CIS-01858; No of Pages 20

Advances in Colloid and Interface Science xxx (2018) xxx–xxx

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Advances in Colloid and Interface Science

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

Historical perspective

The application of atomic force microscopy in mineral flotation

Yaowen Xing a,b,c, Mengdi Xu a, Xiahui Gui b,c, Yijun Cao b,d, Bent Babel e, Martin Rudolph e, Stefan Weber c,
Michael Kappl c, Hans-Jürgen Butt c,⁎
a
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou 221116, China
b
Chinese National Engineering Research Center of Coal Preparation and Purification, China University of Mining and Technology, Xuzhou 221116, China
c
Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany
d
Henan Province Industrial Technology Research Institute of Resources and Materials, Zhengzhou University, Zhengzhou 450001, China
e
Helmholtz-Zentrum Dresden-Rossendorf, Helmholtz Institute Freiberg for Resource Technology, Chemnitzer Str. 40, 09599 Freiberg, Germany

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

Available online xxxx During the past years, atomic force microscopy (AFM) has matured to an indispensable tool to characterize
nanomaterials in colloid and interface science. For imaging, a sharp probe mounted near to the end of a cantilever
Keywords: scans over the sample surface providing a high resolution three-dimensional topographic image. In addition, the
Atomic force microscopy AFM tip can be used as a force sensor to detect local properties like adhesion, stiffness, charge etc. After the inven-
Mineral flotation tion of the colloidal probe technique it has also become a major method to measure surface forces. In this review,
Surface imaging
we highlight the advances in the application of AFM in the field of mineral flotation, such as mineral morphology
Inter-particle force
Bubble-particle interaction
imaging, water at mineral surface, reagent adsorption, inter-particle force, and bubble-particle interaction. In the
coming years, the complementary characterization of chemical composition such as using infrared spectroscopy
and Raman spectroscopy for AFM topography imaging and the synchronous measurement of the force and
distance involving deformable bubble as a force sensor will further assist the fundamental understanding of flo-
tation mechanism.
© 2018 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2. Imaging of minerals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
3. Water at mineral surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
3.1. Water structure near the interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
3.2. Surface nanobubbles characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
4. Reagent adsorption on mineral surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
4.1. Structure of adsorbed reagent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
4.2. Single molecule force spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
5. Quantification of inter-particle force . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
6. Bubble-particle interaction and thin liquid film drainage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
7. Other applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
8. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0

1. Introduction

Froth flotation, belonging to the family of heterocoagulation separa-

⁎ Corresponding author.
tion techniques, is based on the difference in surface hydrophobicity of
E-mail addresses: guixiahui1985@163.com (X. Gui), yijuncao@126.com (Y. Cao), dispersed particles. It has been widely used in mineral processing [1–4],
kappl@mpip-mainz.mpg.de (M. Kappl), butt@mpip-mainz.mpg.de (H.-J. Butt). fine coal upgrading [5–7], wastewater treatment [8,9], oil sands

https://doi.org/10.1016/j.cis.2018.01.004
0001-8686/© 2018 Elsevier B.V. All rights reserved.

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org/10.1016/j.cis.2018.01.004
2 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
processing [10,11], fly ash decarburization [12–14] and pulp-deinking
[15,16]. For mineral flotation, when the raw minerals are collected
from the underground, crushing and grinding is required for liberating
the valuable components from the interlocking particles. Then, these
fine particles are mixed with water and conditioned with appropriate
reagents (collectors, frothers, depressants and regulators). Air is finally
introduced and hydrophobic particles are captured by the rising bubbles
while hydrophilic particles remain in the pulp.
The essential sub-processes in flotation are: wetting, reagents ad-
sorption on minerals, inter-particle force, and bubble-particle interac-
tion. Each step plays a critical role in the final flotation recovery. A
comprehensive understanding of these sub-processes is of great funda-
mental and practical importance to design high-efficiency flotation
process. Up to now, a number of studies have been carried out to inves-
tigate these sub-processes [17–28]. Contact angle measurement is the
most commonly used method in the study of mineral-water wetting
[29]. Spectroscopic techniques such as infrared spectroscopy, X-ray
photoelectron spectroscopy and sum-frequency generation spectros-
copy (SFG) are usually applied to better understand reagent adsorption
on mineral surface and water structure at mineral-water interface
[17–21]. Zeta potentials are measured to characterize the charge on par-
ticles which is essential to predict inter-particle electrostatic interaction.
Theory and computational fluid dynamics are reported to study hydro-
dynamic inter-particle or bubble-particle interaction [22–28]. However,
the flotation mechanisms at the nanoscale are still not well understood
due to the difficulty in experimental verification.
Particularly, surface and interfacial forces (van der Waals, electrical
double layer, hydrophobic force, hydration, hydrodynamic, and adhe-
sion forces) are of great importance to understand inter-particle or
bubble-particle interaction in flotation cells [1,30]. According to the
classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, the sta-
bility of a colloidal system is controlled by two components [30,31],
namely van der Waals dispersion and electrostatic double layer forces.
The van der Waals force between different bodies depends on their
differences in optical properties and can be characterized by the
Hamaker constant. For the interaction of a solid/liquid with a liquid/
gas interface, the van der Waals force is repulsive; it favors thickening
of the liquid film. For the electrostatic double layer force, surface charges
and the salt concentration are the key parameters for determining its
value.
In addition, non-DLVO forces such as hydration and hydrophobic
forces are present in flotation system. A short-ranged repulsive hydra-
tion force emerges when two hydrophilic surfaces are brought into con-
tact and the structure of water is required to change upon approach
[32–34]. In contrast, between two hydrophobic surfaces attractive
forces are observed [35–38]. Hydrophobic forces are usually the driving
force for the attachment of solid particles to bubbles. Laskowski and
Kitchener [39] first found that the water films present on methylated
silica surfaces were unstable and the film ruptured spontaneously.
Their experiment indicates that in addition to the traditional DLVO
forces, an attractive force also acts between the bubbles and the hydro-
phobic solid particles. Three years later, Blake and Kitchener [40] exper-
imentally measured the thickness of the water film when a small gas
bubble was slowly advanced towards a polished silica plate with differ-
ent hydrophobicity. They showed that the film rupture thickness on
methylated silica ranged from 60 to 220 nm. In this case, the thin
water film on the methylated silica surface was unstable due to a
long-range attractive force. The first direct evidence for long-range at-
tractive hydrophobic forces between solid surfaces was provided by
Pashley and Israelachvili using the Surface Force Apparatus (SFA)
[35,36]. In SFA, the force between two hydrophobized mica surfaces
was measured. To date, attractive hydrophobic forces have been ac-
cepted as the reason for bubble-particle attachment, although its origin
remains under debate. Measuring the hydrophobic force between a
bubble and a particle versus distance is, however, challenging. Due to
its strong attractive characteristics and the softness of the bubble
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
surface usually an instability accors once a certain distance has been
reached [41,42].
With the invention of Atomic force microscopy (AFM) a new tool be-
came available for measuring the interaction between particles and
bubbles and for imaging the surface structure of minerals. (Fig. 1).
AFM was first developed by Binnig et al. [43] in 1986, for imaging the
surface topography at nanometer resolution [44]. A sharp probe
mounted near the end of a cantilever is raster scanned along the sample
surface. A laser beam was used to monitor the deflection of the cantile-
ver via a position sensitive diode detector (PSD). Cantilever deflection is
proportional to the force acting on the tip. Usually a feedback loop is
used to keep the force between tip and sample constant by moving
the sample up and down during scanning. In that case the height of
the sample is plotted versus the lateral position to obtain a three-
dimensional topographic image both in air or liquid condition [45–47].
Typically, three common imaging modes, i.e., contact mode, tapping
mode, and non-contact mode, are available in commercial AFMs based
on the way in which the tip scans over the sample [47,48]. In contact
mode, the tip remains in contact with the sample surface by applying
a constant load between tip and the sample (Fig. 1. b). Due to the
large contact pressure, the tip or the sample may get damaged during
the imaging, leading to the decrease in resolution [48,49]. For the soft
surface, contact mode imaging will underestimate the height of the
sample due to the deformation effect. For tapping mode, the tip is oscil-
lated with a value close to its resonance frequency. The tip comes into
and out of contact with the sample repeatedly at the lower turning
point. This intermittent contact between tip and sample leads to a
damping of the tip oscillation, reflected both by a reduction in ampli-
tude and a shift of the resonance frequency. Depending on the feedback
used during intermittent mode, one discriminates between amplitude
modulation (AM) and frequency modulation (FM). In the more com-
mon AM mode, the tip is approached to the sample until a preset ampli-
tude reduction of cantilever oscillation is reached, and this reduced
amplitude is kept constant during scanning using a feedback loop. In
FM mode, a preselected shift of the resonance frequency is used for
the feedback during approach and scanning. FM mode was originally
developed for AFM in ultra-high vacuum (UHV), where AM mode suf-
fers from a slow response time of the feedback due to a much higher
quality factor of the oscillating cantilever, as damping by a fluid is miss-
ing [50]. Recently it was demonstrated, that FM mode can also be used
in liquids [51], allowing imaging and force measurements with atomic
resolution. Compared with contact mode, intermittent contact mode
allows to image soft surface with a higher resolution, as interaction
between tip and sample is minimized and especially lateral shear is
eliminated.
Soon after its introduction, AFM was used as a force sensor to mea-
sure forces, including surface forces, adhesion force, and hydrodynamic
force, between different surfaces or molecules of interest, especially
with the aid of the so called “colloidal probe technique” [47,52–54].
The force is obtained by multiplying the measured probe deflection by
the spring constant of the cantilever. In the colloid probe technique, a
micrometer-size particle is attached to the end of the cantilever and re-
places the sharp tip. Usually the particle is spherical to facilitate the
quantitative analysis. Thus, the interaction geometry between the
probe and surface is greatly simplified.
AFM has also been widely used by flotation scientists to imaging
mineral morphology and measure the force between single particles.
However, it is difficult to predict flotation recovery directly from force
measurements because a large number of particles are involved in
flotation practice. Still, force measurements can provide useful input
parameters for computational fluid dynamics simulation to design
high efficiency flotation process.
The aim of this review is to demonstrate the versatility, flexibility,
and future potential of AFM in order to shed new light on the flotation
mechanisms. We highlight the current state of the art in the application
of AFM in the field of mineral flotation, such as mineral morphology
 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx 3

Fig. 1. a), The working schematic of an AFM [30]; b), The force regimes governing AFM imaging.
Reprinted with permission from [48], Copyright 2004, Elsevier.

imaging, water at mineral surface, reagent adsorption, inter-particle
force, and bubble-particle interaction. Limitations and future
perspectives are also discussed. This review is presented in a way that
is accessible and valuable to flotation researchers with basic knowledge
background regarding AFM.
2. Imaging of minerals
AFM was used to image pure mineral surfaces such as mica, galena,
molybdenite and phyllosilicate. All can be easily cleaved [55–61], to
prepare clean, atomically flat surfaces. For example, Gupta et al.
[59,62] used AFM for imaging the crystal lattice of silica and alumina
faces of phyllosilicate (kaolinite). Negatively charged glass or mica and
positively charged alumina were used as the substrates for kaolinite de-
position. Due to the electrostatic double-layer attraction, the positively
charged alumina face of kaolinite particles attached to the glass or
mica surface, thus exposing the silica faces. In contrast, the alumina
face of kaolinite particles was exposed, when alumina was used as a
substrate. It was found that tetrahedral oxygen atoms on the silica
face formed a closed hexagonal ring-like network with a vacancy in
the centre. On the alumina face, the hexagonal lattice ring of hydroxyls
surrounded a hydroxyl. The atomic spacing between neighboring
hydroxyls was determined as 0.36 ± 0.04 nm. Siretanu et al. [61]
used AM-AFM to image the basal (001) planes of various types of

Fig. 2. Atomic resolution AFM images of clays basal plane: (a) gibbsite, (b) Na-montmorillonite, (c) illite and (d–f) kaolinite clay particles obtained with super sharp tip at
room temperature equilibrated in ultrapure water. Scale bars, 2 nm. Top insets represent zooms of atomic scale images after processing with Fourier transformation superimposed
with X-ray crystal structure of clays along the ab plane.
Reprinted with permission from [61], Copyright 2016, The Royal Society of Chemistry.

Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
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4 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
phyllosilicates, namely gibbsite, kaolinite, illite, and Na-montmorillonite,
in water (Fig. 2). All images show the characteristic hexagonal structure
with a periodicity ≈0.5 nm that arises from the quasi-hexagonal arrange-
ment of silica-tetrahedra and alumina-octahedra, the classical building
units of all clay materials.
In sulfide mineral flotation the oxidation state is of great importance.
The floatability of sulfide minerals is directly related to the degree of its
surface oxidation [63]. For example, fresh galena is hydrophilic. How-
ever, it was found that slight surface oxidation increased the hydropho-
bicity and floatability of galena due to the formation of sulphur rich
layers [60,64]. Therefore, collectorless flotation of sulfide minerals
becomes possible by adjusting the surface oxidation. Xie et al. [57]
studied the effect of applied electrochemical potential, with regard to
the Ag/AgCl/3.4 M KCl reference electrode, on the galena surface
morphology at pH 5.6. It was found that surface roughness increased
significantly when the potential exceeded +300 mV (Fig. 3). This was
due to the agglomeration of electrochemical oxidation products on
the galena surface. Hampton et al. [60] studied the effect of applied
potential on electrochemical oxidation of the galena surface at pH 4.5
(Fig. 4). Sulphur domains were observed and surface roughness in-
creased when the electrochemical potential increased to +258 mV.
Hampton et al. [60] concluded that the electrochemical oxidation of
galena is a two-step process: First, sulphur is released into the solution
and then the sulphur deposits on favourable sites; the sulphur domains
are distributed heterogeneously (Fig. 4), while in Xie's report [57], the
sulphur domains were more homogeneously distributed. The reason
for this discrepancy may be due to the increased surface roughness
of galena in Hampton's experiment. Surface heterogeneity led to a
heterogeneous distribution of oxidation products.
For non-pure minerals which do not have a cleavage face, pre-
treatment such as careful polishing is needed to lower the surface
roughness so that it can be imaged by AFM. Bruening and Cohen [65]
applied AFM to identify the surface roughness variations before and
after coal oxidation. Morga [66] used AFM to study the effect of heat
treatment on the surface roughness of semifusinite and fusinite. Heating
increased the surface roughness of both semifusinite and fusinite.
Fig. 3. Surface topographies of galena surfaces under different applied potentials in 0.5 M NaCl: (A) −700 mV, (B) −300 mV, (C) 0 mV, (D) 300 mV, and (E) 450 mV.
Adapted with permission from [57], Copyright 2016, American Chemical Society.
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
AFM also has the ability to characterize the pore structure on coal
surfaces [67]. Dun et al. [68] found that magmatic intrusions have a
great impact on the pore structures of coal. The pore size of low-rank bi-
tuminous coal was much larger than high-rank anthracite. As a result,
the small molecular weight alkanes (collectors) are easily lost in the
pores due to the capillary effect [6]. Indeed, a higher concentration of
collector is usually required for low-rank coal flotation than that of
high-rank anthracite.
Both the sharpness and the aspect ratio of the probe influence im-
ages obtained with an AFM due to the convolution and broadening ef-
fect. Only probes with a high aspect ratio and small probe radius are
suitable to quantitatively characterize the roughness and pore structure
on mineral surfaces.
3. Water at mineral surface
3.1. Water structure near the interface
AFM is capable of imaging mineral surfaces in liquid. In flotation,
both hydrophilic and hydrophobic particles are in contact with water.
The interaction of the water molecules with the surface atoms of the
solid has an influence on the structure of the interfacial water. Knowing
the water structure at the solid-water interface is essential to under-
stand the flotation mechanisms. Currently, the interfacial water struc-
ture is attracting great interest from researchers in the colloid and
flotation area, and numerous studies have focused on it [69–76].
Water molecules close to a hydrophilic surface have a strong attractive
interaction with surface atoms, e.g. via hydrogen bonds, increasing the
surface free energy. This interaction also leads to a structuring of the
interfacial water, where water molecules on average reside longer at
positions with strong interaction than at positions with lower
interaction force. Such hydration layers typically consist of 3–5 water
molecular layers [69–78].
Hydration layers are dynamic structures i.e., the water molecules in
hydration film are always movable. The water molecules of the first hy-
dration layer are typically completely exchanged within nanoseconds
 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx 5

Fig. 4. Surface topographies of galena surfaces under different applied potentials: A, +8 mV; B, +258 mV; C, +308 mV; D, +358 mV.
Adapted with permission from [60], Copyright 2011, American Chemical Society.

[79]. At the hydrophobic solid-liquid interfaces, in contrast, a water ex-
clusion zone with several angstroms was observed using high-
resolution X-ray reflectivity and neutron reflectivity [80–82].
To map hydration structures with the tip of AFM is challenging be-
cause the tip-sample forces induced by the presence of the hydration
layers can be of the same order as the thermal fluctuations in standard
AFM cantilevers. In 2005, Fukuma et al. [83] demonstrated true atomic
resolution imaging on a mica surface in aqueous buffer solution by
using an AFM with very low detector noise. The low noise in the system
was important because to obtain atomic scale resolution, the amplitude
of the cantilever oscillation had to be on the order of the size of a water
molecule, i.e. less than 1 nm. Using small amplitude force distance spec-
troscopy, they also observed oscillations in the tip-sample force which
they ascribed to the layering of water molecules in the tip-sample gap.
This layering is consistent with earlier reports by Israelachvili and
Pashley [32] and Zachariah et al. [84]. Israelachvili and Pashley [32]
found that the short-range hydration force between two mica surfaces
in water showed an oscillatory profile with a mean periodicity of the
water molecule diameter indicating the existence of ordered water
layers. In contrast, Zachariah et al. [84] suggested that the hydrated
ion layering is responsible for the oscillatory hydration force. However,
information on the potential lateral ordering of water molecules at the
interface was still missing. Thus, a couple of years later Fukuma ex-
tended his high-resolution AFM to enable three dimensional mapping
of the tip-sample force [85]. In this three-dimensional scanning force
microscopy (3D-SFM, Fig. 5), the tip is scanned up and down like the
needle of a sewing machine while the lateral position is slowly changed
in a scanning motion, which enables to visualize 3D distribution of
water at a mica water interface in a region of 2 × 2 μm in 53 s with an
atomic-scale resolution. In the first 3D-SFM investigation on a mica sur-
face in aqueous buffer solution, a Si cantilever with a resonance fre-
quency of 123 kHz, a Q factor of 5.8, and 14.2 N/m spring constant in
liquid was used. Once complete 3D force field was obtained, any 1D pro-
file or 2D cross sections could be extracted. A hexagonal pattern of force
peaks with the same periodicity as the mica substrate was observed.
Above this first hydration layer, a second and a third layer of force
peaks was observed with a lateral shift. Later, similar hydration struc-
tures were observed on hydrophilic surfaces like calcite, fluorite, and
dolomite [73,78,86]. Most authors so far have used for 3D SFM in fre-
quency modulation, mostly because the force reconstruction from the
observables frequency and phase shift, and oscillation and drive ampli-
tude are well established [87,88]. Recently, reliable force reconstruction
methods for amplitude modulation AFM have also become available
[89].
Although 3D-SFM imaging is always carried out on an atomically flat
interface, the necessity of this technique becomes more evident when it
is applied to the systems having a larger corrugation and inhomogene-
ity. Recently, several groups have investigated theoretically by molecu-
lar dynamics simulations how the measured force field is connected to
the overlap of hydration layers of tip and surface [79,90,91]. It was

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6 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
Fig. 5. Schematics of (a) 2D-SFM and (b) 3D-SFM. (c) Experimental setup for the developed 3D-SFM [85]. A phase-locked loop (PLL) circuit is used for the resonance frequency shift
detection while an automatic gain control (AGC) circuit is used for keeping the amplitude of the cantilever oscillation constant. The inset shows a 3D force image obtained at a mica-
water interface (2 × 2× 0.78 nm3).
Adapted with permission from [85], Copyright 2010, American Physical Society.
found that the force maxima correspond to the undisturbed positions of
water molecules at the surface and that the presence of the tip has only
a minor influence on the measured water structure. Further improve-
ments in terms of the measurement technique could be achieved by
using small cantilevers combining high resonance frequency and low
spring constant [92,93], which provide a better signal-to-noise ratio.
Furthermore, Söngen et al. have improved the 3D scanning method by
introducing a tip protection mechanism that retracts the tip when a
threshold force is exceeded at the lower turning point, providing more
stable imaging [94].
3.2. Surface nanobubbles characterization
When hydrophobic mineral surfaces are submerged in water,
nanobubbles or air are easily formed when the dissolved gas becomes
oversaturated for example by increasing temperature or mixing differ-
ent liquids. Such nanobubbles can be stable for many hours [95,96].
Nanobubbles at solid-water interface are an important subject since
studies show that an enhanced flotation recovery can be obtained by
using nanobubbles [97,98]. Parker et al. [99] first suggested that the dis-
continuities in AFM force curves between two hydrophobic surfaces
were due to the presence of nanobubbles. Experimentally, surface
nanobubbles were firstly imaged by using AFM tapping mode by Ishida
et al. [100] and Lou et al. [101]. Subsequently, force mapping mode AFM
[102–104], peak-force tapping mode AFM1 [105–107], and peak-force
quantitative nano-mechanics mode AFM2 [108] were all reported as
being capable to image nanobubbles (Fig. 6). In parallel, non-invasive
techniques have confirmed the existence of nanobubbles such as
infrared spectroscopy [109,110], total internal reflection fluorescence
1
In peak-force tapping the cantilever is periodically moved up and down. In contrast to
normal tapping mode, the cantilever is oscillated below resonance frequency.
2
In peak-force quantitative nano-mechanics mode, a series of force-distance curves is
recorded. While keeping the peak force constant, a several properties such as modulus,
adhesion force, and deformation depth can be extracted and quantified from the force-
distance curve at each pixel.
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
microscopy [111], cryo-scanning electron microscopy [112,113], quartz
crystal microbalance [114], time-resolved fluorescence microscopy
[115], scanning synchrotron based scanning transmission soft X-ray mi-
croscopy [116] and small angle X-ray scattering [117]. The height of
nanobubbles has been reported in the range of 10–100 nm, while the
length of the three-phase contact line is in general between 50 and
500 nm [118]. It is anticipated that nanobubbles should rapidly dissolve
into surrounding water due to a high internal Laplace pressure. How-
ever, surprisingly long lifetimes of nanobubbles have been observed
experimentally [95,96]. However, it is out of the scope of this paper to
review the stability theory of nanobubbles; an excellent recent review
is [95].
Using AFM, the effects of production methods, substrate properties,
salts, solution pH, dissolved gas, surfactants, and temperature on
nanobubbles can be studied. Previous studies showed that degassing
pre-treatment reduces nanobubble formation [119,120]. The gas type
was also found to have great impact on nanobubble nucleation [121].
Zhang et al. [103,122] found that pH, salts, and sodium dodecyl sulfate
has little effect on nanobubbles stability, thus refuting the stability
mechanism of the contamination skin hypothesis. Xu et al. [123]
observed that the formation of surface nanobubbles was temperature-
dependent. More nanobubbles were observed at high temperature
than that at low temperature due to the lower solubility of gas satura-
tion at high temperature.
4. Reagent adsorption on mineral surface
4.1. Structure of adsorbed reagent
The interaction between flotation reagents and mineral surfaces are
of particular interest. In flotation practice, various kinds of flotation re-
agents, i.e., collectors, frothers, dispersants, and flocculants, are used to
regulate interfacial properties and thus the interaction between bubble
and particle or inter-particle. Here, AFM can help analyzing the adsorp-
tion conformation of surfactants or polymers on mineral surface
[56,124–131]. A molecular layer or agglomerate can be identified from
AFM imaging. For example, the adsorption of the surfactants sodium
 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx 7

Fig. 6. Nanobubbles pictures imaged using different AFM working modes: (a) tapping mode, Reprinted with permission from [101], Copyright 2000, American Vacuum Society; (b) force
mapping mode, Reprinted with permission from [102], Copyright 2013, American Chemical Society; (c) Peak-force tapping mode, Reprinted with permission from [106], Copyright 2016,
American Chemical Society; (d) Peak-force QNM mode.
Reprinted with permission from [108], Copyright 2013, The Royal Society of Chemistry.

dodecyl sulphate (SDS) and hexadecyltrimethyl ammonium bromide
(CTAB) at graphite–water interfaces has been studied using AFM by
Parachuri et al. [132]. For both surfactants with either positively or neg-
atively charged head group, the AFM images show the adsorbed surfac-
tant structures as linear parallel hemi-cylindrical micelles when the
concentration is below the CMC concentration. Parachuri et al. [133] fur-
ther studied the effect of cosurfactants (non-ionic 1-dodecanol and cat-
ionic dodecyl trimethyl ammonium bromide) on the SDS surface
micelle structures. The orderliness of the SDS hemicylinders was re-
placed by a herring-bone pattern for the SDS/C12OH system. However,
in the case of the SDS/C12TAB system, the structures were more similar
to the SDS only system. Jaschke et al. [134] used AFM imaged the linear
aggregates of ionic surfactant aggregates at a gold surface in aqueous so-
lution. The orientation of these aggregates was determined either by
monatomic steps on the gold surface or by the gold lattice itself.
Chennakesavulu et al. [128] visualized the conformation of oleate col-
lector on a fluorite crystal surface. Both monolayer and bilayer struc-
tures were observed even at low oleate concentration of 10−7 M.
Paiva et al. [129] studied the effect of calcium ions on the adsorption
of potassium oleate onto apatite surfaces. They found that calcium
ions play a critical role in potassium oleate adsorption, since the adsorp-
tion was completed by forming calcium dioleate agglomerates.
Beaussart et al. [56] explored the effect of three kinds of dextrins, a
regular wheat dextrin (TY), carboxymethyl (CM) dextrin, and hydroxy-
propyl (HP) dextrin, on molybdenite flotation. Topographies of
adsorbed dextrins on molybdenite surface were imaged using AFM
(Fig. 7). The surface coverages of the modified dextrins (CM and HP)
were much higher than that of regular TY, leading to a lower contact
angle and flotation recovery.
As common practice, guar gum is used as the depressant for molyb-
denite flotation. The effect of guar gum on molybdenite flotation was
studied by Xie et al. [135]. The presence of polymer aggregates on
molybdenite surfaces could be correlated with molybdenite flotation re-
sults. The flotation recovery of molybdenite decreased sharply from 69%
to 11% and 3% after guar gum adsorption at concentrations of 1 and
5 ppm. Mierczynska-Vasilev and Beattie [136] studied the adsorption
of three kinds of substituted carboxymethyl cellulose on talc and
chalcopyrite. The wettability depressions of three polymers on talc
were always more effective than on chalcopyrite since more polymers
adsorbed onto talc surface from AFM images. More specifically, low
carboxymethyl cellulose coverage on both minerals was observed for
a high substitution of the carboxymethyls.
4.2. Single molecule force spectroscopy
Polymers are often used as flocculants in ultra-fine particle flotation
and filtration. Fine particles form large-size flocs under the bridging
function of high-molecular-weight polymer. Theoretically, hydrogen
bonding, the hydrophobic interaction, electrostatic attraction, and
chemical bonding are the possible driving forces for flocculation. In
early times it was, however, difficult to measure the force between floc-
culant and mineral particle. With the introduction of single molecule
force spectroscopy (SMFS) it became possible to measure inter- and in-
tramolecular interaction forces in polymer and supramolecular system
with pN resolution using AFM [137–140]. Typically in such experiments,
a polymer bridges the AFM probe and substrate. Then the bridge is
stretched by slowly retracting the tip while measuring the force (Fig. 8).

Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
8 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx

Fig. 7. Topographies of adsorbed dextrins on molybdenite surface: (a) bare molybdenite, (b) Dextrin TY, (c) CM Dextrin, (d) HP Dextrin.
Reprinted with permission from [56], Copyright 2012, Elsevier.

Measuring the force between polymer flocculant molecule and min-
eral surface is of great importance to understand the selective adsorp-
tion mechanism of the flocculant and thus develop new high
efficiency flocculants. Sun et al. [141] carried out SMFS experiments be-
tween a novel hybrid polymer Al(OH)3-polyacrylamide (Al-PAM) and a
silica surface. In this case, the Al(OH)3 served as the core connecting a
number of PAM chains. It was found that the adhesion force between
Al(OH)3 and silica was much higher than that between PAM chain and
silica due to electrostatic attraction. A partially hydrolyzed polyacryl-
amide (HPAM) was found to be beneficial to bitumen extraction not
only improving bitumen recovery but also accelerating fine solids set-
tling in the tailings stream. Long et al. [142] measured the adhesion
force between a partially hydrolyzed polyacrylamide (HPAM) molecule
and different kinds of surfaces (silica, mica, and bitumen). To obtain
more representative results for single-molecule desorption, for each
test condition, the measurement was performed at a number of
different surface locations, and 2 to 3 substrate-tip pairs were used.
N1000 force curves were recorded for each test condition in Long's re-
port. In deionized water, the adhesion forces were reported to be 40,
200, and 80 pN on silica, mica, and bitumen surfaces, respectively
(Fig. 9). When the process water from oil sand processing plant, con-
taining various kinds of ions, was used, the forces changed to 50, 100,
and 40 pN, respectively. The adsorption strength between HPAM and
mica was much higher than that on the bitumen surface. This indicated
that a selective flocculation between clay particles, such as mica, can
achieve when HPAM is added to bitumen-clay mixture suspensions.
Pensini et al. [143] directly coated carboxymethyl cellulose polymer
on a fresh mica surface and a silica/borosilicate/iron oxide particle was
attached to a tip-less cantilever. They recorded retraction forces be-
tween particles and carboxymethyl cellulose coated mica. Different rup-
ture events could be identified from the shape of the force curves
(Fig. 10). Compared to SMFS experiments, the bridge between the

Fig. 8. (a) Schematic of SMFS; (b) Stretching force curves between a polyprotein molecule and a copper surface. ΔLc is the contour length increment.
Reprinted with permission from [138], Copyright 2012, Nature Publishing Group.

Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
Fig. 9. Adhesion forces between HPAM and different kinds of surfaces in DI water and
commercial plant process water.
Reprinted with permission from [142], Copyright 2006, American Chemical Society.
colloidal probe and mica surface is no longer formed by a single mole-
cule. Instead a number of molecules interact due to the large contact
area. It was found that the adhesion force between iron oxide and
carboxymethyl cellulose coated mica in Milli-Q water was always
higher than that between silica/borosilicate. Solution pH and ions
were found to have great impact on the adhesion force.
High molecular-weight flocculants can be attached to the tip and
their interaction with a mineral surface is relatively easy to measure. It
is, however, difficult to directly measure the force between a single sur-
factant molecule (collector) and a mineral surface. Therefore, some sub-
stitutes were used to model collector-mineral interaction. Fa et al.
[144,145] prepared a calcium dioleate micro-sphere to model the inter-
action between the oleate collector and calcite/fluorite. A 10 μm diame-
ter calcium dioleate micro-sphere with a surface roughness Ra of 36 nm
for a given 10 μm2 surface area was used. More specifically, strong long-
range attractive forces in approach curves and adhesion forces in retrac-
tion force curves were observed between calcium dioleate and fluorite;
the force between calcium dioleate and calcite was much weaker. In-
deed, such studies indicate that, in the presence of calcium, calcium
dioleate forms firstly in bulk solution and then adsorbs in the form of
calcium dioleate [146].
Xing et al. [147] used solid-state paraffin and stearic acid to repre-
sent conventional hydrocarbon oil and fatty acid collector in fine coal
flotation. A coal particle with diameter of approximately 35 μm was at-
tached to the end of a tip-less cantilever. The interactions between par-
affin/stearic acid and fresh/oxidized coal particles were measured
directly using atomic AFM colloidal probe technique. In this case, the
paraffin substrate for AFM experiments was prepared using section-
cutting while stearic acid substrate was prepared by the pellet method.
More specifically, a significant jump-into contact between oxidized coal
particles and stearic acid was observed due to the hydrogen bonding
Fig. 10. a), Schematics of different rupture events during particle pull-off from carboxymethyl cellulose coated mica. Each minimum indicates a detachment event occurs. The last
minimum is the adhesion force between one polymer molecule and colloid particle; b), AFM force curves between carboxymethyl cellulose and iron oxide particles in milli-Q water
buffered with NaHCO3 to pH = 8.
Reprinted with permission from [143], Copyright 2013, Elsevier.
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
9
while a monotonous repulsive force between oxidized coal and paraffin.
Consequently, a fatty acid collector is more suitable for oxidized coal flo-
tation than hydrocarbon oil.
5. Quantification of inter-particle force
Inter-particle interaction in flotation pulp is also an important issue
affects the final separation efficiency. For example, coating of micro-fine
slimes on targeted mineral particles has a detrimental effect on flotation
selectivity [148,149]. These slimes follow bubble-particle aggregates
and enter the froth, lowering the concentrate grade. On the other
hand, such slime coatings make targeted particles become hydrophilic
and prevent bubbles or collectors from adhering to particles, reducing
flotation recovery. Selective flocculation was also widely used for
ultra-fine particle flotation to increase bubble-particle collision effi-
ciency or reduce gangue minerals entrainment [150]. Measuring the
driving force responsible for these inter-particle interactions is of both
academic and practical importance in flotation engineering.
The quantification of inter-particle force in colloid science is one of
the most important applications of AFM [54]. Early work mainly focused
on studying surface forces and verifying the correctness of the
Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The critical step
in AFM force measurement is to update the sensitivity and calibrate
the spring constant of the cantilever. During the data analysis, how to
convert force-displacement curve to force-distance one is also a critical
step. However, great attention should be paid to the surface roughness
effect since it would influence the force results and thus the repeatabil-
ity of the experiments. Ducker et al. [52] used AFM to measure the force
between a hydrophilic silica sphere and a silica plane in presence of so-
dium chloride. The measured force at long range could be well predicted
by the classical DLVO theory. However, a repulsive force at short range
was observed probably due to the strong hydration of the surfaces. As
the DLVO theory treats the intervening medium as continuous, the indi-
vidual properties of molecules involved are not taken into consider-
ation. Therefore, it cannot describe the hydration force that is required
to remove the water molecules at the interface when the distance
decreases to a few molecular diameters. Butt [53] also measured the
force between a silicon nitride tip, alumina, glass, and diamond particle
and glass/mica surface in presence of different salt concentrations. A re-
pulsive hydration force with 3 nm decay length between silicon nitride
tip and mica was observed at a high salt concentration (N3 M).
Another kind of non-DLVO force is the hydrophobic force. A vast
amount of hydrophobic force results can be found in the literature.
Pashley and Israelachvili found that the hydrophobic force is much
stronger than the van der Waals attraction and a single exponential
10 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
function gave the best fit to the experimental data [35,36]. Rabinovich
and Yoon [151] found that the hydrophobic force between a hydropho-
bic glass sphere and a silica plate, could be described with both
exponential and power laws.
Up to date, the origin of the hydrophobic force remains unclear. Both
sample preparation methods and experimental techniques have great
impact on the result [37]. Nanobubble bridging is one of the most
representative mechanisms [152]. Hampton and Nguyen [153,154]
used a capillary mathematical model to fit the force curves between a
1-octanol esterified silica sphere and a silica plane, which supports
nanobubble bridge hypothesis. Another possible mechanism for the
long-range hydrophobic force is the spontaneous formation of cavities.
Cavitation due to metastability of the intervening liquid during ap-
proach or separation was proposed by Christensen and Claesson [155].
However, detailed discussion about these origin mechanisms is beyond
the scope of this review. Readers who are interested in this topic can
refer to the excellent reviews by Christenson and Claesson [37] and
Meyer et al. [38].
In many cases it is problematic to quantitatively describe inter-
particle forces because of irregular particle structure and surface hetero-
geneity of practical minerals. Still, the force curves can be qualitatively
compared with varying the concentration of salt or pH and may provide
guidance for flotation engineering. Xing et al. [148,149] studied the ef-
fect of calcium ions on coal flotation in the presence of kaolinite clay.
The interaction force between coal and kaolinite was measured using
AFM (Fig. 11). No jump-in was observed in de-ionized water and the
repulsive force corresponded to that in the case of no kaolinite coating.
A sudden jump-in was found when Ca2+ was added to a concentration
of 3 mM. The repulsive electrostatic force was suppressed by excessive
Ca2+ addition, and the attractive force began to dominate the
kaolinite-particle interaction. Therefore, the presence of Ca2+ in practical
flotation aggravates slime coating and deteriorates flotation selectivity.
The effect of clay types, i.e., kaolinite and montmorillonite on fine
coal flotation was further studied [156]. Only a short jump-into-
contact was observed in de-ionized water for coal-montmorillonite.
This low weak attraction correlates with a lower flotation recovery
and worse selectivity for the coal-montmorillonite system compared
with that of coal-kaolinite system where a repulsive force dominated.
Shrimali et al. [157] prepared two kinds of hematite colloidal probes
of around 15 μm in diameter. In one case, the hematite was glued in a
way that the (001) crystal face was exposed, while in the other case
the hematite particle was oriented so that the (100) crystal surface
was exposed. AFM force measurements between the (001) hematite
crystal surface and the above two colloidal probe were carried out in
Fig. 11. Force curves between coal substrate and a ~50-μm-diameter kaolinite particle in presence of different calcium concentrations: (a) approach curves; (b) retraction curves. Both
attractive force and adhesion force increased with increasing calcium concentration.
Reprinted with permission from [148], Copyright 2016, American Chemical Society.
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
0.001 M KCl solution with varying pH values. Strong long-range attrac-
tive hydrophobic forces at pH 5.5 and pH 2.7 were observed, confirming
that hematite is hydrophobic at these pH values. At alkaline pH values,
only repulsive forces were found indicating that surface hydroxylation
takes place at alkaline pH making the hematite surface hydrophilic.
Often it is more difficult to measure the inter-particle force in the
presence of polymer due to experimental difficulties in controlling the
polymer dose and the often irreversible adsorption [158,159]. Never-
theless, Abraham et al. [160] measured the force between silica surfaces
in the presence of copolymers of acrylamide and negatively charged
acrylic acid with three different negative charge densities (i.e, 15%,
40%, and 70% acrylic acid fraction in copolymers). More specifically, at
low charge density the force was repulsive in the range of experimental
polymer concentrations (from 0.1 ppm to 50 ppm). Increasing the
charge density to 40% or 70%, an attractive adhesion force was observed
at a low polymer concentration due to polymer bridging. A purely repul-
sive force was observed again when the concentration increased to
higher levels.
Zhou et al. [161] also studied the effect of charge density (10, 40, and
100%) of cationic polymers on the force between silica surfaces using
AFM. The 10% charged polymer produced steric repulsion upon ap-
proach and long-range adhesion force at the optimum flocculation con-
centration. In contrast, the 40 and 100% charged polymers produced
attraction during the approach, due to the attractive electrostatic
force, and strong adhesion during the retraction stage at optimum poly-
mer dosages. It was also found that the polymer dose that produced the
optimum flocculation and the maximum compressive yield stress typi-
cally corresponded to the polymer concentration that produced the
maximum adhesion force in AFM force measurement for each polymer.
Ofori et al. [162] examined the coal tailings flocculation performance
using different types and concentrations of flocculants. Averaged jump-
out distances were statistically determined from thousands of AFM
force curves. The optimal flocculant concentration would be the point
corresponding to the maximum jump-out distance in AFM force curves.
However, flocculation and sedimentation tests showed optimum
flocculant concentrations were much higher than those corresponding
to the optimum adhesive strength found in the AFM measurements.
This was probably due to the large surface area of particles in the con-
centrated suspension used in the settling tests compared with just a
few particles used in the atomic force measurement. In concentrated
suspension, so much polymer adsorbs to the particle surface that
polymer is depleted. This would also lead to less polymer at the particle
surfaces. It should be noted that this effect is only important at low
polymer concentrations.
 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
Recently, a multi-particle colloidal probe technique (MPCPT) based
on AFM-inverted optical microscope has been developed to measure
inter-particle forces in situ [159,163]. MPCPT works in a colloidal
suspension in presence of a number of particles, which simplifies the
precise dosing of polymers and makes this approach less sensitive to
impurities. Note that still one particle was attached to the end of canti-
lever in MPCPT. In these experiments, silane reagents are used to
hydrophobize a glass substrate and a tip-less AFM cantilever. A number
of polystyrene latex particles are injected into the liquid cell. The parti-
cles deposit onto glass surface. Then, a particle is picked up by moving
the cantilever on its upside. Finally, force measurement is conducted be-
tween this colloid probe and another deposited particle. The main ad-
vantage of MPCPT, compared with that of traditional colloid particle
probe only with one or two colloidal particles, is that the adsorption of
polyelectrolyte on particles can be controlled precisely, due to the larger
internal surface area in multi-particle suspension system.
Flotation is also used for oil sands separation engineering. Oil sand
separation has been studied, e.g. by Xu's and his team from Edmonton
[164]. In oil sand processing, the first step is to liberate oil from the
sand. The sand typically consists of carbonate rocks and silica. Air bub-
bles are introduced to capture the heavy oil (bitumen) leaving sand par-
ticles in the pulp. Clays account for 15–30% in raw oil sands [165].
Important sub-processes are: bitumen-sand liberation, bitumen-
bubble interaction, and bitumen-fine particle interaction (clay coating).
Here, we treat bitumen as the targeted particle similar to mineral flota-
tion; therefore, we also briefly discuss the application of AFM in
bitumen-sand liberation and clay coating in this section.
Liu et al. [166] coated a thin bitumen film on a flat silica wafer with a
spin coater and then measured the force between bitumen and silica
particle in 1 mM KCl solution. They found that both pH and calcium con-
centration play an important role in bitumen-silica interaction (Fig. 12).
Not only did the repulsive barrier increase, but also the adhesion force
decreased with increasing pH or decreasing calcium concentration.
Temperature is an important parameter in oil sand processing.
Increasing temperature reduces bitumen viscosity and thus decreases
the adhesion force [167]. Alkaline solution with high temperature
and low ion concentrations promotes bitumen liberation. Zhang et al.
[168] further suggested a synergistic effect between surfactants
(dodecyltrimethylammonium chloride and sodium dodecylbenzene
sulfonate) and divalent cation ions (Ca2+ or Mg2+) for bitumen–
silica interaction. More specifically, in alkaline solution, sodium
dodecylbenzene sulfonate does not adsorb on negatively charged silica
and bitumen surfaces due to the strong repulsive double-layer force.
However, this is not the case when divalent cation ions were added.
Ca2+ or Mg2+ prefers adsorbing on silica and bitumen surface in the
Fig. 12. The effect of pH and calcium concentration on the interaction between bitumen substrate and a ~5–10 μm silica particle in 1 mM KCl solution: (left) pH; (right) calcium
concentration. The dashed and solid lines represent the experimental and theoretical fitting results, respectively.
Reprinted with permission from [166], Copyright 2005, Elsevier.
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
11
form of CaOH+ and MgOH+. Thus, these monohydroxyl species act as
bridges between sodium dodecylbenzene sulfonate and the solid
surface.
Liu et al. [169] measured the force between bitumen and different
kinds of irregular clay particles (montmorillonite and kaolinite). When
using irregular particles as a colloidal probe a quantitative comparison
of measured forces with the standard DLVO theory of colloid stability
is difficult because the effectively interacting areas and the contact
area are unknown. Consequently, the force curves have to be only
qualitatively compared. In Liu's experiments [169] the adhesion force
between bitumen and montmorillonite was always higher than that be-
tween bitumen and kaolinite, especially in in the presence of Ca2+. This
is probably due to the large capacity of adsorption of calcium for
montmorillonite, depressing the repulsive force barriers and enhancing
the adhesion force.
A related subject which should be briefly mentioned is bacteria-
mineral interaction. A deep understanding of bacteria-mineral interac-
tion force is critical to mineral bioleaching engineering. To measure
the force between individual bacteria and a mineral surface by AFM,
the main challenge is to anchor the bacteria onto the cantilever or flat
substrate without affecting cell activity [170–172].
Lower et al. [173] introduced a new technique named biologically-
active-force probe (BAFP) to measure the force between bacteria and
different mineral surfaces (muscovite, goethite, and graphite). They
used poly-D-lysine to functionalize glass beads; the negatively charged
glass and cell-surfaces were bridged by positive charged poly-D-lysine
in situ (Fig. 13). It was found that ions, mineral surface charge, and
hydrophobicity significantly affected the interaction. Diao et al. [174]
compared adhesion forces between chalcopyrite and acidithiobacillus
thiooxidans/acidithiobacillus ferrooxidans under various pH conditions.
The average adhesion force for acidithiobacillus ferrooxidans was
always stronger than that of acidithiobacillus thiooxidans, especially at
low pH.
6. Bubble-particle interaction and thin liquid film drainage
Bubble-particle interaction is the critical step for flotation. It is well
accepted that the hydrophobic force is responsible for successful
bubble-particle attachment [42]. AFM is a unique tool to directly
measure bubble-particle interaction. Note that AFM force measurement
between an air bubble and a solid particle is accompanied with the
deformation of gas/liquid interface under both the hydrodynamic and
surface forces. The dynamic coupling between force, bubble deforma-
tion and film drainage makes both theoretical analysis and experimen-
tal verification challenging [41,175].
12 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx

Fig. 13. (A) Schematic of BAFP, (B) Scanning laser confocal image of BAFP. The green particle is the cell coated glass. Scale bar is 10 μm. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
Reprinted with permission from [173], Copyright 2005, Elsevier.

Ducker et al. [176] and Butt [177] first used AFM to measure the
force between a bubble and a particle in 1994. A small hydrophilic or hy-
drophobic silica particle was attached to the end of AFM cantilever and
then approached to the bubble surface at a low speed in pure water. The
observed attractive force between a hydrophilic particle and an air
bubble in Ducker's experiment [176] probably due to contamination.
When surfactant was added, the long range attractive force disappeared
and a monotonous repulsive force emerged. In Butt's report [177], he
found that a repulsive force acted between bubble and a hydrophilic
glass. In contrast, a jump-into contact was observed when hydrophobic
particles approached the bubble surface and a three-phase contact was
formed. In general, particles with finite contact angle towards water
form a three-phase contact and attach to the air/water interface.
The determination of zero distance is an essential step to convert
AFM force-displacement curve to force-distance curve [178–181]. For
the interaction between solid surfaces, the zero distance is deduced
from constant compliance regime in a hard contact system. For the
interaction of a particle with an air/water interface zero distance is a
matter of definition. It is convenient to set zero distance to the
equilibrium position of a particle in the air/water interface. The bubble
is assumed to behave as a Hookean spring under external force
[180,182–186]. To illustrate the situation we consider a small spherical
particle at a planar air/water interface as a model. For particles much
pffiffiffiffiffiffiffiffiffiffiffi
smaller than the capillary length κ ¼ γ=ρg capillary forces dominate;
gravity, buoyancy and inertia can usually be ignored. With typical
values for the density of the liquid ρ ≈ 1000 kg/m3, the acceleration
of gravity g = 9.81 m/s and a surface tension of γ = 0.072 N/m, the
capillary length for water in a gas is 2.7 mm. “Planar” implies that the
bubble radius is much larger than the particle size. For a sphere being
pulled out of an infinitely deep and extended liquid pool (Fig. 14), this
force increases linearly with the length of the capillary bridge
[187–190] and can be approximated by [191]:
attractive force increased whereas the wetting film rupture thickness
did not changed significantly. Preuss and Butt [195,196] studied the in-
fluence of dodecyltrimethylammonium bromide (DTAB) and sodium
dodecyl sulfate (SDS) on bubble-silica interaction. When DTAB was
added at concentrations below the CMC a hydrophobic attraction was
observed caused by the strong adsorption of trimethylammonium
head group to the silica. The exposed dodecyl group rendered the
particles hydrophobic. When the DTAB concentration exceeded 6 mM,
the repulsive force dominated bubble-silica interaction again. Above
6 mM DTAB adsorbs as a double layer to silica exposing the positively
charged head group to the water phase. The air water interface is also
positively charged due to adsorption of DTAB, leading to a strong
electrostatic repulsion. In the experimental concentration range of
SDS, no attractive force was observed between hydrophilic silica and
bubble. For a hydrophobic particle, hydrophobic force dominated the
total force. However, the range and magnitude of the attractive force
decreased as SDS concentration increased and SDS adsorbs to the
hydrophobic solid surface and the air/water interface.
Nguyen et al. [180–182] did a series of experiments on bubble-
particle interaction using AFM. For a hydrophilic silica particle, the
forces at different electrolyte concentrations could be well fitted by
using classical DLVO theory. With increasing ion concentration, the
electrostatic force decreased due to the compression of the double
electrostatic layer. The effect of approach velocity on the force between

2πγδ
F¼ ð1Þ
0:809 þ ln ðκ=RÞ

Eq. (1) has been derived on theoretical grounds. It agrees with

experimental results, e.g. for the interaction of a microparticle with a
bubble [176,181], for a microparticle moved against the surface of
water from the water side [192,193], and for particles being drawn
out of a liquid-air interface [194]. When the contact line is pinned,
Eq. (1) is also valid, only R has to be replaced by Rsinβ, where β denotes
the position of the pinned contact line (Fig. 14). Fig. 14. Schematic of a small particle at a liquid surface in equilibrium (bottom) and when
Ishida [183] studied the effect of surface hydrophobicity on bubble- a force is pulling the particle upwards (top). The contact line, characterized by the angle β,
particle interaction force. With increasing contact angle, the range of the is assumed to slide over the particle surface at constant contact angle Θ.

Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
a hydrophilic glass sphere and bubble was also studied [180]. The
repulsive hydrodynamic force increased monotonically as the ap-
proach speed increased. When piezo approach speeds were lower
than 0.6 μm/s, the hydrodynamic force was negligible and instead
surface forces were dominant. When the particle became hydrophobic,
a sudden jump-into contact due to the attractive hydrophobic force al-
ways observed at a low approach speed. The attractive hydrophobic
force also increased as water contact angle increased. Nguyen et al.
[197] used AFM to determine the contact angle of a micrometer-sized
polyethylene sphere according to the depth of the particle penetration
into the bubble at the zero force. They observed that the contact angle
measured by AFM changes with the speed of the AFM piezo.
Ishida [183] explored the particle hydrophobicity on the force be-
tween a silica particle and an air bubble. It was found that the hydropho-
bicity of the particle did not significantly change the film rupture
thickness, whereas the pH of the solution played a critical role in critical
film rupture thickness. Assemi et al. [181] used AFM to measure the
force between a silica and an air bubble in deionized water and KCl so-
lutions with a low piezo speed. By fitting the force curves using DLVO
theory, the surface potential on the bubble surface was obtained. The
force curves at the edge of the bubble could fit very well to theory,
even at high applied forces due to the less bubble deformation effect.
However, the simple assumption that the bubble surface behaves as
a linear spring will not always be appropriate [175,198]. Chan [175]
derived a no-linear force-displacement relation from the solution
of the Young-Laplace equation between a bubble probe and a solid
plane, as shown in Eq. (2):
       
F F 1 1 þ cosθ 1 profiles of air-water interface were reconstructed using RICM with
ΔD ¼ log þ 2 1 þ log − −1
4πγ 8πγRb 2 1−cosθ 2 þ cosθ
The additional logarithmic term leads to a weak deviation from a
linear-distance relationship when the compression ΔD is not negligible
compared to the radius of the bubble.
In recent years, significant progress has been achieved on both
hydrodynamic drainage modelling and AFM-based experimental
techniques. It has become possible to measure the force, bubble
deformation, and liquid film drainage simultaneously [41].
Chan et al. [175,199] derived a model called augmented Stokes-
Reynolds-Young-Laplace model to predict the force and the evolution
of the wetting film profile before the formation of three-phase contact
line in dynamic AFM experiments. The defining equations of the
augmented Stokes-Reynolds-Young-Laplace model under a no-slip
boundary condition are [175]:
 
∂h 1 ∂ 3 ∂p
¼ rh
∂t 12μr ∂r ∂r
 
2γ γ ∂ ∂h
p¼ −Π− r ð4Þ
Rb r ∂r ∂r
Eqs. (3) and (4) can be solved numerically in the region 0≤r ≤ rmax
when h b bRb. rmax is selected as the value where the local separation
h is so large that the contribution of disjoining pressure could be
neglected. The Stokes-Reynolds-Young-Laplace model has the ability
to capture the essential physical characteristics in AFM force measure-
ments and provides a basic understanding of bubble-particle interaction
force and film drainage dynamics.
Shi et al. [200] measured the force between an air bubble and mica
hydrophobized with octadecyltrichlorosilane (OTS) with different
hydrophobicity in 500 mM NaCl solution. AFM force curves were fitted
by using the Stokes-Reynolds-Young-Laplace model. A jump-into
contact at 7.5 nm was experimentally observed for a partially
hydrophobized mica with 45° water contact angle. The model
reproduced the force results assuming a hydrophobic force with a
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
13
decay length of 0.8 nm. Increasing the contact angle to 85°, both the crit-
ical film rupture thickness and hydrophobic force decay length in-
creased, illustrating that the hydrophobic force increased with water
contact angle. Force measurements between air bubbles and sphalerite
and molybdenite surfaces of different water contact angle were also
conducted by Xie et al. [135,201]. More specifically, the effect of poly-
mer depressant (guar gum) on the bubble-molybdenite attachment
was studied. When 1 ppm guar gum was added, polymer aggregates
on the surface became visible from AFM images, resulting in a decreased
bubble-particle attachment. Further increasing guar gum concentration
to 5 ppm, the contact angle of molybdenite surface decreased from
≈74° to 65°. A monotonic repulsive force was observed. The AFM
force results were consistent with the practical molybdenite flotation
results. The final flotation recovery decreased from 69% to 11% and to
3% after guar gum adsorption at 1 and 5 ppm concentration solutions.
The other effective approach complementary to AFM force measure-
ment is optical interferometry. Clark et al. [202–205] first described the
use of evanescent wave scattering to measure the separation between a
solid surface and a particle that was attached to an AFM cantilever. The
evanescent scattering apparatus was essentially identical to that used in
the original total internal reflection microscopy except that the light
scattered back into the incident medium was collected. However, for
bubble-particle interaction, the evanescent wave scattering is not suit-
able because the liquid has a higher refractive index than air. In 2015,
Shi et al. [206] first combined a reflection interference contrast micro-
scope (RICM) with an AFM to measure the force and the thin water
film profile between a bubble and mica surface simultaneously
(Fig. 15). A bubble was attached on the end of a cantilever. The dynamic
nanometer resolution in normal direction. It was found that the
ð2Þ Stokes-Reynolds-Young-Laplace model can predict both the force and
film drainage with a no-slip boundary condition. A stable wetting film
was observed between an air bubble and a hydrophilic mica surface.
In contrast, jump-in events where the interaction force drastically
turned from repulsive to attractive were observed for hydrophobized
mica with both 45° and 90° contact angle (Fig. 16). Again, the critical
film rupture thickness increased as contact angle increased. Due to the
short range of van der Waals force and the suppression of the electro-
static force at 500 mM NaCl, an additional attractive hydrophobic
force was considered as the reason for triggering film rupture. From
the Stokes-Reynolds-Young-Laplace model, the effective hydrophobic
decay length was inferred to be 0.8 and 1.0 nm for the 45° and 90°
water contact angle, respectively. These results are explained in terms
ð3Þ
Fig. 15. Schematic of the AFM-RICM experimental setup.
Adapted with permission from [206], Copyright 2015, American Chemical
Society.
14 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
Fig. 16. Temporal evolution of the force (left), film profile (middle) and disjoining pressure (right) during approach between an air bubble and hydrophobized mica surfaces (A–C: 45°
contact angle, D–E: 90° contact angle) in 500 mM NaCl solution. Open circles denote the experimental results and solid curves represent the theoretical calculation results.
Adapted with permission from [206], Copyright 2015, American Chemical Society.
of a different water structure at the solid-water interface with different
surface contact angle.
Combining AFM with RICM is a landmark in our full understanding
of bubble-particle interaction [207]. In the next few years, synchronous
measurement of the force and the spatiotemporal evolution of thin
water film profile between bubble and particle in presence of flotation
reagents will shed new light on flotation mechanism [41].
7. Other applications
In recent years, several studies aimed to determine the mineral sur-
face charge and wetting characteristics using direct AFM force measure-
ment [208]. Historically, a colloid probe has usually been employed and
the surface charge information was obtained by fitting the force curves
with the DLVO theory. Ducker et al. [52] applied AFM to measure the
force between silica surfaces at different salt concentrations and pH
values. The force curves were fitted using DLVO theory, where the
surface potential of silica was used as the fitting parameter. The similar
procedure was also adopted to determine the surface potentials of mica/
silica and the isoelectric point of fluorite by Hartley et al. [209] and
Assemi et al. [210].
Another aspect is to measure the point of zero charge (PZC) of
different faces of anisotropic layered silicates such as kaolinite, talc,
pyrophyllite and illite. Traditional zeta potential measurements by
electrophoresis or streaming potential assume a uniform charge density
on these layered silicate particles. Often, however, macroscopic coagula-
tion of dispersed particles is not necessarily observed at the PZC. The
reason for coagulation lies in the fact that the surface charge is not dis-
tributed evenly and that on one particle regions with positive and neg-
ative charge density may exist. However, the problem can be solved
using AFM since with the AFM local charge densities can be measured
[211,212]. Zhao et al. [213] used an ultramicrotome cutting technique
to prepare an edge surface of muscovite, while a smooth basal face
was easily prepared by cleavage. A silica sphere with an 8 μm diameter
was attached to the cantilever and a series of force curves were ob-
tained. The force profiles between the silica and basal face were well
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
fitted with classical DLVO theory. They found that pH has little effect
on the surface potential of muscovite basal face. However, on the edge
they could not get good results due to the roughness of the mica edge
surface over the large contact area.
To overcome the surface roughness effect, Gupta and Miller [62] di-
rectly used a pyramid-shaped silicon nitride tip as the probe to map the
surface potential of two kaolinite basal faces (silica face and alumina
face). The silicon tip was modeled as a cone with a spherical cap at its
apex. Then, the DLVO forces between tip and flat surface could be rea-
sonably approximated as the sum of the conical-substrate interaction
force and the cap-substrate interaction force [214]. The isoelectric
point of the silica tetrahedral face was lower than that of the alumina
octahedral face. Yan et al. [215] further used this approach to explore
the surface potentials of both basal and edge faces of talc and muscovite.
The ultramicrotome cutting technique was applied to prepare the edge
face. The surface potentials of basal faces of both talc and muscovite
were always more negatively charged than that of edge faces in the
range of experimental pH (5.6–10.1) (Fig. 17). This is due to the differ-
ent charging mechanisms between basal and edge faces. The permanent
negative charge of basal faces is attributed to fixed isomorphic substitu-
tion while protonation-deprotonation reactions are responsible for the
pH-dependent properties of the edge face. The anisotropic surface po-
tentials of scheelite crystal and molybdenite were also studied using
AFM force measurements [58,216]. The 101 face of scheelite crystal
was the most negatively charged surface, followed by 112 and 001
faces. For molybdenite, it was found that the surface potentials of both
edge and basal faces are highly pH-dependent.
One can use a hydrophobized probe to map the surface hydropho-
bicity by fitting the force profile using extended DLVO theory with an
additional hydrophobic force taken into consideration. A high attractive
force corresponds to high surface hydrophobicity (large local water
contact angle). Lu et al. [58] used a single exponential function to fit
the experimental hydrophobic force curve between an OTS-coated tip
and a molybdenite surface in 10 mM NaCl solution at various pH
(Fig. 18). An attractive hydrophobic force at all pH ranges was observed.
However, this was not the case between the tip and edge surface. This
 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx 15

Fig. 17. Force curves between AFM tip and different faces in 1 mM KCl solution: A, talc basal plane; B, talc edge plane; C, muscovite basal plane; D, muscovite edge plane. Symbols represent
experimental data and the solid lines represent theoretical fits.
Adapted with permission from [215], Copyright 2011, American Chemical Society.

illustrated that the basal surface of molybdenite shows a hydrophobic CuSO4 activation and amyl xanthate conditioning. Amyl xanthate ad-
character, while the edge surface is hydrophilic. This observation is con- sorption increased surface hydrophobicity.
sistent with the contact angle results. Xie et al. [217] adopted the same Colloidal probe AFM can also be applied to characterize hydrophobic
approach to map the sphalerite surface hydrophobicity before and after surface heterogeneities on a micro scale. The colloidal probe-sample

Fig. 18. Hydrophobic force between OTS-coated tip and (a) face and (b) edge of molybdenite in 10 mM NaCl solution. The dash line is the theoretical fitting result.
Adapted with permission from [58], Copyright 2015, American Chemical Society.

Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
16 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
Fig. 19. Schematic diagram of AFM-IR. IR laser is focused on a sample near the tip of an
AFM. The AFM tip is used as a local detector of IR absorption.
Adapted with permission from [221], Copyright 2016, American Chemical Society.
interaction [218] and parameters derived from force-distance curves
[219] in the context of flotation or other processes like filtration can
be obtained. Rudolph and Peuker [220] combined hydrophobic colloidal
probe AFM with Raman spectroscopy to evaluate the wettability of min-
erals in finely inter-grown ore in situ. The type of mineral phase, where
force measurements were conduct, could be identified by Raman mi-
croscopy. They proposed that adhesion force mapping is a more precise
indicator for the floatability of practical minerals. The combined colloi-
dal probe AFM and Raman technique will also be a powerful tool to in-
vestigate mineral-reagent interactions in flotation systems.
8. Conclusions and perspectives
AFM is an established tool in mineral flotation used both for imaging
and a force sensing. It can be successfully used to image the minerals, to
characterize the water structure at mineral-water interface, to study the
adsorption of flotation reagents on mineral surfaces, to measure inter-
particle forces directly, and characterize bubble-particle interaction. De-
tailed information at the nanoscale has been obtained, greatly assisting
the fundamental understanding of flotation. One challenge is to mea-
sure precise shapes of water/air interfaces in particle-bubble experi-
ments due to the absence of hard contact point.
Fig. 20. (a) AFM topographic image of a self-assembled PEG monolayer on gold (b) AFM-IR absorption image at 1340 cm−1 peak, corresponding to the CH2 peak as shown in the (c) AFM-IR
spectrum of the monolayer. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Image reprinted with permission, Copyright 2014, Anasys Instruments.
Please cite this article as: Xing Y, et al, The application of atomic force microscopy in mineral flotation, Adv Colloid Interface Sci (2018), https://doi.
org/10.1016/j.cis.2018.01.004
The main drawback of AFM is the absence of a chemical imaging ca-
pability. It is necessary to develop new AFM-based techniques that have
the ability to analyze both surface morphology and chemical composi-
tion in the contact area. Optical spectroscopy analysis will be the opti-
mal choice. Recently, significant progress has been achieved on the
hybrid AFM techniques such as the combination of AFM and infrared
spectroscopy (IR) and Raman spectroscopy, which show great poten-
tials in flotation research [221–223]. For AFM-IR, the AFM tip itself
acts as the IR detector and thus can overcome the spatial resolution
limits of conventional IR due to the existence of optical diffraction limi-
tation (Fig. 19). IR laser is pre-set to a wavelength corresponding to an
absorbing wavelength or quickly scanned in wavelength and focused
onto the AFM tip region. By using metallic AFM tips, a local enhance-
ment of the electromagnetic field at the tip end can be achieved. The
IR absorption of the substrate will cause a local thermal expansion and
an additional dipolar interaction between tip and sample. By measuring
the response of the cantilever to IR absorption as a function of wave-
length, IR absorption spectra of a nano-scale region are obtained. The
IR laser can be also fixed at a constant wavelength and IR absorption
as a function of position across the sample to create chemical images
that show the distribution of chemical species [221]. AFM-IR is typically
performed by detecting the oscillation amplitude of the cantilever as a
function of sample position or wavelength. Detailed information on
AFM-IR can be seen in [221]. Fig. 20 shows a resonance-enhanced
AFM-IR image of a self-assembled monolayer of alkyl thiol ethoxylate
(PEG) on gold surface. The IR absorption band at 1340 cm−1 was attrib-
uted to a CH2 peak, and the AFM-IR image directly confirmed the loca-
tion of the PEG island regions.
Raman spectroscopy, complementary to IR, is an alternative tool for
identifying chemical species. The combination of AFM and Raman also
offers the opportunity to obtain both surface morphology and chemical
composition of the sample [222]. In this context, more complementary
information on mineral surface/mineral-water interface can be ob-
tained. For example, the specific adsorption of flotation reagents on
mineral surface can be identified successfully. Note that the chemical
image obtained by AFM-IR is always affected by surface characteristic
such as roughness. Tip-enhanced IR spectroscopy is difficult to operate
in aqueous medium due to the strong IR absorption bands of water.
By contrast, AFM-Raman may allow the experiments conducted in
aqueous environments, while the reproducibility of the Raman signal
 Y. Xing et al. / Advances in Colloid and Interface Science xxx (2018) xxx–xxx
enhancement is still a problem. Nevertheless, the complementary char-
acterization of chemical composition using optical spectroscopy for
AFM topography imaging and the synchronous measurement of the
force and distance involving deformable bubble as a force sensor will
become an active area over the coming years and further shed new
light on flotation mechanism.
Symbols
F force
g acceleration of gravity
h thickness of the intervening water film or separation distance
p hydrodynamic pressure difference
R radius of particle
Rb radius of bubble before deformation
r radial distance from the center of the film
δ the distance the particle moved from its equilibrium position
ρ density
κ capillary length
ΔD AFM piezo displacement
γ surface tension
θ water contact angle
μ viscosity
Π disjoining pressure
Acknowledgments
This research was supported by the National Natural Science Foun-
dation of China (grant no. 51774286, 51574236, 51574240), a project
funded by the China Postdoctoral Science Foundation (2015T80606,
2014M550317) for which the authors express their appreciation.
Yaowen Xing also appreciates China Scholarship Council for the finan-
cial support for their research stay at Max Planck Institute for Polymer
Research. HJB also acknowledges support by the Max Planck Center
for Complex Fluid Dynamics Fluid Dynamics of Complexity.
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