The application of atomic force microscopy in mineral flotation

Yaowen Xing, Mengdi Xu, Xiahui Gui, Yijun Cao, Bent Babel, Martin
Rudolph, Stefan Weber, Michael Kappl, Hans-Jürgen Butt

PII: S0001-8686(17)30410-4
DOI: doi:10.1016/j.cis.2018.01.004
Reference: CIS 1858

To appear in: Advances in Colloid and Interface Science

Please cite this article as: Xing Yaowen, Xu Mengdi, Gui Xiahui, Cao Yijun, Babel Bent,
Rudolph Martin, Weber Stefan, Kappl Michael, Butt Hans-Jürgen, The application of
atomic force microscopy in mineral flotation, Advances in Colloid and Interface Science
(2018), doi:10.1016/j.cis.2018.01.004

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The application of atomic force microscopy in mineral flotation

Yaowen Xing1,2, 3, Mengdi Xu1, Xiahui Gui2,3, Yijun Cao2,4, Bent Babel5, Martin Rudolph5,

Stefan Weber3, Michael Kappl3, Hans-Jürgen Butt3,*

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1. School of Chemical Engineering and Technology, China University of Mining and Technology,

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Xuzhou 221116, China;

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2. Chinese National Engineering Research Center of Coal Preparation and Purification, Xuzhou

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221116, China;

3. Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany;

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4. Henan Province Industrial Technology Research Institute of Resources and Materials, Zhengzhou

University, Zhengzhou 450001, China

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5. Helmholtz-Zentrum Dresden-Rossendorf, Helmholtz Institute Freiberg for Resource Technology,

Chemnitzer Str. 40, 09599 Freiberg, Germany.

*Corresponding author: butt@mpip-mainz.mpg.de (Butt H.); kappl@mpip-mainz.mpg.de (Kappl. M)

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yijuncao@126.com (Cao Y.); guixiahui1985@163.com (Gui X.)

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Abstract
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During the past years, atomic force microscopy (AFM) has matured to an indispensable tool
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to characterize nanomaterials in colloid and interface science. For imaging, a sharp probe
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mounted near to the end of a cantilever scans over the sample surface providing a high

resolution three-dimensional topographic image. In addition, the AFM tip can be used as a

force sensor to detect local properties like adhesion, stiffness, charge etc. After the invention

of the colloidal probe technique it has also become a major method to measure surface forces.

In this review, we highlight the advances in the application of AFM in the field of mineral

flotation, such as mineral morphology 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
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and distance involving deformable bubble as a force sensor will further assist the fundamental

understanding of flotation mechanism.

Keywords: atomic force microscopy, mineral flotation, surface imaging, inter-particle force,

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bubble-particle interaction

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Contents

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1. Introduction ............................................................................................................................ 3
2. Imaging of minerals ............................................................................................................... 8
3 Water at mineral surface ........................................................................................................ 12

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3.1 Water structure near the interface ................................................................................... 12
3.2 Surface nanobubbles characterization ............................................................................ 15
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3 Reagent adsorption on mineral surface ................................................................................. 18
3.1 Structure of adsorbed reagent ......................................................................................... 18
3.2 Single molecule force spectroscopy ............................................................................... 20
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4 Quantification of inter-particle force ..................................................................................... 24

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5 Bubble-particle interaction and thin liquid film drainage ..................................................... 32

6 Other applications ................................................................................................................. 40
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7. Conclusions and perspectives............................................................................................... 44

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Acknowledgments .................................................................................................................... 46
Symbols .................................................................................................................................... 47
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References ................................................................................................................................ 47

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1. Introduction

Froth flotation, belonging to the family of heterocoagulation separation techniques, is based

on the difference in surface hydrophobicity of dispersed particles. It has been widely used in

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mineral processing [1-4], fine coal upgrading [5-7], wastewater treatment [8, 9], oil sands

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processing [10, 11], fly ash decarburization [12-14] and pulp-deinking [15, 16]. For mineral

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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

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fine particles are mixed with water and conditioned with appropriate reagents (collectors,
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frothers, depressants and regulators). Air is finally introduced and hydrophobic particles are

captured by the rising bubbles while hydrophilic particles remain in the pulp.
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The essential sub-processes in flotation are: wetting, reagents adsorption on minerals,

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inter-particle force, and bubble-particle interaction. Each step plays a critical role in the final
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flotation recovery. A comprehensive understanding of these sub-processes is of great

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fundamental and practical importance to design high-efficiency flotation process. Up to now,

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a number of studies have been carried out to investigate 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 spectroscopy (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 particles which is

essential to predict inter-particle electrostatic interaction. Theory and computational fluid

dynamics are reported to study hydrodynamic inter-particle or bubble-particle interaction

[22-28]. However, the flotation mechanisms at the nanoscale are still not well understood due
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to the difficulty in experimental verification.

Particularly, surface and interfacial forces (van der Waals, electrical double layer, hydrophobic

force, hydration, hydrodynamic, and adhesion forces) are of great importance to understand

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inter-particle or bubble-particle interaction in flotation cells [1, 30]. According to the classical

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Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, the stability of a colloidal system is

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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

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differences in optical properties and can be characterized by the Hamaker constant. For the
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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
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and the salt concentration are the key parameters for determining its value.
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In addition, non-DLVO forces such as hydration and hydrophobic forces are present in
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flotation system. A short-ranged repulsive hydration force emerges when two hydrophilic
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surfaces are brought into contact and the structure of water is required to change upon
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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 hydrophobic solid particles. Three years later, Blake and

Kitchener [40] experimentally measured the thickness of the water film when a small gas

bubble was slowly advanced towards a polished silica plate with different hydrophobicity.

They showed that the film rupture thickness on methylated silica ranged from 60 to 220 nm.
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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 attractive hydrophobic

forces between solid surfaces was provided by Pashley and Israelachvili using the Surface

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Force Apparatus (SFA) [35, 36]. In the SFA, the force between two hydrophobized mica

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surfaces was measured. To date, attractive hydrophobic forces have been accepted as the

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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,

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challenging. Due to its strong attractive characteristics and the softness of the bubble surface
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usually an instability accors once a certain distance has been reached [41, 42].

With the invention of Atomic force microscopy (AFM) a new tool became available for
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measuring the interaction between particles and bubbles and for imaging the surface structure
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of minerals. (Fig. 1). AFM was first developed by Binnig et al. [43] in 1986, for imaging the
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surface topography at nanometer resolution [44]. A sharp probe mounted near the end of a
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cantilever is raster scanned along the sample surface. A laser beam was used to monitor the
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deflection of the cantilever 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
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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 oscillated with a value close to its

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resonance frequency. The tip comes into and out of contact with the sample repeatedly at the

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lower turning point. This intermittent contact between tip and sample leads to a damping of

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the tip oscillation, reflected both by a reduction in amplitude and a shift of the resonance

frequency. Depending on the feedback used during intermittent mode, one discriminates

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between amplitude modulation (AM) and frequency modulation (FM). In the more common
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AM mode, the tip is approached to the sample until a preset amplitude reduction of cantilever

oscillation is reached, and this reduced amplitude is kept constant during scanning using a
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feedback loop. In FM mode, a preselected shift of the resonance frequency is used for the
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feedback during approach and scanning. FM mode was originally developed for AFM in
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ultra-high vacuum (UHV), where AM mode suffers from a slow response time of the
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feedback due to a much higher quality factor of the oscillating cantilever, as damping by a
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fluid is missing [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.

a) b)

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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

Soon after its introduction, AFM was used as a force sensor to measure forces, including

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surface forces, adhesion force, and hydrodynamic force, between different surfaces or

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molecules of interest, especially with the aid of the so called “colloidal probe technique” [47,

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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

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attached to the end of the cantilever and replaces the sharp tip. Usually the particle is spherical
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to facilitate the quantitative analysis. Thus, the interaction geometry between the probe and

surface is greatly simplified.

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AFM has also been widely used by flotation scientists to imaging mineral morphology and
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measure the force between single particles. However, it is difficult to predict flotation
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recovery directly from force measurements because a large number of particles are involved
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in flotation practice. Still, force measurements can provide useful input parameters for
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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

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.

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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

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example, Gupta et al. [59, 62] used AFM for imaging the crystal lattice of silica and alumina

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faces of phyllosilicate (kaolinite). Negatively charged glass or mica and positively charged

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alumina were used as the substrates for kaolinite deposition. Due to the electrostatic

double-layer attraction, the positively charged alumina face of kaolinite particles attached to

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the glass or mica surface, thus exposing the silica faces. In contrast, the alumina face of
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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
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a vacancy in the centre. On the alumina face, the hexagonal lattice ring of hydroxyls
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surrounded a hydroxyl. The atomic spacing between neighboring hydroxyls was determined
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as 0.36 ± 0.04 nm. Siretanu et al. [61] used AM-AFM to image the basal (001) planes of
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various types of phyllosilicates, namely gibbsite, kaolinite, illite, and Na-montmorillonite, in

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water (Fig. 2). All images show the characteristic hexagonal structure with a periodicity ≈0.5

nm that arises from the quasi-hexagonal arrangement of silica-tetrahedra and

alumina-octahedra, the classical building units of all clay materials.

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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
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room temperature equilibrated in ultrapure water. Scale bars, 2 nm. Top insets represent
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zooms of atomic scale images after processing with Fourier transformation superimposed with
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X-ray crystal structure of clays along the ab plane. Reprinted with permission from [61],
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Copyright 2016, The Royal Society of Chemistry

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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. However, it was found that slight surface oxidation increased the

hydrophobicity and floatability of galena due to the formation of sulfur 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

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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

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observed and surface roughness increased when the electrochemical potential increased to

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+258 mV. . Hampton et al. [60] concluded that the electrochemical oxidation of galena is a

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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

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report [57], the sulphur domains were more homogeneously distributed. The reason for this
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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.

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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

A B

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C

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

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For non-pure minerals which do not have a cleavage face, pre-treatment such as careful
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polishing is needed to lower the surface roughness so that it can be imaged by AFM. Bruening
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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.

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 bituminous 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

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flotation than that of high-rank anthracite.

Both the sharpness and the aspect ratio of the probe influence images obtained with an AFM

due to the convolution and broadening effect. Only probes with a high aspect ratio and small

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probe radius are suitable to quantitatively characterize the roughness and pore structure on

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mineral surfaces.

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3 Water at mineral surface

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3.1 Water structure near the interface
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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
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the surface atoms of the solid has an influence on the structure of the interfacial water.
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Knowing the water structure at the solid-water interface is essential to understand the flotation
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mechanisms. Currently, the interfacial water structure is attracting great interest from
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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
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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 hydration layer are typically completely exchanged

within nanoseconds [79]. At the hydrophobic solid-liquid interfaces, in contrast, a water

exclusion zone with several angstroms was observed using high-resolution X-ray reflectivity

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and neutron reflectivity [80-82].

To map hydration structures with the tip of AFM is challenging because the tip-sample forces

induced by the presence of the hydration layers can be of the same order as the thermal

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fluctuations in standard AFM cantilevers. In 2005, Fukuma et al. [83] demonstrated true

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atomic resolution imaging on a mica surface in aqueous buffer solution by using an AFM with

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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

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of a water molecule, i.e. less than one nanometer. Using small amplitude force distance
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spectroscopy, 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
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reports by Israelachvili and Pashley [32] and Zachariah et al. [84]. Israelachvili and Pashley
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[32] found that the short-range hydration force between two mica surfaces in water showed an
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oscillatory profile with a mean periodicity of the water molecule diameter indicating the
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existence of ordered water layers. In contrast, Zachariah et al. [84] suggested that the hydrated
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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 extended 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 x 2 µm in 53 sec with an atomic-scale

resolution. In the first 3D-SFM investigation on a mica surface in aqueous buffer solution, a

Si cantilever with a resonance frequency of 123 kHz, a Q factor of 5.8, and 14.2 N/m spring
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constant in liquid was used. Once complete 3D force field was obtained, any 1D profile 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

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a third layer of force peaks was observed with a lateral shift. Later, similar hydration

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structures were observed on hydrophilic surfaces like calcite, fluorite, and dolomite [73, 78,

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86]. Most authors so far have used for 3D SFM in frequency modulation, mostly because the

force reconstruction from the observables frequency and phase shift, and oscillation and drive

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amplitude are well established [87, 88]. Recently, reliable force reconstruction methods for
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amplitude modulation AFM have also become available [89].

Although 3D-SFM imaging is always carried out on an atomically flat interface, the necessity
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of this technique becomes more evident when it is applied to the systems having a larger
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corrugation and inhomogeneity. Recently, several groups have investigated theoretically by

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molecular dynamics simulations how the measured force field is connected to the overlap of
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hydration layers of tip and surface [79, 90, 91]. It was found that the force maxima correspond
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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 improvements 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].

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Fig. 5 Schematics of (a) 2D-SFM and (b) 3D-SFM. (c) Experimental setup for the developed
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3D-SFM [85]. A phase-locked loop (PLL) circuit is used for the resonance frequency shift
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detection while an automatic gain control (AGC) circuit is used for keeping the amplitude of
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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
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Physical Society

3.2 Surface nanobubbles characterization

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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 different 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 discontinuities 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].

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Subsequently, force mapping mode AFM [102-104], peak-force tapping mode AFM 1

[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

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confirmed the existence of nanobubbles such as infrared spectroscopy [109, 110], total

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internal reflection fluorescence microscopy [111], cryo-scanning electron microscopy [112,

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113], quartz crystal microbalance [114], time-resolved fluorescence microscopy [115],

scanning synchrotron based scanning transmission soft X-ray microscopy [116] and small

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angle X-ray scattering [117]. The height of nanobubbles has been reported in the range of
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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
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due to a high internal Laplace pressure. However, surprisingly long lifetimes of nanobubbles
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have been observed experimentally [95, 96]. However, it is out of the scope of this paper to
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review the stability theory of nanobubbles; an excellent recent review is [95].

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a b
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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.
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c d

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Fig. 6 Nanobubbles pictures imaged using different AFM working modes: (a) tapping mode,

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Reprinted with permission from [101], Copyright 2000, American Vacuum Society; (b) force

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mapping mode, Reprinted with permission from [102], Copyright 2013, American Chemical

Society; (c) Peak-force tapping mode, Reprinted with permission from [106], Copyright 2016,
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American Chemical Society; (d) Peak-force QNM mode. Reprinted with permission from
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[108], Copyright 2013, The Royal Society of Chemistry

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Using AFM, the effects of production methods, substrate properties, salts, solution pH,
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dissolved gas, surfactants, and temperature on nanobubbles can be studied. Previous studies
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showed that degassing pre-treatment reduces nanobubble formation [119, 120]. The gas type
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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 saturation at high temperature.

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3 Reagent adsorption on mineral surface

3.1 Structure of adsorbed reagent

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The interaction between flotation reagents and mineral surfaces are of particular interest. In

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flotation practice, various kinds of flotation reagents, i.e., collectors, frothers, dispersants, and

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flocculants, are used to regulate interfacial properties and thus the interaction between bubble

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and particle or inter-particle. Here, AFM can help analyzing the adsorption conformation of

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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
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dodecyl sulphate (SDS) and hexadecyltrimethyl ammonium bromide (CTAB) at

graphite–water interfaces has been studied using AFM by Parachuri et al. [132]. For both
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surfactants with either positively or negatively charged head group, the AFM images show the

adsorbed surfactant structures as linear parallel hemi-cylindrical micelles when the

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concentration is below the CMC concentration. Parachuri et al. [133] further studied the effect
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of cosurfactants (non-ionic 1-dodecanol and cationic dodecyl trimethyl ammonium bromide)

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on the SDS surface micelle structures. The orderliness of the SDS hemicylinders was replaced

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 solution. 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 collector on a fluorite crystal surface. Both monolayer and bilayer

structures were observed even at low oleate concentration of 10-7 M. Paiva et al. [129] studied

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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

adsorption was completed by forming calcium dioleate agglomerates. Beaussart et al. [56]

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explored the effect of three kinds of dextrins, a regular wheat dextrin (TY), carboxymethyl

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(CM) dextrin, and hydroxypropyl (HP) dextrin, on molybdenite flotation. Topographies of

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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,

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leading to a lower contact angle and flotation recovery.
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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

As common practice, guar gum is used as the depressant for molybdenite flotation. The effect

of guar gum on molybdenite flotation was studied by Xie at al. [135]. The presence of

polymer aggregates on molybdenite surfaces could be correlated with molybdenite flotation

results. The flotation recovery of molybdenite decreased sharply from 69% to 11% and 3%

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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

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effective than on chalcopyrite since more polymers adsorbed onto talc surface from AFM

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images. More specifically, low carboxymethyl cellulose coverage on both minerals was

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observed for a high substitution of the carboxymethyls.

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3.2 Single molecule force spectroscopy

Polymers are often used as flocculants in ultra-fine particle flotation and filtration. Fine
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particles form large-size flocs under the bridging function of high-molecular-weight polymer.

Theoretically, hydrogen bonding, the hydrophobic interaction, electrostatic attraction, and

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chemical bonding are the possible driving forces for flocculation. In early times it was,

however, difficult to measure the force between flocculant and mineral particle. With the
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introduction of single molecule force spectroscopy (SMFS) it became possible to measure

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inter- and intramolecular interaction forces in polymer and supramolecular system with pN
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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).

a b

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Fig. 8 (a) Schematic of SMFS; (b) Stretching force curves between a polyprotein molecule

and a copper surface. ∆𝐿𝑐 is the contour length increment. Reprinted with permission from

[138], Copyright 2012, Nature Publishing Group

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Measuring the force between polymer flocculant molecule and mineral surface is of great

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importance to understand the selective adsorption mechanism of the flocculant and thus

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develop new high efficiency flocculants. Sun et al. [141] carried out SMFS experiments

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between 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
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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 polyacrylamide (HPAM)
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was found to be beneficial to bitumen extraction not only improving bitumen recovery but

also accelerating fine solids settling in the tailings stream. Long et al. [142] measured the
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adhesion force between a partially hydrolyzed polyacrylamide (HPAM) molecule and

different kinds of surfaces (silica, mica, and bitumen). To obtain more representative results
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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. More than

1000 force curves were recorded for each test condition in Long’s report. 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,

containing 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

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as mica, can achieve when HPAM is added to bitumen-clay mixture suspensions.

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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,

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American Chemical Society.
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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
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retraction forces between particles and carboxymethyl cellulose coated mica. Different

rupture events could be identified from the shape of the force curves (Fig. 10). Compared to
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SMFS experiments, the bridge between the colloidal probe and mica surface is no longer

formed by a single molecule. Instead a number of molecules interact due to the large contact
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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.
a) b)

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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

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curves between carboxymethyl cellulose and iron oxide particles in milli-Q water buffered

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with NaHCO3 to pH = 8. Reprinted with permission from [143], Copyright 2013, Elsevier

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High molecular-weight flocculants can be attached to the tip and their interaction with a

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mineral surface is relatively easy to measure. It is, however, difficult to directly measure the

force between a single surfactant molecule (collector) and a mineral surface. Therefore, some
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substitutes were used to model collector-mineral interaction. Fa et al. [144, 145] prepared a

calcium dioleate micro-sphere to model the interaction between the oleate collector and
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calcite/fluorite. A 10 µm diameter 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
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attractive forces in approach curves and adhesion forces in retraction force curves were

observed between calcium dioleate and fluorite; the force between calcium dioleate and
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calcite was much weaker. Indeed, 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 represent conventional

hydrocarbon oil and fatty acid collector in fine coal flotation. A coal particle with diameter of

approximately 35 μm was attached to the end of a tip-less cantilever. The interactions between

paraffin/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

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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 while a monotonous repulsive force between

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oxidized coal and paraffin. Consequently, a fatty acid collector is more suitable for oxidized

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coal flotation than hydrocarbon oil.

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4 Quantification of inter-particle force

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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
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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
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coatings make targeted particles become hydrophilic and prevent bubbles or collectors from

adhering to particles, reducing flotation recovery. Selective flocculation was also widely used
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for ultra-fine particle flotation to increase bubble-particle collision efficiency or reduce

gangue minerals entrainment [150]. Measuring the driving force responsible for these
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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

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surface roughness effect since it would influence the force results and thus the repeatability 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 sodium chloride. The measured force at long

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range could be well predicted by the classical DLVO theory. However, a repulsive force at

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short range was observed probably due to the strong hydration of the surfaces. As the DLVO

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theory treats the intervening medium as continuous, the individual properties of molecules

involved are not taken into consideration. Therefore, it cannot describe the hydration force

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that is required to remove the water molecules at the interface when the distance decreases to
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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
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concentrations. A repulsive hydration force with 3 nm decay length between silicon nitride tip
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and mica was observed at a high salt concentration (>3 M).

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Another kind of non-DLVO force is the hydrophobic force. A vast amount of hydrophobic
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force results can be found in the literature. Pashley and Israelachvili found that the
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hydrophobic force is much stronger than the van der Waals attraction and a single exponential

function gave the best fit to the experimental data [35, 36]. Rabinovich and Yoon [151] found

that the hydrophobic force between a hydrophobic 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
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possible mechanism for the long-range hydrophobic force is the spontaneous formation of

cavities. Cavitation due to metastability of the intervening liquid during approach or

separation was proposed by Christensen and Claesson [155]. However, detailed discussion

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about these origin mechanisms is beyond the scope of this review. Readers who are interested

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in this topic can refer to the excellent reviews by Christenson and Claesson [37] and Meyer et

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al. [38].

In many cases it is problematic to quantitatively describe inter-particle forces because of

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irregular particle structure and surface heterogeneity of practical minerals. Still, the force
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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 effect of calcium
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ions on coal flotation in the presence of kaolinite clay. The interaction force between coal and
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kaolinite was measured using AFM (Fig. 11). No jump-in was observed in de-ionized water
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and the repulsive force corresponded to that in the case of no kaolinite coating. A sudden
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jump-in was found when Ca2+ was added to a concentration of 3 mM. The repulsive
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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
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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

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two colloidal probe were carried out in 0.001 M KCl solution with varying pH values. Strong

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long-range attractive hydrophobic forces at pH 5.5 and pH 2.7 were observed, confirming that

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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.
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Fig.11 Force curves between coal substrate and a ~50-µm-diameter kaolinite particle in
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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.

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]. Nevertheless, 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

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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

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due to polymer bridging. A purely repulsive force was observed again when the concentration

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increased to higher levels.

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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

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produced steric repulsion upon approach and long-range adhesion force at the optimum
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flocculation concentration. In contrast, the 40 and 100% charged polymers produced

attraction during the approach, due to the attractive electrostatic force, and strong adhesion
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during the retraction stage at optimum polymer dosages. It was also found that the polymer
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dose that produced the optimum flocculation and the maximum compressive yield stress
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typically corresponded to the polymer concentration that produced the maximum adhesion
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force in AFM force measurement for each polymer.

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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 concentrated

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

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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.

Recently, a multi-particle colloidal probe technique (MPCPT) based on AFM-inverted optical

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microscope has been developed to measure inter-particle forces in situ [159, 163]. MPCPT

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works in a colloidal suspension in presence of a number of particles, which simplifies the

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precise dosing of polymers and makes this approach less sensitive to impurities. Note that still

one particle was attached to the end of cantilever in MPCPT. In these experiments, silane

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reagents are used to hydrophobize a glass substrate and a tip-less AFM cantilever. A number
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of polystyrene latex particles are injected into the liquid cell. The particles deposit onto glass

surface. Then, a particle is picked up by moving the cantilever on its upside. Finally, force
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measurement is conducted between this colloid probe and another deposited particle. The
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main advantage of MPCPT, compared with that of traditional colloid particle probe only with
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one or two colloidal particles, is that the adsorption of polyelectrolyte on particles can be
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controlled precisely, due to the larger internal surface area in multi-particle suspension
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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

bubbles are introduced to capture the heavy oil (bitumen) leaving sand particles in the pulp.

Clays account for 15-30 percent 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 flotation;

therefore, we also briefly discuss the application of AFM in bitumen-sand liberation and clay
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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

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that both pH and calcium concentration play an important role in bitumen-silica interaction

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(Fig. 12). Not only did the repulsive barrier increase, but also the adhesion force decreased

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with increasing pH or decreasing calcium concentration.

Temperature is an important parameter in oil sand processing. Increasing temperature reduces

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bitumen viscosity and thus decreases the adhesion force [167]. Alkaline solution with high
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temperature and low ion concentrations promotes bitumen liberation. Zhang et al. [168]

further suggested a synergistic effect between surfactants (dodecyltrimethylammonium

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chloride and sodium dodecylbenzene sulfonate) and divalent cation ions (Ca2+ or Mg2+) for
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bitumen–silica interaction. More specifically, in alkaline solution, sodium dodecylbenzene

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sulfonate does not adsorb on negatively charged silica and bitumen surfaces due to the strong
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repulsive double-layer force. However, this is not the case when divalent cation ions were
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added. Ca2+ or Mg2+ prefers adsorbing on silica and bitumen surface in the 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
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between 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.

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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
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concentration. The dashed and solid lines represent the experimental and theoretical fitting
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results, respectively. Reprinted with permission from [166], Copyright 2005, Elsevier
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A related subject which should be briefly mentioned is bacteria-mineral interaction. A deep

understanding of bacteria-mineral interaction force is critical to mineral bioleaching

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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

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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

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acidithiobacillus thiooxidans, especially at low pH.

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Fig. 13 (a) Schematic of BAFP, (b) Scanning laser confocal image of BAFP. The green
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particle is the cell coated glass. Scale bar is 10 µm. Reprinted with permission from [173],
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Copyright 2005, Elsevier

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5 Bubble-particle interaction and thin liquid film drainage

Bubble-particle interaction is the critical step for flotation. It is well accepted that the
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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 deformation and film drainage makes both theoretical analysis and experimental

verification challenging [41, 175].

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 hydrophobic silica particle was attached to the end

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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

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attractive force disappeared and a monotonous repulsive force emerged. In Butt’s report [177],

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he found that a repulsive force acted between bubble and a hydrophilic glass. In contrast, a

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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

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water form a three-phase contact and attach to the air/water interface.
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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
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distance is deduced from constant compliance regime in a hard contact system. For the
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interaction of a particle with an air/water interface zero distance is a matter of definition. It is

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convenient to set zero distance to the equilibrium position of a particle in the air/water
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interface. The bubble is assumed to behave as a Hookean spring under external force [180,
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182-186]. To illustrate the situation we consider a small spherical particle at a planar air/water

interface as a model. For particles much smaller than the capillary length     g

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  = 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]:

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2
F (1)
0.809  ln  R 

Eq. (1) has been derived on theoretical grounds. It agrees with experimental results, e.g. for

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the interaction of a microparticle with a bubble [176, 181], for a microparticle moved against

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the surface of water from the water side [192, 193], and for particles being drawn out of a

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liquid-air interface [194]. When the contact line is pinned, Eq. (1) is also valid, only R has to

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be replaced by Rsin, where  denotes the position of the pinned contact line (Fig. 14).

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Fig. 14. Schematic of a small particle at a liquid surface in equilibrium (bottom) and when a
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force is pulling the particle upwards (top). The contact line, characterized by the angle , is
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assumed to slide over the particle surface at constant contact angle .

Ishida [183] studied the effect of surface hydrophobicity on bubble-particle interaction force.

With increasing contact angle, the range of the attractive force increased whereas the wetting

film rupture thickness did not changed significantly. Preuss and Butt [195, 196] studied the

influence 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.

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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

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charged due to adsorption of DTAB, leading to a strong electrostatic repulsion. In the

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experimental concentration range of SDS, no attractive force was observed between

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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

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concentration increased and SDS adsorbs to the hydrophobic solid surface and the air/water
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interface.

Nguyen et al. [180-182] did a series of experiments on bubble-particle interaction using AFM.
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For a hydrophilic silica particle, the forces at different electrolyte concentrations could be
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well fitted by using classical DLVO theory. With increasing ion concentration, the
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electrostatic force decreased due to the compression of the double electrostatic layer. The
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effect of approach velocity on the force between a hydrophilic glass sphere and bubble was
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also studied [180]. The repulsive hydrodynamic force increased monotonically as the

approach 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 always 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.

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Ishida [183] explored the particle hydrophobicity on the force between a silica particle and an

air bubble. It was found that the hydrophobicity of the particle did not significantly change the

film rupture thickness, whereas the pH of the solution played a critical role in critical film

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rupture thickness. Assemi et al. [181] used AFM to measure the force between a silica and an

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air bubble in deionized water and KCl solutions with a low piezo speed. By fitting the force

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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.

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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
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from the solution of the Young-Laplace equation between a bubble probe and a solid plane, as
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shown in Eq. (2):

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𝐹 𝐹 1 1+𝑐𝑜𝑠𝜃 1
∆𝐷 = 4𝜋𝛾 {log (8𝜋𝛾𝑅 ) + 2(1 + 2 log (1−𝑐𝑜𝑠𝜃) − 2+𝑐𝑜𝑠𝜃) − 1} (2)
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The additional logarithmic term leads to a weak deviation from a linear-distance relationship
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when the compression D 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]:
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𝜕ℎ 1 𝜕 𝜕𝑝
= 12𝜇𝑟 𝜕𝑟 (𝑟ℎ3 𝜕𝑟 ) (3)
𝜕𝑡

2𝛾 𝛾 𝜕 𝜕ℎ
𝑝 = 𝑅 − 𝛱 − 𝑟 𝜕𝑟 (𝑟 𝜕𝑟 ) (4)
𝑏

Eqs. (3) and (4) can be solved numerically in the region 0≤ 𝑟 ≤ 𝑟𝑚𝑎𝑥 when h<<𝑅𝑏 . 𝑟𝑚𝑎𝑥 is

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selected as the value where the local separation ℎ is so large that the contribution of

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disjoining pressure could be neglected. The Stokes-Reynolds-Young-Laplace model has the

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ability to capture the essential physical characteristics in AFM force measurements and

provides a basic understanding of bubble-particle interaction force and film drainage

dynamics.
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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

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force curves were fitted by using the Stokes-Reynolds-Young-Laplace model. A jump-into

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contact at 7.5 nm was experimentally observed for a partially hydrophobized mica with 45°
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water contact angle. The model reproduced the force results assuming a hydrophobic force
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with a decay length of 0.8 nm. Increasing the contact angle to 85°, both the critical film
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rupture thickness and hydrophobic force decay length increased, 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 polymer 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
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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 measurement is optical

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interferometry. Clark et al. [202-205] first described the use of evanescent wave scattering to

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measure the separation between a solid surface and a particle that was attached to an AFM

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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

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incident medium was collected. However, for bubble-particle interaction, the evanescent wave
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scattering is not suitable because the liquid has a higher refractive index than air. In 2015, Shi

et al. [206] first combined a reflection interference contrast microscope (RICM) with an AFM
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to measure the force and the thin water film profile between a bubble and mica surface
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simultaneously (Fig. 15). A bubble was attached on the end of a cantilever. The dynamic
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profiles of air-water interface were reconstructed using RICM with nanometer resolution in
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normal direction. It was found that the Stokes-Reynolds-Young-Laplace model can predict
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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 electrostatic 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
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results are explained in terms of a different water structure at the solid-water interface with

different surface contact angle.

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Fig. 15 Schematic of the AFM-RICM experimental setup. Adapted with permission from
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[206], Copyright 2015, American Chemical Society.
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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.

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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

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flotation reagents will shed new light on flotation mechanism [41].

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6 Other applications

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In recent years, several studies aimed to determine the mineral surface charge and wetting

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characteristics using direct AFM force measurement [208]. Historically, a colloid probe has

usually been employed and the surface charge information was obtained by fitting the force
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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
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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
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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
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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 coagulation of dispersed

particles is not necessarily observed at the PZC. The reason for coagulation lies in the fact that

the surface charge is not distributed evenly and that on one particle regions with positive and

negative 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

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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 obtained. The force profiles

between the silica and basal face were well fitted with classical DLVO theory. They found

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that pH has little effect on the surface potential of muscovite basal face. However, on the edge

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they could not get good results due to the roughness of the mica edge surface over the large

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contact area.

To overcome the surface roughness effect, Gupta and Miller [62] directly used a

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pyramid-shaped silicon nitride tip as the probe to map the surface potential of two kaolinite
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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
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reasonably approximated as the sum of the conical-substrate interaction force and the
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cap-substrate interaction force [214]. The isoelectric point of the silica tetrahedral face was
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lower than that of the alumina octahedral face. Yan et al. [215] further used this approach to
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explore the surface potentials of both basal and edge faces of talc and muscovite. The
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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 different

charging mechanisms between basal and edge faces. The permanent negative charge of basal

faces is attributed to fixed isomorphic substitution while protonation-deprotonation reactions

are responsible for the pH-dependent properties of the edge face. The anisotropic surface

potentials 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
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potentials of both edge and basal faces are highly pH-dependent.

A B

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

One can use a hydrophobized probe to map the surface hydrophobicity 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 illustrated

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that the basal surface of molybdenite shows a hydrophobic character, while the edge surface is

hydrophilic. This observation is consistent with the contact angle results. Xie et al. [217]

adopted the same approach to map the sphalerite surface hydrophobicity before and after

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CuSO4 activation and amyl xanthate conditioning. Amyl xanthate adsorption increased surface

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hydrophobicity.

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D
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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
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permission from [58], Copyright 2015, American Chemical Society.

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Colloid probe AFM can also be applied to characterize hydrophobic surface heterogeneities

on a micro scale. The colloid probe-sample 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 colloid probe AFM with Raman

spectroscopy to evaluate the wettability of minerals in finely inter-grown ore in situ. The type

of mineral phase, where force measurements were conduct, could be identified by Raman

microscopy. They proposed that adhesion force mapping is a more precise indicator for the

floatability of practical minerals. The combined colloid probe AFM and Raman technique will

also be a powerful tool to investigate mineral-reagent interactions in flotation systems.

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7. Conclusions and perspectives

AFM is an established tool in mineral flotation used both for imaging and a surface force

sensing. It can be successfully used to image the minerals, to characterize the water structure

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at mineral-water interface, to study the adsorption of flotation reagents on mineral surfaces, to

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measure inter-particle forces directly, and characterize bubble-particle interaction. Detailed

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information at the nanoscale has been obtained, greatly assisting the fundamental

understanding of flotation. One challenge is to measure precise shapes of water/air interfaces

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in particle-bubble experiments due to the absence of hard contact point.
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The main drawback of AFM is the absence of a chemical imaging capability. It is necessary to

develop new AFM-based techniques that have the ability to analyze both surface morphology
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and chemical composition in the contact area. Optical spectroscopy analysis will be the
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optimal choice. Recently, significant progress has been achieved on the hybrid AFM
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techniques such as the combination of AFM and infrared spectroscopy (IR) and Raman
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spectroscopy, which show great potentials in flotation research [221-223]. For AFM-IR, the
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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 limitation (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

enhancement 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 wavelength, 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
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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

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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

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attributed to a CH2 peak, and the AFM-IR image directly confirmed the location of the PEG

island regions.

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Fig. 19 Schematic diagram of AFM-IR. IR laser is focused on a sample near the tip of an
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AFM. The AFM tip is used as a local detector of IR absorption. Adapted with permission

from [221], Copyright 2016, American Chemical Society.

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Fig. 20 (a) AFM topographic image of a self-assembled PEG monolayer on gold (b) AFM-IR
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absorption image at 1340 cm−1 peak, corresponding to the CH2 peak as shown in the (c)

AFM-IR spectrum of the monolayer. Image reprinted with permission, Copyright 2014,

Anasys Instruments

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Raman spectroscopy, complementary to IR, is an alternative tool for identifying chemical

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species. The combination of AFM and Raman also offers the opportunity to obtain both

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surface morphology and chemical composition of the sample [222]. In this context, more

complementary information on mineral surface/mineral-water interface can be obtained. For

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example, the specific adsorption of flotation reagents on mineral surface can be identified
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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

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aqueous medium due to the strong IR absorption bands of water. By contrast, AFM-Raman
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may allow the experiments conducted in aqueous environments, while the reproducibility of
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the Raman signal enhancement is still a problem. Nevertheless, the complementary

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characterization of chemical composition using optical spectroscopy for AFM topography

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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.

Acknowledgments

This research was supported by the National Nature Science Foundation 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 financial support for their

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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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Symbols

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F force

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g acceleration of gravity

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h thickness of the intervening water film or separation distance

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𝑝 hydrodynamic pressure difference

𝑅 radius of particle
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Rb radius of bubble before deformation

𝑟 radial distance from the center of the film

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 the distance the particle moved from its equilibrium position

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𝜌 density

𝜅 capillary length
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∆𝐷 AFM piezo displacement

𝛾 surface tension

𝜃 water contact angle

𝜇 viscosity

𝛱 disjoining pressure

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Graphical abstract NU
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Highlights

● Advances in the application of AFM in mineral flotation are reviewed

● Mineral surface and mineral-water interface imaging are discussed

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● Reagent adsorption, inter-particle force, and bubble-particle interaction are reviewed

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● Complementary chemical characterization and distance measurement are necessary

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