37 74.15 80.83 85.02 78.04

Table 17. Chemical composition and surface properties of iron

ores.51)

Chemical composition Surface properties

Materials Contact
SLS SBET
TFe SiO2 CaO Al2O3 MgO LOI angle
(m 2/g) (m 2/g)
(°)
Ore A 65.29 1.36 0.02 1.49 0.09 2.18 0.51 6.84 53.84
Ore B 58.27 5.55 0.04 1.37 0.08 10.13 0.21 24.54 76.30
Ore C 64.51 4.3 0.02 0.68 0.05 2.04 0.18 1.60 69.58
Ore D 59.14 4.38 0.05 1.5 0.08 9.52 0.40 23.97 79.47
Fig. 29. Capillary rise curves, wicking weight versus time for dif-
ferent test liquids using the column wicking method.53)
Table 18. Contact angle of Fe3O4 micropowders.

Powder contact angle (°)

Powder (μm)
H 2Odist. EG/H 2O(50/50) FADEE
Fe3O4 (0–20) 75.38 62.16 54.1
Fe3O4 (20–40) 75.10 60.10 52.63
Fe3O4 (40–63) 74.01 58.71 50.53
Fe3O4 (63–80) 73.50 54.80 47.46
Fe3O4 (80–100) 72.44 50.95 45.59
Fe3O4 (unsieved) 73.65 57.60 49.81

Fig. 30. The slope w2 versus time for three different surfactant
solutions on iron powder.87) Table 19. Properties of test liquids at 25°C.

Density Viscosity Surface tension

Test liquid
Liu100) used the Washburn method to determine contact [g/cm3] [mPa s] [mN/m]
angles of iron ore concentrate particles of different fractions. Fumeric acid diethyl ester 1.045 2.85 31.40
They found that contact angle decreased with the increase of Ethylene glycol-water (50/50) 1.064 3.81 57.89
particle size, and this opinion has been confirmed in litera-
Dist. water 0.998 1.00 72.30
ture. The contact angle values of four size grades were given
in Table 15. There is a great difference between the contact
angle measured by WCR and contact angle measured by Mao51) obtained contact angles of natural iron ore par-
sessile drop which is nearly 37.7° in the research result. The ticles with water. The chemical composition and surface
packing and tapping operations and the great roughness and properties of iron ore particles are shown in Table 17. Ore
surface properties of particles are the two aspects caused the A and ore C are hematite, ore B and ore D are limonite,
great difference in their idea. The contact angle of LIMS respectively. The particle size is less than 0.125 mm.
iron ore concentrate particles versus CTAB (cetyl trimethyl The effects of the particle shape, size and size distribution
ammonium bromide, which as an absorbate to improve the on the wetting behavior of soft magnetic micropowders are
interfacial behaviors of iron ore particles) concentration investigated in the experiment of Kirchberg.71) Calculated
were also studied in this paper. The Table 16 shows that the contact angles of different particle sizes of Fe3O4 powders
wettability of sample particles would get better if increasing with different test liquids are summarized in Tables 18,
CTAB concentration continuously. and 19 shows the properties of test liquid. From the test

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Table 20. Mdeasurement methods with contact angles of different 75.38c

iron ore particles.
Fe3O47 – – 62.16d
Contact 54.1e
Hematite Goethite
Author Method Sample angle 75.10c
(Vol.%) (Vol.%)
(degree) 8
Fe3O4 – – 60.10d
88) Washburn
Potapoya Magnetite – – 50–60 52.63e
method
S1 – 63.47 63 74.01c
S2 – 24.87 71 Fe3O49 – – 58.71d
S3 – 23.45 73 The mass 50.53e
The Kirchberg67)
method 73.50c
Huang48) pressure S4 – 92.27 57
method S5 – 90.02 59 Fe3O410 – – 54.80d
S6 – 62.41 66 47.46e
S7 – 22.68 67 72.44c
Washburn Fe3O411 – – 50.95d
Qiu97) Magnetite – – 46
method 45.59e
The height 73.65c
Akdemir 98) Hematite – – 47
method Fe3O412 – – 57.60d
A 8.6 87.2 0 49.81e
B 15.6 78.6 12
1: Iron ore powders with a size of 42.24 μm.
C 55.6 42.0 23 2: Iron ore powders with a size of 129.36 μm.
D 19.2 79.2 27 3: LIMS iron ore concentrate with a size of 25–45 μm.
F 22.4 77.4 30 4: LIMS iron ore concentrate with a size of 45–62 μm.
G 71.6 28.0 32 5: LIMS iron ore concentrate with a size of 62–96 μm.
6: LIMS iron ore concentrate with a size of 96–150 μm.
The H 53.2 41.0 37 ± 5
7: Fe3O4 micropowders with a size of 0–20 μm.
Iveson47) pressure I 77.6 22.4 37 8: Fe3O4 micropowders with a size of 20–40 μm.
method J 93.4 5.0 40 ± 13 9: Fe3O4 micropowders with a size of 40–63 μm.
K 97.2 1.4 43 ± 10 10: Fe3O4 micropowders with a size of 63–80 μm.
11: Fe3O4 micropowders with a size of 80–100 μm.
L 94.0 1.0 46
12: unsieved Fe3O4 micropowders.
M 92.2 2.8 48 ± 3 a: The test liquid is 85.7 wt.% sodium silicate.
N 88.2 7.0 49 ± 4 b: The test liquid is 85.7 wt.% potassium silicate.
O 98.6 0.6 49 ± 10 c: The test liquid is dist. water.
P 85.0 12.4 54 d: The test liquid is ethylene glycol-water (50/50).
e: The test liquid is fumeric acid diethyl ester.
The E 20.0 – 29
Iveson46) pressure Q 86.0 6.0 56 ± 10
method R 92.8 3.2 74 ± 3 result, they concluded that contact angles decreased with the
Thin–layer increasing of particle size and increased with the increasing
Shang51) wicking Goethite – – 34.1 ± 3.4 of particle porosity, which is agree with the conclusion of
method
literature.114) Finally it was found that higher liquid surface
67.35a tension results in higher contact angle and worse wetting of
Fe1 – –
Washburn 71.03b the different powder beds.
Susana82)
method 45.41a
Fe2 – – Contact angles of iron ore particles and test liquid by
63.13b using capillary rise method are shown in Table 20. By
A – – 57.70 analyzing the data of contact angles, some important infor-
B – – 62.83 mation can be obtained:
C – – 67.17 From the results of authors, contact angles vary from
D – – 73.19 0 to 87.25 with chemical compositions. Most samples are
The E – – 66.79
Zhang99) pressure complex of hematite, goethite and magnetite.
method F – – 79.19 There’s a strong relation between water contact angle and
G – – 77.86 the ratio of goethite and hematite from the results of Huang
H – – 80.30 and Iveson.48–50) Unfortunately, content of these chemical
I – – 83.00 compositions didn’t be obtained by other authors to support
J – – 87.25 this opinion.
The
Vanadium– For capillary rise methods, totally wetting liquid is of
Titanium
Long100) pressure
magnetite
– – 71 great important for contact angle measurements. The con-
method stant C can be counteracted by citing a prefect wetting liquid
concentrate
73.93 ± 7.263 which contact angle is assumed to be zero, and then the
Washburn
LIMS iron 69.35 ± 4.034 contact angle of test liquid is obtained. The pivotal thing to
Liu96) ore concen- – –
method
trate 67.01 ± 3.485 choose the totally wetting liquid is that the reference liquid
64.92 ± 2.356 should not have a lower wettability than the test water, or
contact angles can’t be calculated. For different reference
liquid, the contact angle is different. As reported, values of

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 ISIJ International, Vol. 58 (2018), No. 3

cosθ exceed unity when using n-heptane as the reference
liquid, and in addition, the situation improves little as the
water is the reference liquid.53) It is because n-heptane is an
apolar fluid and water is a polar fluid, as polarity of these
liquids is a limitation for them to determine contact angles
of powders which are lipophilic or hydrophilic. Surface ten-
sions of surfactant solutions are extremely low and it’s great
for the calculation of contact angles.
4.3. Captive Bubble and Wihelmy Plate Method
The test particles are natural and synthesized in labora-
tory in the paper of Copeland C R et al.115) and Shang J et
al.,53) respectively. The content of Taconite is 67% hema-
tite (Fe2O3), 10% magnetite (Fe3O4), few silica and other
gangue minerals. Hematite and goethite were pure.
Contact angle of taconite and water is 18 ± 3° by cap-
tive bubble method, and for Wihelmy plate method con-
tact angles of hematite and goethite are 71.7 ± 2.0° and
14.2 ± 2.4°, respectively. As the same result of calcium
chloride, adding acetylenic glycol lowered the contact angle
of taconite and water. The Wilhelmy plate method generally
leads to an underestimation of the advancing contact angle
when the plate surface is rough, because the effective plate
perimeter is larger than that determined by a caliper.
above theory that roughness will make it more hydrophilic.
Contact angle is influenced by the two significant factors:
surface chemical compositions and surface morphology.
The effect on contact angle of both factors will be described
in the coming sections.
5.1. Chemical Compositions
Iron oxides are hydrophilic materials. Due to the fact that
in the atmosphere, surface hydroxyl groups exist at the sur-
faces of most metal oxides, these metallic oxides have dif-
ferent effect on wettability. For pure hematite, magnetite and
goethite, the major ingredient are Fe2O3 (α-Fe2O3), Fe3O4
and FeO(OH) (α-FeOOH). The schematic diagrams of
crystal structures of the three iron oxides are shown in Fig.
31. Both α-Fe2O3 and α-FeOOH has an octahedral structure
that each iron atom is bonded to six oxygen atoms or three
oxygen atoms and three hydroxyls. In the case of magnetite,
the crystal structure is complicated inverse spinel structure,
where each unit cell contained 32 O2 − and 24 iron atoms. 8
Fe3 + and 8 Fe3 + with 8 Fe2 + are filled into the interspace of

5. Influencing Factors
Various methods have used to determine contact angles
of iron ore particles and liquids. According to the results
obtained in these methods, it can be observed that there exist
some differences between contact angles measured by the
two typical approaches: direct method and indirect method.
The reason may be settled in the chemical compositions and
physical properties of particles.
According to Yong’s equation, contact angle is related to
solid-gas interfacial energy, liquid-solid interfacial energy
and liquid-gas interfacial.
 SG   LS
cos Y  ......................... (16)
 LG
The liquid-gas interfacial and solid-gas interfacial energy
are constant values which only vary with different liquid
and materials. In other words, different kinds of liquid and
materials indicates different chemical compositions or phase
constitution possess discrepant free enthalpy. The liquid-
solid interfacial is related to the whole interfacial energy
of the contact surface. For an ideal material, which surface
is flat and homogeneous, the liquid-solid interfacial energy
is a fix value and only varies with chemical composition
or phase constitution. But in an actual surface, the surface
roughness increases the specific surface area thus changes
the surface free enthalpy of solid materials making the varia-
tion of contact angle.
Wenzel defined roughness factor r as the ratio of the area
of the actual surface to that of a smooth surface having the
same geometric shape and dimensions.110) It is assumed that
roughness makes hydrophilic surface a better wettability, but
for hydrophobic a worse wettability.110) By developing the
theory of Wenzel, Cassie116) proposed that a rough surface
of low interface energy possesses super-hydrophobicity. The Fig. 31. Crystal structures of hematite (α -Fe2O3),118) goethite
iron ore particles are hydrophilic materials so based on the (α -FeOOH)119) and magnetite (Fe3O4).120)

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 ISIJ International, Vol. 58 (2018), No. 3
tetrahedrons and octahedrons, respectively. It can be found
both tetrahedral structure and octahedral structure in a unit
cell of Fe3O4. Tetsuo Morimoto117) figured out the mecha-
nism of formation of surface hydroxyl groups on the surface
of metal oxides. Firstly, water is adsorbed on the surface of
metal oxide to form adsorption complex, and then, it transfer
to surface hydroxyl groups. The two neighboring surface
hydroxyl groups adsorb water through hydrogen bonding.
More surface hydroxyl groups means more water mol-
ecules absorbed on the oxide surface by hydrogen bonding,
partly, which suggests a lower contact angle or a better
wettability.
Generally, natural ores contain most iron oxides and
some other metallic oxides such as silicon oxide, calcium
oxide, alumina and magnesium oxide. In the theory of
Iveson,49) natural iron oxides are complex mixture of dif-
ferent iron oxides, and these oxides can be divided into
oxides and oxy–hydroxides. Considering the hydration in
oxy–hydroxides, there are more surface hydroxyl groups
generated in the surface of oxy–hydroxides than hydroxides.
For goethite after highly weathered and roughed will
wet better than magnetite. So, in the surface of goethite, an
oxy–hydroxide, density of surface hydroxide groups would
be expected to be probably higher than that in hematite and
magnetite. It agrees with the results of authors that goethite
has the lowest water contact angle among these iron oxides.
However, other oxy-hydroxides, such as Al2Si2O5(OH)4Si
an Ca(OH)2, which constituted by element Ca, Mg, Si and
Al in iron ore particles are too little to contribute to the den-
sity of surface hydroxyl groups. From the statistical analysis
of contact angles with different chemical compositions, it
shows that SiO2, CaO, MgO and Al2O3 have not significant
effect on contact angles.
As Fig. 32 shows, there is a clear trend that contact angles
decreased with the decreasing of the volume fraction of
goethite. It confirms that the increasing amount of goethite
decreased contact angles,50) performing a better wettability.
5.2. Surface Morphology
Surface morphology is a general designation of surface
feature of material, such as particle size, surface roughness
and porosity. On account of multiple thermodynamic equi-
Fig. 32. The volume fraction of goethite with contact angles
obtained by Huang50) and Iveson.49)
397
librium states exist, these surface features make different
wetting behaviors on material surface when contacted water.
Pores, whether in sessile drop method or capillary rise
methods, are exist in test samples for individual particles
were generally made into a closely united tablet or a lump
in column to measure contact angle.
Actually, according to the testing principle of sessile drop
method, it is not suitable for contact angle measurement of
natural iron ore particles with water. In sessile drop method,
natural iron ore particles show a different behavior in con-
tact angle measurements compared to synthetic particles.
The above-mentioned two typical behaviors of droplet
in contact angle measurements are shown in Fig. 33. As
shown in picture, for synthetic particles, contact angles stay
constant in the measurement period which suggests that the
shape of droplets doesn’t change. But for natural particles,
the droplet shape changes with time, which indicates that
water is absorbed into bed. These phenomenon due to the
differences in surface morphology of synthetic particle and
natural particle. The synthetic particles are always smooth
in a certain shape. However, natural iron ore particles has a
more complicated surface morphology due to its irregular,
rough and porous. It is said that irregular shape and uneven
size fractions contribute more space between particles due
to its worse anastomosis,121) and thus, the space of inter-
particle can function as pores in contact angle measure-
ments, which means a higher porosity. So, for packed bed of
natural particles, penetration happens as the time the droplet
spread on the surface of bed when it contacts particle bed.
The thermodynamic equilibrium of three phrases doesn’t
exist in this situation and it ends with the complete suction
of droplet. Only at a thermodynamic equilibrium situation,
contact angle is meaningful according to the definition of
contact angle. Thus, sessile drop method is not recom-
mended as contact angle measurement of natural iron ore
particles.
Unlike the sessile drop method, advancing contact angle
is determined in capillary rise methods by penetration.
There is no need to create a thermodynamic equilibrium and
according to the Washburn equation, contact angle seems
to only relate to liquid physical properties (viscosity and
surface tension) and effective capillary radius.
Fig. 33. Two typical behaviors of droplet in contact angle mea-
surements for iron ore particles. (a): Particle bed of natu-
ral iron ore; (b): particle bed of synthetic particles.
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 ISIJ International, Vol. 58 (2018), No. 3
h 2 2 of relative contact angle and SMI was obtained as shown in
cos    ......................... (17)
t  LV reff
In order to avoid calculating reff directly, a reference liq-
uid which contact angle for iron ore particle equals to zero
is used. The assumption is based on the fact that reference
liquid can wet perfectly on the surface of iron ores. This
assumption may not be strict as natural iron ore particles
may contain several different kinds of iron oxides. Thus,
the measured contact angle should be called relative contact
angle, preferably. The second assumption of this method
is that the density and porosity of packing beds stay con-
stant in each measurement. In fact, it’s harsh to meet these
requirements and the best way is to do repeated trials to
reduce errors.
Figure 34 shows the relationship between water contact
angle and particle size in using capillary rise methods. Dif-
ferent color means of results were obtained by different
authors, and the height of floating column is the size range
of used particles. From Fig. 34, most particle size is below
200 μm and a wide range of contact angle were obtained
from 0 to a maximum 87.25. It seems that influence of par-
ticle size on contact angle is invisible for there exists unob-
vious tendency from result. However, it should be noticed
that in Fig. 34, the red one and the light blue one indicate a
phenomenon that contact angle increased with the decreas-
ing of particle size in a settled iron ore particles. Although
slight variations of contact angles exist, particle size is not
a crucial influencing factor for water contact angle of iron
ore particles. It suggests that chemical compositions and
phase constitute are the main influence factors on water
contact angle, for different kinds of iron oxides or mixture,
as discussed in section 4.1. On such conditions, influence
of particle size on water contact angle can be ignored for
natural iron ore particles.
Surface roughness is always regarded as a significant
parameter in measurement of contact angle and was studied
by many authors. According to the theory of Wenzel,110)
surface roughness plays a role of amplification for surface
wettability. Maeda7) found that as a general tendency, the
contact angle of iron ore particle decreases with increasing
the surface roughness. For approximately spherical par-
ticles, roughness factor r can be described by SMI. Rougher
Fig. 34. Relationship between water contact angle and particle
size in using capillary rise methods.
© 2018 ISIJ
particle seems to have a better wettability, and the equation
Eq. (14). Introduce of SMI can express the surface rough-
ness and porosity exactly, which should be recommended
to be measured in future experiments. However, in recent
studies, less attention were paid on the effect of SMI on
contact angle. The mechanisms of the surface morphology
of these ore particles influenced on contact angles are still
poorly understood. It is a complicate interaction effect with
chemical composition on contact angle.
6. Comments and Prospects
Both captive bubble method and Whihelmy plate method
requires determining contact angles under test liquid. Due
to iron ore particles are most hydrophilic, it’s also not a
good choice for this approach makes sample absorbed liquid
which may lead to the swell and dissolution of samples.
Sessile drop method seems to be good with iron ore
particles synthesized in laboratory. Synthetic particles are
regular with a narrow size distribution and can be formed
into a relative flat film. This may meet the hypothesis of
Young’s equation, thus suitable for the measurement of
contact angle for synthetic particles. Because the synthetic
particles are almost pure hematite, goethite or magnetite,
contact angles are constant from literature, which indicates
the availability and accurate of this method. For natural ore
particles, it’s not a good choice because of penetration on
the porous surface.
In capillary rise methods, Iveson,49) Zhang et al.105) and
Huang50) got an agreement that contact angle depends on
ore compositions, and they have concluded equations about
contact angle with the volume fraction of hematite or goe-
thite. Furthermore, Zhang et al.105) obtained a liner relation-
ship between LOI and WLR, and Huang50) combined SMI to
characterize the relation between contact angles and physi-
cal properties. The conclusion contains more details about
contact angle varies with the volume fraction of goethite
and surface morphology compared with results of Iveson.49)
It accords with the opinion which both chemical composi-
tion and surface morphology lead to the variation of contact
angle as they do a complicate interaction on wettability.
The basic requirement in choosing reference liquid is that
the liquid should wet perfectly, as to how reference liquids
influence contact angles, there are not literature summa-
rized. An alternative packing way for column wicking has
been proposed by Galet et al.,114) by this way a centrifugal
was used to prepare samples of uniform density. It may deal
with the packing problems.
Both the results of direct methods and indirect methods
reach an agreement that goethite has the lowest water con-
tact angle. It is reliable and practical to evaluate the value of
contact angle by the volume fraction of goethite. As things
stand, the preferable approach for the measurement of water
contact angle of natural iron ore particles is the capillary rise
method, which is always used in the determination of con-
tact angles between water and porous iron ore particles. This
method takes into account the characteristics of natural ore
particles, porous and rough. The measured relative contact
angle is more reliable than it measured by direct methods.
In the study of Mao et al.,51) they defined the granulation
398
 ISIJ International, Vol. 58 (2018), No. 3
property (k) of ores, which is a parameter relevant contact
angle and increased with the decreasing of it. The results
show that bed permeability can be exactly estimated by
granulation property and mass fraction, namely, contact
angle measured by capillary rise methods are appropriate
for granulation process evaluation.
With the decreasing of high quality hematite, the dosage
of limonite becomes larger and it makes a better wettabil-
ity of iron ore particles as well as a better balling behavior.
However, an extremely good wettability may be not a good
behavior in granulation as there is excess moisture in gran-
ules in the same stacking volume. It should be noted here
that excess moisture makes particles crust on the inner wall
of mixer, which blocking the granulation process. Another
aspect is that excessive moisture increases the thickness
of overdamp layer, reduces sintering temperature, makes
a worse permeability and deteriorates the sinter bed. Thus,
a novel and practical technology adopting low moisture
should be developed based on the research on wettability
of different iron ores.
In order to alter the wettability of iron ores and make
a better granulation behavior, the following methods can
be taken into consideration. According to the above men-
tioned literature, it can be realized by changing the surface
tension of water by adding some reagents, and varying the
surface free energy of iron ore particles by increasing the
SMI of particles. Moreover, coating of iron ore particles,
high-temperature treatment, such as oxidization roasting and
magnetization roasting, are useful approaches to improve
the wettability.
7. Summary
Contact angle is a vital parameter in many fields to pres-
ent the wettability of materials and many methods were
developed for the measurement of contact angle. The con-
tact angle measurement methods for particles can be divided
into two types, direct methods and indirect methods, all
these methods have its features and are summarized. Natural
iron ore particles are almost rough, porous and irregular and
with a wide range of size fraction. It’s difficult to obtain
accurate contact angles for natural particles.
Among these methods, sessile drop method and capillary
rise method are commonly used, because their easy conduct
and clear result. For capillary rise methods, totally wetting
liquid is of great important for contact angle measurements.
Anyway, it’s still the most applicative way for porous
particles like natural iron ore particles. To obtain accurate
results, centrifuge and vibration technique have been used
to get uniform packing beds. So in future, developments of
preferable techniques to get uniform packing beds for capil-
lary methods will be a significant research content.
Many authors have obtained contact angles of iron ore
particles and liquid, and their results show some important
information about contact angle measurement and wettabil-
ity of iron ore particles.
(1) Iron ore oxides (magnetite, goethite and hematite)
are hydrophilic and the contact angles of iron ores var-
ies with chemical composition (phase constitute). Oxy-
hydroxides play a key role in the improvement of wettability
of iron ores, as these species contribute surface hydroxyl
399
groups. There has an agreement that goethite has the small-
est contact angle among hematite and magnetite.
(2) Complicate surface morphology (the specific surface
area, pore volume) makes iron ore particles better wettabil-
ity, which a surface of higher SMI is verified to have a lower
contact angle. But the mechanism of it influenced on contact
angle is still unclear. In reality, contact angle is influenced
by the complicate interaction of chemical compositions and
surface morphology.
(3) For pure synthetic iron oxides, contact angle is
similar in both direct and indirect method. Capillary rise
methods are relatively better for the measurement of natural
iron oxides due to penetration takes place on the surface of
packed lump by sessile drop method.
(4) Surface treatment can alter the wettability of iron
ore particles by varying the surface free energy. The wet-
tability can be improved by increasing the SMI of particles,
coating of iron ore particles, high-temperature treatment.
(5) With growing use of limonite, excess moisture in
granulation process makes particles crust easily on the inner
wall of mixer, causes a bad permeability and deteriorates
the sinter bed. A novel and practical technology adopting
low moisture should be developed based on the research on
wettability of different iron ores.
Acknowledgements
The authors are especially grateful to National Natural
Science Foundation of China (NSFC) (Grant No. 51544203)
for supporting and funding this work.
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