minerals

Review
Recent Developments in Generation, Detection and Application
of Nanobubbles in Flotation
Sabereh Nazari 1 , Ahmad Hassanzadeh 2,3, * , Yaqun He 1, *, Hamid Khoshdast 4
and Przemyslaw B. Kowalczuk 2, *

1 School of Chemical Engineering and Technology, China University of Mining and Technology,
Xuzhou 221116, China; [email protected]
2 Department of Geoscience and Petroleum, Faculty of Engineering, Norwegian University
of Science and Technology, N-7031 Trondheim, Norway
3 Maelgwyn Mineral Services Ltd., Ty Maelgwyn, 1A Gower Road, Cathays, Cardiff CF24 4PA, UK
4 Department of Mining Engineering, Higher Education Complex of Zarand, Zarand 7761156391, Iran;
[email protected]
* Correspondence: [email protected] (A.H.); [email protected] (Y.H.);
[email protected] (P.B.K.)

Abstract: This paper reviews recent developments in the fundamental understating of ultrafine
(nano) bubbles (NBs) and presents technological advances and reagent types used for their generation
in flotation. The generation of NBs using various approaches including ultrasonication, solvent
exchange, temperature change, hydrodynamic cavitation, and electrolysis was assessed. Most
importantly, restrictions and opportunities with respect to the detection of NBs were comprehensively
reviewed, focusing on various characterization techniques such as the laser particle size analyzer



(LPSA), nanoparticle tracking (NTA), dynamic light scattering (DLS), zeta-phase light scattering


(ZPALS), and zeta sizer. As a key feature, types and possible mechanisms of surfactants applied to
Citation: Nazari, S.; Hassanzadeh, A.;
stabilize NBs were also explored. Furthermore, flotation-assisted nano-bubbles was reported as an
He, Y.; Khoshdast, H.; Kowalczuk,
efficient method for recovering minerals, with a special focus on flotation kinetics. It was found that
P.B. Recent Developments in
most researchers reported the existence and formation of NBs by different techniques, but there is not
Generation, Detection and
enough information on an accurate measurement of their size distribution and their commonly used
Application of Nanobubbles in
Flotation. Minerals 2022, 12, 462.
reagents. It was also recognized that a suitable method for generating NBs, at a high rate and with
https://doi.org/10.3390/ a low cost, remains a technical challenge in flotation. The application of hydrodynamic cavitation
min12040462 based on a venturi tube and using the LPSA and NTA in laboratory scales were identified as the
most predominant approaches for the generation and detection of NBs, respectively. In this regard,
Academic Editors: Luis Vinnett and
neither pilot- nor industrial-scale case studies were found in the literature; they were only highlighted
Cesar O. Gomez
as future works. Although the NB-stabilizing effects of electrolytes have been well-explored, the
Received: 14 March 2022 mechanisms related to surfactants remain the issue of further investigation. The effectiveness of the
Accepted: 8 April 2022 NB-assisted flotation processes has been mostly addressed for single minerals, and only a few works
Published: 10 April 2022
have been reported for bulk materials. Finally, we believe that the current review paves the way
Publisher’s Note: MDPI stays neutral for an appropriate selection of generating and detecting ultrafine bubbles and shines the light on a
with regard to jurisdictional claims in profound understanding of its effectiveness.
published maps and institutional affil-
iations. Keywords: nanobubbles; hydrodynamic cavitation; flotation; dynamic light scattering; bubble size

Copyright: © 2022 by the authors.

1. Introduction
Licensee MDPI, Basel, Switzerland.
This article is an open access article
Nanobubbles (NBs), also known as ultrafine bubbles, are extremely small (finer than
distributed under the terms and
1 µm) and have several unique physical and physicochemical properties, making them very
conditions of the Creative Commons different from sub-micron (SMBs < 50 µm), micro- (MBs, 50–1000 µm) and conventional air
Attribution (CC BY) license (https:// bubbles (CBs, >1000 µm) [1]. They can be categorized into surface NBs (formed at solid–
creativecommons.org/licenses/by/ liquid interfaces), bulk NBs (exist in bulk liquid and are spherical with a typical diameter
4.0/). of 100–200 nm), and micro-pancakes (quasi-two-dimensional gaseous domains) [1,2].

Minerals 2022, 12, 462. https://doi.org/10.3390/min12040462 https://www.mdpi.com/journal/minerals

Minerals 2022, 12, 462 2 of 31

The concept of NBs was first proposed in 1954 to explain the growth of NBs as gas
nucleic during cavitation [3]. An analysis of the fast flotation kinetics claimed by the
developed flotation cells in the early 1990s led to the initiation of a research program
at McGill University to explore the role of gas nucleation and cavitation in flotation [4].
The research not only experimentally justified the benefits of applying the two-stage
particle–bubble attachment model for the accelerated flotation kinetics but also developed
the cavitation tube concept for generating an abundance of NBs in flotation to complete the
requirements of the two-stage attachment model [4–6]. In 1997, improved flotation rates
were reported when the NBs co-existed with CBs [5]. Later in 2000, the existence of NBs was
reported using atomic force microscopy (AFM) by Lou et al. [7], when the first image of NBs
on the hydrophobic solid surface was obtained. Since then, NB-adapted technologies have
been applied as a problem-solving alternative for different challenges [7,8]. During recent
years, liquids containing NBs have attracted attention in industry and academia because of
their special properties and wide range of applications, such as nanoscopic cleaning [9],
controlling slip in microfluidics [10], mineral flotation [11–14], chemical industries [15],
and wastewater treatment [16]. Additionally, numerous studies have been conducted
to investigate NB size, shape, surface charge properties, stability, and kinetics [17–19].
A historical overview of developments in theoretical and practical investigations regarding
ultrafine bubbles is given elsewhere [20,21].
The generation of NBs is a complex physicochemical process that depends significantly
on several parameters, including temperature, electrolyte concentration, dissolved gas con-
tent in solution as well as type and concentration of reagents [17,18,22–25]. Many methods,
such as hydrodynamic cavitation [26], chemical reaction [27], ultrasonic oscillation [28],
and electrolysis [29], have been used to generate either MBs or NBs. However, one of
the rarely addressed critical points of using NBs is related to energy consumption and
electrical expenses of their generators. In practice, the high energy consumption, installa-
tion inconvenience and maintenance difficulty encountered in ultrasonic and electrolysis
methods have prevented them from being used in flotation [30]. Among these methods,
hydrodynamic cavitation is considered the most promising method for large-scale mineral
flotation applications due to its simple design and high throughput [31–35].
Over recent decades, a number of bubble size-measurement techniques have been
developed, including X-ray techniques [36], optical microscopic and photographic meth-
ods [37], laser pulse methods [38], fluid dynamics methods [39], and image analysis [40].
Although these methods have been widely applied to characterize NBs, they have several
obvious disadvantages: time-consuming data processes, requirement for a low bubble con-
centration, and a transparent barrier required for image acquisition [41]. Therefore, using
laser diffraction-based technologies, e.g., laser particle size analyzer (LPSA), nanoparticle
tracking analysis (NTA), and dynamic light scattering (DLS) for measuring the bubble
diameter have become the preferred research techniques [42].
In the last two decades, the use of NBs has increasingly driven a lot of attention
towards the mineral processing field because of their high gas solubility [23], high surface
area [43], long lifetime [44], high concentration, improved hydrophobicity of solids [45],
and extensive contact angle [14]. Additionally, it is now proven that they enhance recover-
ability and kinetics of flotation by increasing hydrophobicity of minerals, reducing reagent
consumptions, increasing flotation selectivity of the desirable particles [46,47], and acting as
a secondary collector [11–13]. In flotation, due to a specific movement of NBs in the liquid,
they more easily colloid and attach to the surface of fine and ultrafine particles. Through
this, NB-coated fine particles can be easily attached to the CBs and recovered [48–50].
Figure 1 shows NBs and CBs attaching to fine and coarse particles in flotation with two
different mechanisms [51]. The ultrafine bubbles preferentially nucleate at the surface of
hydrophobic particles [5] because the work of adhesion between a solid particle and water
is always smaller than the work of cohesion of water. Furthermore, the work of adhesion
decreases with increasing the solid surface hydrophobicity measured by the contact angle.
NBs can nucleate on ultrafine particles without the need for collision, which is often the
Minerals 2022, 12, x FOR PEER REVIEW 3 of 30

Minerals 2022, 12, 462

of adhesion decreases with increasing the solid surface hydrophobicity measured 3 of 31
by the
contact angle. NBs can nucleate on ultrafine particles without the need for collision, which
is often the rate-determining step in the froth flotation for ultrafine particles (<20 µm)
[52,53]. Coarse particles attach more easily to CBs in the presence of NBs. Although nano-
rate-determining step in the froth flotation for ultrafine particles (<20 µm) [52,53]. Coarse
bubbles
particles do notmore
attach haveeasily
sufficient
to CBsbuoyancy forceoftoNBs.
in the presence floatAlthough
coarse particles by themselves,
nano-bubbles do not the
surface of a coarse
have sufficient particle
buoyancy forcecoated
to float with
coarseNBs is more
particles hydrophobic
by themselves, than that
the surface of a without
coarse NBs.
The wetting
particle coatedfilm separating
with thehydrophobic
NBs is more colliding CBs and
than NBs
that is more
without NBs.unstable than the
The wetting filmfilm be-
tween the CBs and coarse particles. So, bubble–particle attachment and water film
separating the colliding CBs and NBs is more unstable than the film between the CBs andrupture
can be accelerated in the presence of NBs [26,34,54].
coarse particles. So, bubble–particle attachment and water film rupture can be accelerated
in the presence of NBs [26,34,54].

Figure 1. Representation
Figure 1. Representation ofof possible
possible mechanism
mechanism for coarse
for coarse (left) (left) and
and fine fine (right)
(right) particlesparticles floating in
floating in
the presence of CBs and NBs.
the presence of CBs and NBs.

NB-assisted flotation processes have provided great benefits to conventional flotation

NB-assisted flotation processes have provided great benefits to conventional flota-
systems, as proven for coal [54–57], shale [24,58–60], quartz [61–63], scheelite [32], and chal-
tion systems,
copyrite [64]. as proven
Despite for coal
a wide [54–57],
range shale [24,58–60],
of experimental studies,quartz [61–63],
pilot- and scheelite [32], and
industrial-scale
chalcopyrite [64]. Despite a wide range of experimental studies, pilot- and industrial-scale
applications are still very limited [65]. Further, most of the studies reported in the literature
applications
were conducted areonstill very
single limited [65]. while
mono-minerals, Further, most offlotation
NB-assisted the studies reported
application in the litera-
to actual
ture were conducted
ore samples on singleoverlooked
has been relatively mono-minerals, while NB-assisted
[5,26,53,60,61,64,66,67]. flotation
Figure application
2 displays a to
actual ore samples has been relatively overlooked [5,26,53,60,61,64,66,67]. Figure 2 dis-
number of scientific articles published and indexed by the Web of Science from 1993 to 2021
plays
in the a number
scope of NBsofand
scientific articles published
their application in flotation.and indexed
As seen frombythethe Web
graph, of Science from
researchers
are nowadays paying great attention to assessing NB-assisted flotation processes.
1993 to 2021 in the scope of NBs and their application in flotation. As seen from the graph,
NBs can be generated by several methods, as shown in Figure 3. One of the important
researchers are nowadays paying great attention to assessing NB-assisted flotation pro-
issues in the extended market is the production of NBs by simple, cheap, stable, and scalable
cesses.
methods [68]. Several companies in the USA, South Korea, Canada, and Japan have pro-
duced such bubbles by special methods containing cavitation chambers, electrolysis, shear
planes, pressurized dissolution, and swirling fluids in a mixing chamber [69]. A significant
number of works focused on bubble generation and properties after 2000, initially reported
by Kim et al. [70]. Later, in 2007, Kikuchi and colleagues [29] generated NBs by electrolysis.
NBs were produced by sonication of a perfluorocarbon gas by adding some surfactants,
as reported by Oeffinger and Wheatley [71]. The formation of NBs in a closed cuvette by
increasing the temperature was investigated by Najafi et al. [18]. Ultrafine bubbles were
later generated by the injection of gas (N2 , CH4 , and Ar) into distilled water solution by
Ohgaki et al. [72]. They reported that the concentration of NBs was 1.9 × 1016 bubbles
per dm3 , and they remained stable for up to two weeks. The generation of NBs using a
multiphase pump was studied by Etchepare et al. [73]. The results showed that the bulk
NBs were stable for over 60 days, with no decrease in their concentration and mean size.
Nazari et al. [12] studied NBs generated with different reagents in water by hydrodynamic
cavitation. Bulk NBs generated with oxygen and air in the water and counter flow hydro-
 Minerals 2022, 12, 462 4 of 31

Minerals 2022, 12, x FOR PEER REVIEW 4 of 30

dynamic cavitation was studied by Michailidi et al. [74]. The presence of OH radicals in
low concentration was confirmed for all NBs samples.

Minerals 2022, 12, x FOR PEER REVIEW 5 of 30

Figure
Figure2.2.Number
Numberof ofmanuscripts
manuscripts published in literature
published in literatureononapplication
applicationofof NBs
NBs in in flotation
flotation (from
(from
1993 to 2021) (calculated based on the Web of Science data).
1993 to 2021) (calculated based on the Web of Science data).

NBs can be generated by several methods, as shown in Figure 3. One of the important
issues in the extended market is the production of NBs by simple, cheap, stable, and scal-
able methods [68]. Several companies in the USA, South Korea, Canada, and Japan have
produced such bubbles by special methods containing cavitation chambers, electrolysis,
shear planes, pressurized dissolution, and swirling fluids in a mixing chamber [69]. A
significant number of works focused on bubble generation and properties after 2000, ini-
tially reported by Kim et al. [70]. Later, in 2007, Kikuchi and colleagues [29] generated
NBs by electrolysis. NBs were produced by sonication of a perfluorocarbon gas by adding
some surfactants, as reported by Oeffinger and Wheatley [71]. The formation of NBs in a
closed cuvette by increasing the temperature was investigated by Najafi et al. [18]. Ul-
trafine bubbles were later generated by the injection of gas (N2, CH4, and Ar) into distilled
water solution by Ohgaki et al. [72]. They reported that the concentration of NBs was 1.9
× 1016 bubbles per dm3, and they remained stable for up to two weeks. The generation of
NBs using a multiphase pump was studied by Etchepare et al. [73]. The results showed
that the bulk NBs were stable for over 60 days, with no decrease in their concentration
and mean size. Nazari et al. [12] studied NBs generated with different reagents in water
by hydrodynamic cavitation. Bulk NBs generated with oxygen and air in the water and
counter
Figure3.flow
Figure hydrodynamic
3.AAschematic
schematic overview
overview cavitation
ofof was
commonly
commonly studied
applied
applied by Michailidi
techniques
techniques et al.NBs.
for producing
for producing [74]. The presence
NBs.
of OH radicals in low concentration was confirmed for all NBs samples.
AlthoughNBs
Although NBsplay
play aa vital
vital role
role in
in flotation
flotation of
of fine,
fine, ultrafine,
ultrafine, and
and coarse
coarse particles,
particles, pre-
previous
vious practical studies have mainly focused on the ultimate flotation performanceand
practical studies have mainly focused on the ultimate flotation performance and its
its kinetics
kinetics ininthe
thepresence/absence
presence/absence of of NBs.
NBs. AAfew
fewreview
review papers
papershave recently
have highlighted
recently highlighted
the impact of NBs in flotation [75–78]. Their focus was mainly on the fundamental aspects
the impact of NBs in flotation [75–78]. Their focus was mainly on the fundamental aspects
of bulk NBs and their characteristics, however, to the best of the author’s knowledge,
of bulk NBs and their characteristics, however, to the best of the author’s knowledge, there
there is a lack of thorough review on advancements in generators and detection methods
is aNBs
of lackasofwell
thorough
as the review
effect ofonreagents
advancements in generators
on the production of and
NBs detection
and their methods
application of NBs
as flotation.
in well as the effect of reagents
Therefore, the present on paper
the production of NBs
reviews recent and theirinapplication
advances these areas.inInflotation.
the
Therefore, the present paper reviews recent advances in these
first part of this paper, generation methods, detection techniques, and their areas. In the first partare
accuracies of this
paper, generation methods, detection techniques, and their accuracies
discussed. Commonly used reagents for the production of NBs are described in more detail. are discussed.
Commonly
In used
addition, the reagents
effect for theon
of reagents production of NBs
the flotation are described
process is discussed.in more detail.
The final Inisaddi-
part
tion, the effect of reagents on the flotation process is discussed. The final part is focused
on the application of NBs in mechanical and column flotation. We believe that the data
and conclusions that are driven by this study will guide researchers towards profound
understating, and may aid them to realize NB-assisted flotation systems in full scales.
Minerals 2022, 12, 462 5 of 31

focused on the application of NBs in mechanical and column flotation. We believe that the
data and conclusions that are driven by this study will guide researchers towards profound
understating, and may aid them to realize NB-assisted flotation systems in full scales.

2. Generation Techniques
2.1. Power Ultrasound
A commonly used approach for generating bubbles is via acoustic methods, which
are relatively simple and applicable in large liquid samples of optically non-accessible
media [79]. Ultrasound generators are compact, simple in operation, have a short generation
time, and are contamination-free. Furthermore, the number of bubbles can be controlled
by an appropriate selection of ultrasonic frequency and power [79]. For example, Leroy
and Norisuye [80] proposed that ultrasound is an ideal tool for investigating the existence
of bulk NBs because (i) it is sensitive to minute quantities of gas; (ii) it allows one to
determine the bubble size distribution; and (iii) it discriminates unambiguously between
gaseous and solid/liquid inclusions. Nevertheless, analyzing literature data clarifies that
there is generally no unified statement regarding the creation of NBs by acoustic waves.
Such contradiction is mainly related to the utilization of different experimental apparatus,
studied parameters, and various purposes of the experimental setups [81]. Further in-
depth information regarding the sonication parameters and their effects on the bubble
size distribution can be found elsewhere [81]. Chen et al. [82] classified the ultrasonically
created bubbles into three zones based on the ultrasonication time and frequency, i.e., low
(20–50 kHz), medium (200–1000 kHz), and high (>1 mHz). They found that the NBs were
unstable at low frequencies, owing to the transient cavitation effect, while the medium range
of frequency was selected as the optimum range for acoustic-assisted flotation processes
regarding the formation of stable NBs. Power ultrasound (20–100 kHz) penetrates into
the medium and creates acoustic cavitation bubbles [83]. In this method, the pressure
sharply decreases below the saturated vapor pressure and leads to considerable dissolving
of air and its conversion to bubbles [28,84]. Miastkowska et al. [85] showed that NBs form
from bubble nuclei when the ultrasound irradiates into water, and grow to resonance size
under acoustic pressure fluctuations and collapse (acoustic cavitation). Thus, ultrasound’s
time, frequency, and power substantially impact the size of acoustically generated bubbles.
Additionally, Cho et al. [17] concluded that the effective diameter of NBs generated by
ultrasound in pure water was maintained at 750 nm, without significant change within one
hour. In addition to the creation of ultrafine bubbles, a positive effect of ultrasonic-assisted
flotation either as a pretreatment or simultaneous process has been extensively reported
by many researchers on a wide variety of metallic and non-metallic minerals [83,86,87].
Scientists partially related such improvements to the presence of NBs leading to an increase
in the hydrophobicity of solid surfaces (expressed as a water contact angle) [88,89].

2.2. Solvent Exchange

One of the simplest methods used to create ultrafine bubbles is solvent exchange, which
applies an exchange of two solutions with different gas solubilities such as ethanol and
water. This method is usually used for the production of NBs on a laboratory scale [7,22,75].
The solvent-exchange process includes a few steps, shown in Figure 4, where at first,
a hydrophobic substance should be contacted with water. Then, ethanol replaces water,
and NBs are formed and cover the substance’s surface. Gas molecules do not diffuse into
the atmosphere and stay in the water during the replacing water of with ethanol. Organic
solvents such as ethanol, methanol, and 2-propanol can be applied to produce NBs [90,91].
Because the air has a higher solubility in ethanol than water, the exchange process leads to
gas supersaturation, and consequently, NB nucleation. These NBs form a huge number of
interfaces in the solution. These interfaces can cause the directed arrangement of ethanol
molecules due to their amphiphilic nature [91]. Further, other methods such as exchanging
cold water against warm water and ethanol solution against salt solution have been applied
for producing NBs [75]. Ethanol–water exchange was used for the first time on the surface of
 solvents such as ethanol, methanol, and 2-propanol can be applied to produce NBs [90,91].
Because the air has a higher solubility in ethanol than water, the exchange process leads
to gas supersaturation, and consequently, NB nucleation. These NBs form a huge number
of interfaces in the solution. These interfaces can cause the directed arrangement of etha-
Minerals 2022, 12, 462
nol molecules due to their amphiphilic nature [91]. Further, other methods such as ex-
6 of 31
changing cold water against warm water and ethanol solution against salt solution have
been applied for producing NBs [75]. Ethanol–water exchange was used for the first time
on the surface of mica by Lou et al. [7] to generate ultrafine bubbles. Some researchers
mica by Lou et al. [7] to generate ultrafine bubbles. Some researchers found that the number
offound thatenhanced
NBs was the numberwithofan
NBs was enhanced
increase withconcentration
in the alcohol an increase inup
thetoalcohol
70%, andconcentration
above
up to 70%, and above this concentration, the bubbles disappeared [92]. Xiao
this concentration, the bubbles disappeared [92]. Xiao et al. [91] applied molecular dynamic et al. [91]
(MD) simulations for predicting the NBs generation by the solvent-exchange method. Theyby the
applied molecular dynamic (MD) simulations for predicting the NBs generation
solvent-exchange
showed method.
that there is an interfaceThey showed
between that there
exchanging is an
solvents interface
with differentbetween exchanging
gas solubilities,
solvents
and with different
the interface graduallygasmovessolubilities, and
towards the the interface
substrate, gradually
forming NBs in the moves towards the
bulk solution
substrate,
and/or forming
on the NBs insolid
hydrophobic the bulk solution and/or on the hydrophobic solid surface.
surface.

Figure
Figure 4.4.
AA stepwise
stepwise process
process of of alcohol–water
alcohol–water exchange
exchange method
method and and generation
generation of ultrafine
of ultrafine bubbles.
bubbles.
Reprinted with permission from [68]. Copyright (2015) by the American Physical
Reprinted with permission from [68]. Copyright (2015) by the American Physical Society. Society.

Although the solvent exchange is used for generating bubbles, the exact mechanism of
processing the gas saturation is yet unknown. Furthermore, the solvent-exchange method
cannot control bubble formation precisely because several factors such as the exchange rate,
liquid shear, saturation level of gas, and flow boundary conditions, cannot be controlled
during the experiments [91].

2.3. Temperature Change

Another technique for producing ultrafine bubbles is the temperature difference
method. Changing temperature is one of the important physical and chemical factors
related to bubble generation at the solid–water interface [93,94]. In this method, the gas
solubility in water and heat diffusion reduce due to increased temperature. Through this,
water becomes supersaturated with air, and releasing gas induces the production of fine
bubbles on the solid surface [22,75]. Some researchers have reported that the increase in
the liquid temperature leads to the formation of in situ NBs [22]. They showed that NBs
generated during immersion and at high-water temperatures remain stably on the surface
at low water temperatures. Moreover, such bubbles were sensitive to the cleaning process
used to prepare the substrates [22]. Zhang et al. [95] and Yang et al. [22] showed that when
the temperature was enhanced to 30 ◦ C, the density of bubbles was enhanced very slowly,
but was boosted sharply when the temperature increased further (Figure 5). They also
indicated that the generated bubbles did not disappear when the water cooled down to
ambient conditions, and they were remarkably stable.

2.4. Hydrodynamic Cavitation

In recent years, one of the most critical methods for generating NBs has been hydro-
dynamic cavitation [5,12,53]. This is the process of creation and growth of gas bubbles
in a liquid due to the rupture of either a liquid–liquid or a liquid–solid interface under
the influence of external forces [96]. In other words, when rapid changes in pressure in a
liquid occur in places where the pressure is relatively low, vapor-filled cavities are formed,
and this phenomenon is called cavitation [32,34,97].
 the temperature was enhanced to 30 °C, the density of bubbles was enhanced very slowly,
but was boosted sharply when the temperature increased further (Figure 5). They also
indicated that the generated bubbles did not disappear when the water cooled down to
ambient conditions, and they were remarkably stable.
Minerals 2022, 12, 462 7 of 31

Figure
Figure5.5.AFM
AFMimages
imagesatat different watertemperatures
different water temperaturesininintervals
intervals
of of
5 ◦5C:20–40
°C:20–40
◦ C°C (a–e).
(a–e). (f) (f)
TheThe
NBNB
density
densityasasaafunction
function of
of water temperature.Reprinted
water temperature. Reprintedwith
withpermission
permission from
from [22].
[22].

2.4. Hydrodynamic
The first study Cavitation
of cavitation was carried out in the 1710s, but the term cavitation was
introduced in 1895 by Thornycroft and Barnaby [98]. The first stage of cavitation is defined
In recent years, one of the most critical methods for generating NBs has been hydro-
as nucleation, which is the formation of cavities. In this process, the liquid structure is
dynamic
rupturedcavitation [5,12,53].
to form a hole This isforces.
by external the process of creation
Additionally, andstarts
rupture growth
at aof gas location
weak bubbles in
a where
liquid the
dueintermolecular
to the ruptureforces
of either a liquid–liquid or a liquid–solid interface
approach zero [99,100]. The nucleation of a bubble under
on athe
influence of external
particle surface forcesbubble–particle
increases [96]. In other words,
collision,when
whichrapid changes
is often in pressurestep
a rate-limiting in ainliq-
uid occur in places where the pressure is relatively low, vapor-filled cavities
flotation with CBs. Hence, cavitation and gas nucleation provide a suitable mechanism for are formed,
and
thethis phenomenon
collection is called
in flotation [101]. cavitation
Hydrodynamic [32,34,97].
cavitation is well-described by Bernoulli’s
The first
equation [5]: study of cavitation was carried out in the 1710s, but the term cavitation was
introduced in 1895 by Thornycroft P+and1 Barnaby [98]. The
ρU 2 = C (constant ) first stage of cavitation is defined
(1)
as nucleation, which is the formation of cavities. In this process, the liquid structure is
2
ruptured
where Utoisform a hole flow
the water by external
velocityforces. Additionally,
at a point where the rupture starts
pressure is at
P, aand
weak location
ρ is the
where
liquidthe intermolecular forces approach zero [99,100]. The nucleation of a bubble on a
density.
Cavitation number (K) is normally used for calculating the onset of cavitation in either
equipment or components with flow constrictions, and is defined as follows [4]:


2 Pmin − Pvap
K= (2)
ρ · v2

where Pmin is the minimum pressure occurring in the vicinity of the restriction, Pvap is the
vapor pressure of the liquid, ρ (kg/m3 ) is the density of the liquid, and v (m/s) is the flow
velocity through the restriction. The cavitation phenomenon occurs when the cavitation
number is less than 1.5 [102].
Cavitation is affected by many factors, which include geometric parameters, op-
erational conditions, dissolved gas content, reagent concentrates, and the addition of
solids [101,103]. A venturi tube is typically used as a hydrodynamic cavitation device
(Figure 6). The liquid in the cylindrical throat is higher in flow velocity and lower in
pressure than the liquid in the entrance cylinder, resulting in cavitation. The differen-
tial pressure between the entrance cylinder and the cylindrical throat measured by the
manometers is indicative of cavitation behavior [5,96,101]. Different designs of cavitation
tube technologies have emerged and become commercially available for laboratory research,
flotation machines, and commercial flotation operations. For example, Eriez Manufacturing
Co., (Erie, PA, USA) has sold more than 200 flotation columns using CavTubes for sparging,
and has retrofitted many other columns with the cavitation tube technology [104].
 tween the entrance cylinder and the cylindrical throat measured by the manometers is
indicative of cavitation behavior [5,96,101]. Different designs of cavitation tube technolo-
gies have emerged and become commercially available for laboratory research, flotation
machines, and commercial flotation operations. For example, Eriez Manufacturing Co.,
Minerals 2022, 12, 462
(USA) has sold more than 200 flotation columns using CavTubes for sparging, 8 of 31
and has
retrofitted many other columns with the cavitation tube technology [104].

Figure 6. Schematic
Figure 6. Schematicdiagrams
diagrams of NB
of NB generator
generator based
based on hydrodynamic
on hydrodynamic cavitation
cavitation [103]. [103].

Some companies, such as Canadian Process Technologies (CPT), Coalberg seam coal
Some
in West companies,
Virginia such Energy
[59], CSIRO as Canadian Process
Technology, andTechnologies (CPT), Coalberg
Novatech Consulting seam coal
[105], have
in Westhigh-shear
applied Virginia [59], CSIRO
cavitation Energyflotation
to improve Technology,
of fine and
coal, Novatech Consulting
iron ore, phosphate, [105], have
fluorite,
applied
niobium, high-shear
feldspar, mica,cavitation to improve
and molybdenum. flotation that
They illustrated of fine coal,of iron
recovery ore,
fine and phosphate,
coarse
fluorite,
particles niobium,
was low by feldspar,
CBs, whichmica,
wasand molybdenum.
improved They hydrodynamic
by applying illustrated thatcavitation.
recovery of fine
and
Somecoarse particles
researchers havewas
usedlow
this by CBs, which
mechanism was improved
as a pulp pretreatment bymethod
applying hydrodynamic
before flota-
cavitation. Some researchers have used this mechanism as a pulp pretreatment
tion [6,51,64,106]. Other studies have employed it in flotation separation processes; the testsmethod
were carried out in mechanical and column flotation cells [13,51,53,107,108]. Additionally,
before flotation [6,51,64,106]. Other studies have employed it in flotation separation pro-
recent tests have shown the potential of its application to recover/remove residual bitumen
cesses; the tests were carried out in mechanical and column flotation cells
from oil–sand mature fine tailings [102].
Some researchers have also investigated the effect of different types of gases (e.g., air,
O2 , N2 , Ar, and CO2 ) on NBs generation [97,103]. The results confirmed that the sizes
of ultrafine bubbles were well-correlated to the gas solubility in water. Indeed, larger
bubbles were obtained with gas of a higher solubility, accompanied by more ultrafine
bubbles generated. Li [109] reported that a linear correlation was found between the
volume of generated cavity bubbles and air saturation pressure, further confirming that
NBs generation and stabilization are proportional to the dissolved gas concentration.

2.5. Electrolysis and Chemical Reaction

An alternative method to produce NBs is water electrolysis. In this technique, oxygen
and hydrogen bubbles can be generated at the hydrophobic surface–water interface by
producing oxygen and hydrogen gases at the electrolysis electrodes when the surface acts as
a negative electrode. Changing voltage and reaction time affects the formation, growth, and
size of NBs. The type of gas applied is also an essential factor in controlling the generation
and properties of NBs. The results illustrated that the number of oxygen bubbles generated
was substantially smaller than the hydrogen ones, because oxygen solubility in water is
approximately two times the solubility of the hydrogen during the electrolysis process [110].
Further, oxygen bubbles are more stable than air bubbles, which in turn are more stable
than other NBs [46]. This method is mainly applied in electro-flotation techniques [110,111].
The supersaturation of dissolved gas can further produce bubbles by chemical re-
actions, which liberate a gaseous species. This can be applied as a potential method for
generating ultrafine bubbles (Figure 7). For example, carbon dioxide generated by mixing
acid with carbonate was applied in a reactive flotation technique [100,112]. In this method,
the concentration of reactants and the solution conditions were controlled by the rate of
a chemical reaction that can be enhanced using catalysts. Thus, gas supersaturation by
the chemical reaction provides relatively appropriate conditions for the generation of NBs.
Some researchers have investigated the electrochemical nucleation of bubbles on solid
nano-electrode surfaces [113,114]. The reduction of protons in acidic solutions [113] and
 acid with carbonate was applied in a reactive flotation technique [100,112]. In this method
the concentration of reactants and the solution conditions were controlled by the rate of 
chemical reaction that can be enhanced using catalysts. Thus, gas supersaturation by th
chemical reaction provides relatively appropriate conditions for the generation of NBs
Minerals 2022, 12, 462 Some  researchers  have  investigated  the  electrochemical  nucleation  of  bubbles 
9 of 31 on  soli
nano‐electrode surfaces [113,114]. The reduction of protons in acidic solutions [113] an
oxidation of N2H4 [114] and H2O2 [115] generated gaseous products (hydrogen, nitrogen
and oxygen). In another study, the chemical reaction between ammonium chloride an
oxidation of N2 H4 [114] and H2 O2 [115] generated gaseous products (hydrogen, nitrogen,
sodium 
and nitrite 
oxygen). created 
In another bulk the
study, nitrogen 
chemicalNBs  with between
reaction diameters  of  200–300 
ammonium nm and
chloride [116].  The
concluded that these bubbles formed only when they were trapped between two carbo
sodium nitrite created bulk nitrogen NBs with diameters of 200–300 nm [116]. They con-
cluded
films. that these bubbles formed only when they were trapped between two carbon films.

 
Figure 7. Schematic overview of chemical reaction happening on the bubble surface. Reprinted from
Figure 7. Schematic overview of chemical reaction happening on the bubble surface. Reprinted
[27]. Copyright (2022), with permission from Elsevier. 
from [27]. Copyright (2022), with permission from Elsevier.

3. Bubble Size-Measurement Techniques

One of the important physical properties of bubbles is their size, which can be mea-
sured under various conditions and descriptions along with the gas hold-up and veloc-
  ity [117]. Several methods are available for the detection of bubble size, including optical
methods such as high-speed photography [118,119], image analysis [120], and electrical
impedance [121,122], as well as acoustical methods [108,123–125]. Table 1 presents the
generic methods applied to measure CB sizes in froth flotation, and detailed information
regarding the modern techniques can be found elsewhere [126]. These commonly used
methods are not capable of measuring ultrafine bubble sizes because of their too-small
diameters [69].

Table 1. Comparison of three major techniques to measure the size of CBs.

Analysis Technique Size (µm) Analysis Speed Data Output Advantages and Disadvantages
Available in non-transparent
Acoustical methods 34–1200 Fast and Size, size distribution media. High cost and limited
highly automated
data output.
Small range, limited output and
Light scattering <100 Fast and automated Size, size distribution generally used in
backlighting illumination
Size, size distribution, rise Available for obtaining more
Photographic >50 Slow and manual velocity, shape analysis, information, modifiable, relatively
formation process low cost, viscous liquids.

Recently, several methods have been used for measuring the NB size distribution,
such as the laser particle-size analyzer (LPSA) [34,64,97], nanoparticle tracking analysis
(NTA) [28,127,128], zeta sizer [61], dynamic light scattering (DLS) [129,130], and zeta-phase
light scattering (ZPALS) [46], direct measurement by optical microscopy and indirect
measurement by dissolved oxygen (DO) reverse estimation [69]. Table 2 summarizes
studies that applied these techniques for measuring the presence and size of NBs on
various solid surfaces. Additionally, the studies show that the distribution and size of NBs
depend on the system design and various operational conditions [7].
Minerals 2022, 12, 462 10 of 31

Table 2. Comparison of three major techniques to measure the size of CBs.

Size Analyzer Equipment Material Refs.

Venturi tube Coal [107]
Venturi tube and static mixer Coal and phosphate [11,24,131]
Venturi tube and the static mixer Coal [53]
Static mixer- venturi tube Coal [55]
Venturi tube Chalcopyrite [64]
LPSA Venturi tube Coarse quartz particles [34,51]
Venturi tube and static mixer Coal [101]
Venturi tube Phosphate ore [60,132]
Venturi tube Sub-bituminous coal [56]
Venturi tube Hematite [133]
Venturi tube Coal [35]
Hydrodynamic cavitation Coal [134]
Venturi tube Fine silica and zinc sulphide [5]
DLS Porous membrane system UN * [129]
Hydrodynamic cavitation Coal [135]
Needle valves Ferric hydroxide [73,127]
Depressurization of DI water Quartz and apatitic minerals [63]
Venturi tube UN * [33]
Venturi tube Muscovite [13]
NTA Ultrasonic Mica [86]
Decompression method (Vacuum
Kaolinite [136]
drying oven)
Depressurization
Platinum nanoparticles [137]
with a gas vent
Steel needle valve Quartz [61]
Flow constrictor (needle valve) Quartz [138]
Venturi tube Scheelite [32]
Zetasizer Venturi tube Scheelite [106]
Venturi tube Diaspore and kaolinite [14]
Venturi tube UN * [74]
baffled high intensity agitation
UN * [46]
(BHIA)
ZetaPALS
High speed agitator Alumina and silica [139]
Venturi tube Coal [45]
Solvent-exchange Graphite [140]
Blowing N2 and
Pyrite [141]
AFM CO2 gas into deionized (DI) water
Temperature rise Muscovite [94]
Venturi tube Au, Pb [142]
Beam Reflectance Venturi tube Subbituminous coal [143]
Measurement (FBRM)
Camera Ultrasonic Zinc ore [83]
high-speed camera system Venture cavitation sparger Coal [144]
YBM Fubby (cavitation bubbles and
A 405 nm laser beam
vortex flow) UN * [25]
High speed camera Venturi tube Apatite [57]
Air-in-water
Photocamera- Microscope microdispersion generator Glass beads [145,146]

Temperature rise Bitumen [147]

High-speed venturi nozzles Platinum Group Metal (PGM) tailings [148]
Temperature rise Coal [149]
Ultrasonic cavitation Coal [67]
UN * Ultrasonic cavitation Rutile [150]
Venturi tube Bitumen [151]
Venturi tube High-ash coal [152]
Venturi tube Apatite ore [153]
Venturi tube Pb–Cu–Zn sulfide ore [154]
* UN: unknown or not mentioned in the manuscript. For the type of mineral, this term might suggest the presence
of NBs only in bulk solution.

Among available techniques for measuring NB size, LPSA is the most frequently
used [155]. Measurements with this device can be described based on the Mie’s theory,
considering a refractive index of 1.0 for air NBs and 1.33 for water [51,156]. In recent years,
this technique has been applied to measure NBs in flotation of different solids such as coal,
Minerals 2022, 12, 462 11 of 31

phosphate, hematite, and quartz [12,56,60,133]. LPSA has many advantages, such as quick
measurement (from two seconds to ten minutes), being easily operated, its repeatability
for large numbers of entities, and control of the dispersion process. The limitation of this
technique is the assumption of shape sphericity, which is not valid neither for particles
nor for bubbles. Non-spherical entities can be equivalent to a combination of a series of
spherical ones with different sizes, which leads to a higher proportion of tiny entities,
and the whole distribution becomes broader [157–159].
A nanoparticle tracking analysis (NTA) is a method for the direct and real-time visual-
ization and analysis of NBs in liquids [127]. This method can be used to detect concentration,
zeta potential, fluorescence, and particle size range of approximately 10 nm to 1 µm in
liquid suspension, and requires fast computer systems that are able to cope with the com-
putationally intensive video analyses in reasonable time frames. This method was initially
utilized almost 25 years ago, but bubbles’ size measurement can be considered relatively
new to the market [160,161]. A combination of an ultra-microscope and a laser illumination
unit must be used to estimate bubble diameters accurately. More detailed information re-
garding the measurement mechanism can be found elsewhere [162,163]. Some researchers
have applied NTA as a suitable method for analyzing NBs [33,63,127].
Dynamic light scattering (DLS) is also a well-established method for the measurement
of particle and bubble size distributions in colloidal suspensions and emulsions typically in
the sub-micron region (lower than 1 µm). Some researchers have applied this technique for
bulk and surface-attached NBs [5,127,135]. In a DLS experiment, a sample is illuminated
with a laser beam and the temporal fluctuations are analyzed at a known scattering angle
of θ by means of the intensity of photon autocorrelation function. The scattering signal
is either directly received by the detector or superposed by a reference beam [164,165].
This method has several advantages such as (i) the experiment duration is short and it is
almost fully automatized, so that for routine measurements, extensive experience is not
required; (ii) this method has modest development costs; (iii) and it is possible to obtain
absolute measurements of several parameters of interest, such as molecular weight, a radius
of gyration, and diffusion constant [160,166]. However, this technique has also specific
application limits that restrict its usage, for reasons such as (i) being affected by several
instrumental parameters; (ii) DLS signals allow for only a rather limited resolution of size
distribution, and the results are considerably affected by the employed algorithms; (iii) the
optical models typically rely on the assumption of spherical entities, that is rarely met in
real-life analyses; (iv) and DLS alone does not provide chemical information to distinguish
gas NBs from either particles or droplets [164,165].
A zetasizer is also often applied for the measurement of ultrafine bubble size. Its main
features are automatic optical alignment prior to testing, set measurement positions, and
precise temperature control, which make measurements extremely repetitive and accu-
rate [167]. The zetasizer nano series uses a process called DLS for size measurements. This
is achieved by irradiating entities with a laser to analyze fluctuations in the light strength of
scattered light. For DLS, an important feature of the Brown’s motion is that small bubbles
move quickly and large ones move slowly. As bubbles move around, the constructive
and destructive phase overlay of scattered light causes bright and dark areas to increase
and decrease in a light-strength manner—or in another way, the light appears to fluctu-
ate. It eventually measures the speed at which light strength fluctuates and is then used
to calculate the bubble size. Additionally, this method uses a process called static light
scattering (SLS) to measure the molecular weight to obtain molecular characteristics in a
solution [32,106,168].
The atomic force microscopy (AFM) technique has recently been utilized to measure
the bubble size on the solid surface. Its advantage is the incomparable 3D resolutions of
surface NBs. In particular, the contact angle of NBs can be extracted from the cross-sectional
profile of NBs in the AFM image. However, one of several disadvantages of AFM is the
inevitable perturbation of the examined sample by the probe. Thus, one main concern
was that the bubbles were not present on the surface until the surface was perturbed by
Minerals 2022, 12, 462 12 of 31

the AFM probe. After several complementary measurements, it was proven and generally
accepted that the presence of surface nano-bubbles was not the consequence of the tip
perturbation [68,169].
Another method to measure the bubble size is optical microscopy by transmission
and Scanning Electron Microscopy (SEM). Cyro-EM or freeze-fracture electron microscopy
has been applied as a promising method for the observation of NBs and has shown high
resolution and the capability of providing direct evidence [170,171]. Some researchers have
shown that in the freezing process, bubbles may agglomerate and coalesce [22]. Although
this method has limitations such as being slow, manual, and also that obtaining statistically
significant data can be extremely time-consuming, it is easily modifiable and relatively low
cost, applicable for viscous liquids, and its use in developed lab view-based bubble analysis
processing has led to analysis tailored to specific requirements [159,172]. Furthermore, this
method can accurately measure the size of a single bubble but cannot measure a large
number of bubbles at the same time. Additionally, when the bubble becomes smaller,
progressively more time is required to adjust the light intensity and focus on the individual
bubbles [69].
Karpitschka et al. [173] non-invasively investigated NBs nucleation on glass using
interference-enhanced reflection microscopy. The evidence of surface NBs using total
internal reflection fluorescence microscopy (TIRF) with dye-labeled NBs was studied by
Chan and Ohl [174]. The methods investigated by these researchers do not provide evidence
for the gas content and have diffraction-limited lateral resolution [174].

4. Commonly Used Reagents for Producing NBs

Numerous studies have focused on the influence of different types of reagents on
the physiochemical characteristics of NBs. These reagents may be ionic and nonionic
surfactants, salt and electrolyte solutions, and mixtures thereof. In flotation, different
surface-active substances, mainly frothers, are used to generate bubbles and stabilize the
froth [126,175]. The features of generated bubbles are also affected by temperature, airflow
rate, pH, and pressure. Principally, the stabilizing role of reagents is due to their ability to
reduce the surface energy and surface tension of the air/water boundaries [50].
Although it is well-known that the structure and other physicochemical properties
of surfactants significantly influence the characteristics of bubbles in aqueous solutions,
a few papers have surveyed the real effect of surfactants on the production of NBs and
their application in flotation. Generally, it is well-demonstrated that using a suitable frother
can reduce the size of bubbles by between 13 and 35% [176]. Table 3 presents a summary of
the physicochemical properties of surfactants used for NBs generation. Details on various
physicochemical characteristics of flotation frothers can be found elsewhere [126,177,178].
 of surfactants
few papers have significantly influence
surveyed influence
the real effect the of
characteristics
surfactants on ofthe
bubbles in aqueous
production of NBs solutions,
and their a
of
of surfactants
surfactants significantly
significantly influence the
the characteristics
characteristics of
of bubbles
bubbles in
in aqueous
aqueous solutions,
solutions, aa
few papers
application have surveyed
in flotation. the
Generally,real effect of surfactants
it is well-demonstrated on the
thatproduction of
using a suitable NBs and their
few
few papers
papers have
have surveyed
surveyed the
the real
real effect
effect of
of surfactants
surfactants onon the
the production
production of NBsfrother
of NBs and can
and their
their
application
reduce the inin flotation.
size Generally,
of bubbles by between it is well-demonstrated
13 and 35% [176].that that using
Table a suitable
3 presents frother can
a summary of
application
application in flotation.
flotation. Generally,
Generally, ititis
is well-demonstrated
well-demonstrated that using
using aa suitable
suitable frother
frother can
can
reduce
the the size of bubbles
physicochemical by between
properties of 13 andused
surfactants 35%for[176].
NBs Table 3 presents
generation. a summary
Details on variousof
reduce the size of bubbles by between 13 and 35% [176]. Table 3
reduce the size of bubbles by between 13 and 35% [176]. Table 3 presents a summary ofpresents a summary of
the physicochemical
physicochemical properties
characteristics of surfactants
ofsurfactants used
flotation frothers for
can NBs generation.
be generation.
found elsewhereDetails on various
[126,177,178].
Minerals 2022, 12, 462 the
the physicochemical
physicochemical properties
properties of of surfactants used
used for
for NBs
NBs generation. Details
Details on
on various
various 13 of 31
physicochemical characteristics of flotation frothers can be found elsewhere [126,177,178].
physicochemical
physicochemical characteristics
characteristics ofof flotation
flotation frothers
frothers can
can be
be found
found elsewhere
elsewhere [126,177,178].
[126,177,178].
Table 3. Physiochemical properties of surfactants used for NBs generation.
Tableof3.surfactants
Physiochemical properties of surfactants used for NBs generation.
Table
Table 3.
Table 3. Physiochemical properties 3. Physiochemical
usedproperties
Physiochemical properties of
of surfactants
surfactants used
for NBs generation. used for
for NBs
NBs generation.
generation.
Surfactant Formula Structure MW (g/mol) HLB Used by
Surfactant Formula Structure MW (g/mol) HLB Used by
Surfactant Surfactant
Methyl isobutyl Formula
Surfactant
Formula Formula Structure
Structure
Structure MW
MW (g/mol)MWHLB
(g/mol) HLB
(g/mol) Used
Used bybyHLB Used by
Methyl isobutyl [11,24,26,50,53,
carbinol
Methyl
Methyl isobutyl (CH3)2CHCH2CHOHCH3
isobutyl 102.17 6.00 [11,24,26,50,53,
carbinol (CH 3)2CHCH2CHOHCH3 102.17 102.176.00 60,97]
[11,24,26,50,53,
[11,24,26,50,53,
Methyl isobutyl carbinol
(MIBC)(CH3 )2 CHCH
carbinol
carbinol (CH
(CH 33))22CHCH
2 CHOHCH 3 22CHOHCH
CHCH CHOHCH33 102.17
102.17 6.00
6.00 60,97] 6.00 [11,24,26,50,53,60,97]
(MIBC)
(MIBC) 60,97]
60,97]
(MIBC)
(MIBC)

Pine Oil
Minerals (PO)
2022, CPEER
12, x FOR 10H18O
REVIEW 154.25 5.40 [26] 14 of 30
Pine Oil (PO) C10H18O 154.25 5.40 [26]
Pine Oil (PO) Pine
Pine Oil
OilC(PO)
(PO)
10 H18 O C
C1010H
H1818O
O 154.25
154.25 5.40
5.40
154.25 [26]
[26] 5.40 [26]
Minerals 2022, 12, x FOR PEER REVIEW 14 of 30
Minerals 2022, 12, x FOR PEER REVIEW 14 of 30
Dipropylene
Dodecylamine
Minerals 2022, 12, x FOR C
Dipropylene 6H14REVIEW
PEER O3 134.17 9.30 [26,50]14 of 30
Dipropylene glycol (DPG) glycol (DPG)
Dipropylene
hydrochloride
Dipropylene
Minerals 2022,
C H 12, CC126H
O x FOR H2814ClN
PEER OREVIEW
3 221.81
134.17 134.17 NA
9.30 [18] 14 of 30
[26,50] 9.30 [26,50]
glycol (DPG)
Dodecylamine
6 14 3
C 6 H
C6H14O3 14 O 3 134.17
134.17 9.30
9.30 [26,50]
[26,50]
glycol
(DAH)
glycol (DPG)
Dodecylamine
(DPG)
CCH 3(CH2)11NH2 185.35 185.35 10.70 [18] [13,26] 10.70
Dodecylamine
Dodecylamine
hydrochloride
(DDA)
CH3 (CH2 )11 NH 122H28ClN 221.81 NA [13,26]
(DDA) Dodecylamine
Dodecylamine CH3(CH 3(CH2)11NH2 185.35 10.70 [103][13,26]
Flotigam PEB70 *
Dodecylamine
(DDA) [R–(O–CH2 )3 –NH
hydrochloride
(DAH) CH
CH (CH
C12H3 ]28+ClN
3 22))3
11O(C
11 NH
NH 22H
2– 4 O) nH ~250
185.35
185.35 NA
10.70
10.70
221.81 195.00NA [13,26]
[13,26]
[18] NA ***
EDA 3B * (DDA)
Flotigam
(DDA)
Dodecylamine [R–(O–CH CH32COO )3–NH **3] + Commercial
Commercial cationic
cationic alkyl methyl
alkyl methyl ether monoamine [63,179]
hydrochloride
Flotigam
(DAH)
Dodecyltrimethy C12[R–(O–CH
H28ClN – 2)3–NH3] + Commercial cationic alkyl methyl221.81195.00 NA NA ***[18] [63,179]
EDA
Flotigam
Flotigam3B
* C * H ClN [R–(O–CH
hydrochloride
PEB70 CH
[R–(O–CH
C
CH 123H COO
3(CH28ClN2)32O(C2**
))33–NH
–NH ]] ++nH
2H433O) ether monoamine
Commercial
Commercial cationic
cationic alkyl
alkyl methyl
methyl ~250221.81
195.00 221.81 NA *** [103]
NA [18]
[63,179]NA
Dodecylamine hydrochloride (DAH)
(DAH)
EDA
lEDA 3B *
ammonium
12 28
C CH
15H COO
334 –
ClN2––)** ** ether monoamine 195.00
195.00
263.89 NA
NA
NA ***
*** [63,179]
[63,179]
[180]
[18]
EDA
(DAH)
PEB70 3B
3B* ** CH
CH
CH 33COO
3COO
(CH 3**
O(C2H4O)nH ether
ether monoamine
monoamine ~250 NA [103]
Dodecyltrimethy
chloride (DTAC)
PEB70 * PEB70 * CH 3 (CH2 )3CH
O(C32(CHH4 O)2)n3H O(C2H4O)nH ~250 NA
~250 [103] NA [103]
PEB70
Dodecyltrimethy
lSodium
ammonium*
CCH15H 3(CH
34ClN 2)3O(C2H4O)nH ~250
263.89 NA
NA [103]
[180]
Dodecyltrimethyl ammoniumDodecyltrimethy
l ammonium
chloride
dodecyl C(DTAC) C15H34ClN
15 H34 ClN CH₃(CH₂)₁₁SO₄Na 263.89 263.89
288.37 NA
40 [180] NA
[18,179–181] [180]
chloride (DTAC) Dodecyltrimethy
l ammonium
chloride(SDS)
Sodium (DTAC) C 15 H 34 ClN 263.89 NA [180]
Sodium sulphate
l ammonium C15H34ClN 263.89 NA [180]
dodecyl chloride
Sodium
dodecyl (DTAC)
CH3 (CH2 )11 SO CH₃(CH₂)₁₁SO₄Na
4 Na 288.37 40
288.37 [18,179–181]
40 [18,179–181]
chloride (DTAC) Collector–frother based on Straight structure with long
sulphate (SDS) FLO-YS-20
Sodium
sulphate
*
dodecyl (SDS) fatty CH₃(CH₂)₁₁SO₄Na >300
288.37 NA
40 [60,103]
[18,179–181]
FLO-YS-20 * SodiumCollector–frother acidson fatty acids
based hydrocarbon
Straight structurechain
with long hydrocarbon chain >300 NA [60,103]
dodecyl
sulphate (SDS) CH₃(CH₂)₁₁SO₄Na
Collector–frother based on Straight structure with long 288.37 40 [18,179–181]
dodecyl
FLO-YS-20 * CH₃(CH₂)₁₁SO₄Na 288.37
>300 40
NA [18,179–181]
[60,103]
sulphate (SDS) Collector–frother
fatty acids based on hydrocarbon
Straight structure
chainwith long
F507 sulphate
FLO-YS-20
F507 H(C(SDS) H(C3H6O)6.5OH based on Straight structure with long
*H6 O)6.5 OH >300
425.00 NA
8.63
425.00 [60,103]8.63
[11,24,53,97] [11,24,53,97]
3
Collector–frother
fatty acids hydrocarbon chain
FLO-YS-20* Collector–frother based on Straight structure with long >300 NA [60,103]
FLO-YS-20* fatty acids hydrocarbon chain >300 NA [60,103]
F507 H(C
fatty3Hacids 6O)6.5OH hydrocarbon chain 425.00 8.63 [11,24,53,97]
C64H124O26
F507 H(C3H6O)6.5OH 425.00 8.63 [11,24,53,97]
F507 H(C3H6O)6.5OH 425.00 8.63 [11,24,53,97]
F507 CH(C
64H3124 HO 6O)
26 6.5OH 425.00 8.63 [11,24,53,97]
Polysorbate 80 C64H124O26
C64H124O26 1310.00 15.00 [181]
(Tween 80)
C64H124O26
Polysorbate 80
1310.00 15.00 [181]
Polysorbate
(Tween 80) 80
Polysorbate 1310.00 15.00 [181]
(Tween 80)80 1310.00 15.00 [181]
Polysorbate 80
(Tween 80) * Proprietary formulation. ** R is a hydrocarbon chain with 1310.00 10 carbons. ***15.00 [181]
Not available.
(Tween 80)
Studies formulation.
* Proprietary by Nazari et** al.
R is[182] and Nazari
a hydrocarbon and
chain Hassanzadeh
with [26]
10 carbons. *** Notdemonstrated
available. that
NBs generated
* Proprietary in the presence
formulation. ** R isof dodecyl amine
a hydrocarbon (DDA)
chain are
with 10 more stable
carbons. *** Notthan pine oil (PO),
available.
 Sodium
dodecyl CH₃(CH₂)₁₁SO₄Na 288.37 40 [18,179–181]
sulphate (SDS)
Collector–frother based on Straight structure with long
FLO-YS-20* >300 NA [60,103]
Minerals 2022, 12, 462 fatty acids hydrocarbon chain 14 of 31

F507 H(C3.3HCont.
Table 6O)6.5OH 425.00 8.63 [11,24,53,97]

Surfactant Formula Structure MW (g/mol) HLB Used by

C64CH 124O26
64 H124 O26
Polysorbate 80 (Tween 80) 1310.00 15.00 [181]

Polysorbate 80
1310.00 15.00 [181]
(Tween 80)

* Proprietary
* Proprietary formulation. ** R isformulation.
a hydrocarbon**chain
R is with
a hydrocarbon chain
10 carbons. *** Not with 10 carbons. *** Not available.
available.

Studies by Nazari et al. [182] and Nazari and Hassanzadeh [26] demonstrated that
NBs generated in the presence of dodecyl amine (DDA) are more stable than pine oil (PO),
MIBC, and dipropylene glycol (DPG). According to the results, the mean size of generated
NBs was orderly categorized as DPG < DDA < MIBC< PO and DPG < MIBC < PO < DDA.
These results were ascribed partly to the surface activity of surfactants and partly to the
improved surface charge of NBs and increased hydrophobicity of the solid surface. The
same results were reported by Yasui et al. [79] and Zhou et al. [13], as they demonstrated
that some DDA molecules can adsorb on the NBs surfaces, thus making them more posi-
tively charged. In other studies, it was reported that the effects of NBs generated by MIBC,
PEB70, and FlO-YS-20 were very important in flotation [60,103]. Based on their studies,
the median size of NBs for various frothers was obtained in accordance with the order
FlO-YS-20 < MIBC < PEB70. The generation of NBs with smaller size distribution by MIBC
compared to PEB70 was due to the greater reduction in surface tension of the liquid and
greater foamability of this frother. They also investigated that NBs had a major role in the
gas holdup, and fine bubbles at a given gas holdup decreased the frother consumption.
Moreover, FlO-YS-20, which is a type of fatty acid, generated finer bubbles than MIBC at
lower concentration of reagents [60,103].
The role of MIBC and F507 frothers in flotation of fine coal particles using NBs was
studied by Sobhy and Tao [53]. They revealed that F507 produced finer bubbles than
MIBC (about 20% smaller). This is because the surface tension reduction by F507 is more
significant in comparison to MIBC. Their results were consistent with those formerly re-
ported by Fan et al. [11,24,97]. Calgaroto et al. [179] used a mixture of sodium dodecyl
sulfate (SDS) and a commercial cationic alkyl methyl ether monoamine (Flotigam EDA
3B) as the surfactant solution in their studies. They showed that highly charged and small
NBs (approximately 150–180 nm) were obtained in the presence of surfactants (10–4
mol/dm3). Similar results were reported by other researchers [18,63,180]. Recently, Phan
Minerals 2022, 12, 462 15 of 31

Studies by Nazari et al. [182] and Nazari and Hassanzadeh [26] demonstrated that
NBs generated in the presence of dodecyl amine (DDA) are more stable than pine oil (PO),
MIBC, and dipropylene glycol (DPG). According to the results, the mean size of generated
NBs was orderly categorized as DPG < DDA < MIBC < PO and DPG < MIBC < PO < DDA.
These results were ascribed partly to the surface activity of surfactants and partly to the
improved surface charge of NBs and increased hydrophobicity of the solid surface. The
same results were reported by Yasui et al. [79] and Zhou et al. [13], as they demonstrated that
some DDA molecules can adsorb on the NBs surfaces, thus making them more positively
charged. In other studies, it was reported that the effects of NBs generated by MIBC,
PEB70, and FlO-YS-20 were very important in flotation [60,103]. Based on their studies,
the median size of NBs for various frothers was obtained in accordance with the order
FlO-YS-20 < MIBC < PEB70. The generation of NBs with smaller size distribution by MIBC
compared to PEB70 was due to the greater reduction in surface tension of the liquid and
greater foamability of this frother. They also investigated that NBs had a major role in the
gas holdup, and fine bubbles at a given gas holdup decreased the frother consumption.
Moreover, FlO-YS-20, which is a type of fatty acid, generated finer bubbles than MIBC at
lower concentration of reagents [60,103].
The role of MIBC and F507 frothers in flotation of fine coal particles using NBs was
studied by Sobhy and Tao [53]. They revealed that F507 produced finer bubbles than MIBC
(about 20% smaller). This is because the surface tension reduction by F507 is more signifi-
cant in comparison to MIBC. Their results were consistent with those formerly reported
by Fan et al. [11,24,97]. Calgaroto et al. [179] used a mixture of sodium dodecyl sulfate
(SDS) and a commercial cationic alkyl methyl ether monoamine (Flotigam EDA 3B) as
the surfactant solution in their studies. They showed that highly charged and small NBs
(approximately 150–180 nm) were obtained in the presence of surfactants (10–4 mol/dm3 ).
Similar results were reported by other researchers [18,63,180]. Recently, Phan et al. [181]
studied the effect of sodium dodecyl sulfate and polysorbate 80 (Tween 80) on the gen-
eration of CO2 NBs in an aqueous system. They observed smaller diameter and higher
zeta potential magnitudes of NBs in the SDS medium. These results were attributed to the
increased CO2 concentration and the decreased surface tension of the solution. However,
NBs disappeared with the incorporation of Tween 80.
According to the results reported in the literature, it is observed that surfactants that
have little tendency to interact with the particle surface produce larger bubbles than soli-
dophilic surfactants. These surfactants include a variety of alcohols and ethers. The effect of
these surfactants can be examined from the perspective of two useful terms: selectivity and
frothing power [183]. There are several methods for classifying frothers in these two groups,
the simplest of which is the use of molecular weight (MW) and hydrophilic–lipophilic
balance (HLB) diagrams [184]. The position of the surfactants reported in Table 3 in the
MW-HLB diagram is shown in Figure 8. In general, selective frothers are surfactants
that have lower MW and HLB. These frothers are suitable for stabilizing small bubbles
due to their lower frothing power and less surface activity, and as a result, they might
improve the flotation of fine particles. In contrast, frothers with higher MW, due to the
increased elasticity of the thin film of bubbles, keep the bubbles stable in larger dimensions,
and therefore might be suitable for flotation of large particles [183,185,186]. A compari-
son of the results reported in the literature show that heavy surfactants such as PEB70
are not suitable to produce NBs. However, contrary results have been reported by other
researchers [11,24,53,97]. Although many efforts have been made to interpret the effect
of frothers on the size of MBs (generally coarser than 500 µm) [187,188] based on more
efficient factors such as critical coalescence concentration (CCC), the issue needs more
explorations in the field of NBs generation.
 parison of the results reported in the literature show that heavy surfactants such as PEB70
are not suitable to produce NBs. However, contrary results have been reported by other
researchers [11,24,53,97]. Although many efforts have been made to interpret the effect of
frothers on the size of MBs (generally coarser than 500 µm) [187,188] based on more effi-
Minerals 2022, 12, 462 cient factors such as critical coalescence concentration (CCC), the issue needs16more
of 31 explo-
rations in the field of NBs generation.

Figure
Figure 8. 8. Classification of surfactants
Classification of surfactantsbased
basedononHLB–molecular
HLB–molecular weight
weight diagram
diagram (drawn
(drawn for for HLB
values
HLB values< 15<and MW
15 and MW< 1000 g/mol;
< 1000 g/mol;Grey
Greydots correspondtoto
dots correspond other
other frothing
frothing surfactants
surfactants reported in
reported
the literature
in the literature[126,184].
[126,184].

The effect of solidophilic surfactants, such as DDA and FLO-YS-20, can be examined
The effect of solidophilic surfactants, such as DDA and FLO-YS-20, can be examined
from two perspectives: film elasticity and ionic strength. Cho and Laskowski [189] found
from two
that the perspectives:
effect of frothers film elasticity
on the andresults
bubble size ionic strength.
from theirCho andtoLaskowski
ability [189] found
prevent bubble
that the effect
coalescence. Theof frothers
stability on the
of such bubble
systems size results
is determined by from
surfacetheir ability
elasticity to prevent
forces [23,189]. bubble
coalescence.
Comparing the structure of these solidophilic surfactants with more effective frothers such forces
The stability of such systems is determined by surface elasticity
[23,189].
as MIBC and Comparing the that
pine oil shows structure of these have
these surfactants solidophilic surfactants
a much simpler with
structure. more effective
Therefore,
frothers such asof MIBC
more molecules and pine can
these surfactants oil be
shows that at
adsorbed these surfactants
a certain haveofabubbles
surface area much simpler
and can improve the elasticity and stability of the bubble thin film by creating a more
compact adsorption layer [190]. However, the dominant mechanism for improving the
production efficiency of NBs in the presence of these surfactants can be attributed to the
ionic strength of the surfactant in the aqueous system and its effect on the zeta potential of
the NBs/particle system.
Many experimental techniques such as AFM [191], rapid cryofixation/freeze-fracture [192],
neutron reflectivity measurements [193], dynamic light scattering [23], and optical visu-
alization [173] have proven that NBs can be stable for a long time. The results illustrate
that the type of surfactant can influence the stability, surface charge, and size of NBs [117].
The stability of NBs is affected by the type and number of polar groups, i.e., OH− and H+
ions, because the solution pH has an important role in the zeta potential and physicochem-
ical features of NBs [194]. It is well-demonstrated that the surface of NBs is negatively
charged due to the orientation of water dipoles at the air/water interface, and thus the
selective adsorption of OH− ions at the surface of the bubbles [70]. The type and concentra-
tion of surfactant molecules are the other important factors affecting the surface charge of
NBs [179]. For example, Kim et al. [70] performed a detailed study on the effect of different
types of polyoxyethylene methyl ether, glucopyranosides and polypropylene glycol surfac-
tants on the zeta potential and surface charge of NBs. They showed that the zeta potentials
of NBs in the presence of glucopyranosides with different lengths of alkyl chain and head
group numbers were negatively charged in a wide range of pH conditions. Under acidic
conditions, the surface charge of NBs was negative with polyoxyethylene dodecyl ether
and positive in the presence of polyoxyethylene methyl ether, whereas polypropylene
glycol provided a negative charge at the surface of NBs under alkaline conditions. They
 Minerals 2022, 12, 462 17 of 31

also introduced two factors to explain the effect of surfactants on the surface charge of
NBs: (i) the chemical characteristics of the nonionic surfactant’s head group, and (ii) the
polarity level of surfactant molecules [70]. They also demonstrated that basic ether linkages
encourage the adsorption of H+ ions where the molecules of polyoxyethylene nonionic
surfactants tend to attach to the air/water interface under acidic conditions. Contrary to
the common myth, glucopyranosides also showed similar overall trends with pH, while
it was expected that the surface charge of NBs should be positive at acidic pH due to the
higher ratio of oxygen to carbon. The fact behind this phenomenon (Figure 9) is that the
acidic OH− groups in competition with basic ether groups preserve HC ions in the bulk
water phase during the adverse interactions between H+ and OH− functions. It was also
observed that hydroxyl groups in glucopyranosides have no clouding effect on the structure
of glucopyranosides, but their competitive adsorption with H+ ions may be influenced by
the surfactant polarity. These studies revealed that the zeta potentials and critical micelle
concentration (CMC) of glucopyranosides with different alkyl chain lengths and glucose
ring numbers were of the same order at given pH values. As shown in Figure 9B,C, the mag-
nitude of the negative charge of the glucopyranoside molecules is directly proportional to
their hydrophobicity. Generally, the surface charge of NBs is significantly influenced by the
hydrophile–lipophile balance (HLB) number of the surfactant, such that polyoxyethylene
dodecyl ethers with HLBs higher than 17 reveal negative zeta potential from pH 3 to 12.
Minerals 2022, 12, x FOR PEER REVIEW
However, they suggested further studies to explore the possible relationship between HLB 17 of 3
and the zeta potential and pH to find a predictable HLB point at which the positive surface
charge appears [70].

Figure9. 9.Proposed
Figure Proposed mechanisms
mechanisms ofair/water
of the the air/water interface
interface charging
charging process:process: (A) Repelling
(A) Repelling of HC of HC
ionsby
ions byOH OH groups
− − groupsofofAGAG under
under acidic
acidic pHs,pHs,
(B) (B) enhanced
enhanced adsorption
adsorption of OHof OH
− − ionshighly
ions for for highly hy
drophobic surfactants,
hydrophobic and(C)
surfactants, and (C)reduced
reduced interaction
interaction between
between anions
anions and air/water
and air/water interface
interface for for hy
drophilic surfactants.
hydrophilic Reprintedfrom
surfactants. Reprinted from [70].
[70]. Copyright
Copyright (2022),
(2022), withwith permission
permission from Elsevier.
from Elsevier.

Calgaroto
Calgaroto et al.
et [179] studied
al. [179] the effect
studied of a commercial
the effect alkyl methyl
of a commercial alkylether monoamine
methyl ether monoam
with cationic character and SDS on the zeta potential of NBs. By comparing similar results
ine with cationic character and SDS on the zeta potential of NBs. By comparing simila
reported by Najafi et al. [18] and Jia et al. [180], they concluded that in the presence of
results reported by Najafi et al. [18] and Jia et al. [180], they concluded that in the presenc
of cationic derivatives from amines, the positive surface charge of NBs reduced the rate o
surfactant adsorption up to the isoelectric point (IEP), after which the negative charge wa
significantly neutralized. Conversely, SDS significantly neutralized the positive surfac
charge of NBs under acidic conditions where the overall charge of NBs reversed to th
Minerals 2022, 12, 462 18 of 31

cationic derivatives from amines, the positive surface charge of NBs reduced the rate of
surfactant adsorption up to the isoelectric point (IEP), after which the negative charge was
significantly neutralized. Conversely, SDS significantly neutralized the positive surface
charge of NBs under acidic conditions where the overall charge of NBs reversed to the
negative value. Studies showed that surfactants adsorb at the surface of NBs such that polar
heads orient towards the bubble through electrostatic forces and chains rearrange outwards
by hydrophobic forces and lead to a change in the zeta potential of NBs, depending on the
charge of their polar groups [179]. Similarly, Cho et al. [17] showed that the equilibrium
state between partially ionized micelles and fully ionized monomers of surfactants can
stabilize NBs.
Moreover, alkaline conditions may lead to the formation of finer and more stable NBs
because highly negatively charged bubbles will repulse each other and prevent inter-bubble
aggregation and coalescence, as reported by various researchers [20,195,196]. As mentioned
earlier, the repulsion forces among NBs due to their negative surface charge can encourage
bubble stability and decrease the rate of bubble coalescence. The zeta potentials of bubbles
with different electrolytes, reported by numerous authors, show similarities, and their
results are reviewed elsewhere [197]. For example, Uchida et al. [198] showed that a
solution containing 100 mM NaCl can improve the stability of O2 NBs for over a week;
however, an excess concentration over an optimal amount may shorten the durability of
NBs and accelerate the rate of coalescence. The stabilizing effect of surface charge can also
be attributed to the relative arrangement of the water structure at the air/water interface.
Bui et al. [117] performed a detailed study on the effect of different chemicals on the
average size and zeta potential of NBs. They showed that bubbles in the presence of EDTA
(ethylenediaminetetraacetic acid), glucose, and Na+ remained nano-sized because of the
lower adsorption of possible species at the bubble surface, whereas bubbles in DODAB
(dimethyldioctadecylammonium bromide) and trivalent metal ions became submicron-
sized after 90 min. The stability of NBs in the presence of Na+ was in agreement with
results reported elsewhere [198]. EDTA, glucose, and Na+ gave a negative surface charge
to NBs, whereas DODAB, Al3+ , and Fe3+ provided NBs with negatively charged surfaces.
Interestingly in all solutions, the zeta potential of NBs declined as the solution pH increased
from 2 to 12. Based on the works by Bui et al. [117], the possible mechanism for the creation
of negative charge at the surface of NBs can be attributed mainly to OH− (from EDTA)
and the total charge of the inner surface and adsorption layer, or to a lesser extent, to Na+
added to the solution due to the balance between inner surface charges and those of Na+
adsorbed at the air/water interface. Moreover, the positive charge at the surface of NBs
can be attributed to the partial balance between the negatively charged inner NBs surface
and cations (R+ ) adsorbed (from trivalent metal ions or the cationic surfactants) at the
air/water interface. Generally, the NBs zeta potential may shift positively, provided the
sum of the adsorbed cations’ positive charges is greater than the sum of negative charges
on the inner surface.
Hewage et al. [197] investigated the effect of ionic strength of electrolyte solutions
on the stability of NBs. They examined various electrolytes including NaCl, Na2 SO4 ,
Na3 PO4 , CaCl2 , and FeCl3 , and concluded that compared to the bulk liquid, cations have
higher concentrations at the surface of NBs. They also demonstrated that the adsorption
of low-valence cations provides a negative charge at the surface of NBs under neutral-to-
alkaline pH.

5. NB-Assisted Flotation
Traditionally used mechanical flotation cells dramatically decrease the recoverability
of ultrafine and coarse particles in the presence of CBs due to the low probability of particle–
bubble collision and high efficiency of detachment [34,64,187,188,199]. Studies have proven
that creating small bubbles can successfully increase the flotation recovery of different
mineral types (Figure 10). Improved flotation recoveries have been obtained for both
ultrafine (<10–20 µm) and coarse (>200 µm) particles [11–13,24,64,106,132,133,200]. Most
 Minerals 2022, 12, 462 19 of 31

attempts have been performed on mono-minerals, and mostly quartz, while little attention
has been given to bulk samples. For instance, Zhou et al. [5] investigated the effect of
hydrodynamic cavitation on fine silica recovery, which increased in the presence of ultrafine
bubbles from 30 to 53% at a low flow velocity of 15 m/s. Nazari et al. [34] obtained an
elevation of 21% for coarse quartz particles (−425 + 106 µm). For the same type of mineral,
Rosa and Rubio [63] attained a significant increase (from 52 to 75%) in quartz (d50 = 290 µm)
recovery in the presence of ultrafine bubbles. Following this, Calgaroto et al. [61] found
12, x FOR PEER REVIEW that the injection of NBs (200–720 nm) along with CBs (400–800 µm) improved19 of 30 flotation
recoveries of fine- and ultrafine-sized quartz particles. According to the results, flotation
with single NBs was not effective due to their very low lifting power and poor buoyancy.

Figure 10. Studies Figure

conducted on NBs-assisted
10. Studies conducted on flotation in mechanically
NBs-assisted agitated flotation
flotation in mechanically cells
agitated in cells in
flotation
1997–2021 [5,13,14,32,35,51,60,61,63,64,66,67,131,133–136,148,150,153,154,201].
1997–2021 [5,13,14,32,35,51,60,61,63,64,66,67,129,131–136,148,150,152–154,201,202].

In addition to quartz, several studies have reported a similar trend for metallic and
In addition to quartz, several studies have reported a similar trend for metallic and
non-metallic minerals. A study showed an increase of 13% in the recovery of ZnS particles
non-metallic minerals. A study showed an increase of 13% in the recovery of ZnS particles
compared to flotation with CBs [5]. Ahmadi et al. [64] confirmed that the flotation recovery
compared to flotation
of finewith
(−38 CBs
+ 14 [5].
µm)Ahmadi et al.(−[64]
and ultrafine 14 +confirmed that theparticles
5 µm) chalcopyrite flotation recov-
with NBs increased
ery of fine (−38 +by14approximately
µm) and ultrafine
16–21%. (−14 + 5enhancement
Such µm) chalcopyrite particles
was linked to thewith NBs in-
improved probability
creased by approximately 16–21%. Such enhancement was linked to the improved
of particle–bubble attachment. Additionally, collector and frother consumption were prob-
ability of particle–bubble
decreased byattachment.
50% and 75%, Additionally,
respectively.collector and frother
An improvement of 30%consumption
was reported for fine
were decreased by 50%
P2 O and 75%,
5 particles [63].respectively.
The presence An of NBsimprovement
increased the offlotation
30% was reported
recovery for particles
of coal
fine P2O5 particles [63]. The presence of NBs increased the flotation recovery of coal parti-
by approximately more than 35% [134]. NBs also played a crucial role in the entrainment
cles by approximately more than 35% [134]. NBs also played a crucial role in the entrain-efficiently
of kaolinite particles in flotation [136]. Zhou et al. [14] found that NBs could
remove the sodium oleate (NaOl) from diaspore surfaces. Li et al. [67] proposed that in
ment of kaolinite particles in flotation [136]. Zhou et al. [14] found that NBs could effi-
the presence of NBs and polyaluminum chloride, the final combustible recovery of coal
ciently remove the sodium
particles oleate by
increased (NaOl)
about from
13%. diaspore surfaces. Li et al. [67] proposed
that in the presence ofSome
NBs studies
and polyaluminum
have shown that chloride,
the NBs the final combustible
produced recovery
by hydrodynamic of
cavitation can
coal particles increased by about 13%.
improve the flotation performance of fine and coarse particles as well as decrease the
Some studies have shown
consumption that the [5,109,182,202].
of reagents NBs producedThey by hydrodynamic
concluded that the cavitation
hydrophobiccan bridging
improve the flotation
effectperformance of fine
of NBs can promote and coarse
flotation of fineparticles
particles.as well
For as decrease
example, Zhou etthe con-found that
al. [32]
sumption of reagents [5,109,182,202].
ultrafine They concluded
bubbles can improve that the
ultrafine scheelite hydrophobic
particles’ bridging
aggregation ef- recovery
and their
fect of NBs can promote flotation of fine particles. For example, Zhou et al. [32] found that
ultrafine bubbles can improve ultrafine scheelite particles’ aggregation and their recovery
to ca. 17% when the concentration of NaOl was low. The adsorption behavior of bulk NBs
produced using hydrodynamic cavitation on the muscovite surface in the presence of do-
 Minerals 2022, 12, 462 20 of 31

to ca. 17% when the concentration of NaOl was low. The adsorption behavior of bulk
NBs produced using hydrodynamic cavitation on the muscovite surface in the presence
of dodecylamine (DDA) was investigated by Zhou et al. [13]. They reported that ultrafine
bubbles adsorb on the muscovite surface in the presence of DDA, changing its surfaces to
more hydrophobic and finally increasing the flotation performance by approximately 18%.
However, this study did not discuss the interaction between generated bubbles and the
12, x FOR PEER REVIEW collector or the adsorption behavior of bubbles on the muscovite surface. 20 Seemingly,
of 30 the
NBs are surface-modified with a collector and can provide selective adsorption of the ionic
active sites exposed to the mineral surface.
Tao et al. [133] studied the influence of ultrafine bubbles on reverse anionic flotation
all varying reagent dosages. They found that starch dosage had an important effect on the
of hematite particles. NBs significantly increased the Fe recovery (approximately 16%) at
concentrate Fe grade and recovery
all varying in reverse
reagent dosages. hematite
They flotation.
found that starch dosage had an important effect on the
In addition to
concentrate Fe grade and recovery in reverseflotation
the mechanical flotation cells, column hematiteexperiments
flotation. performed
by some researchers have demonstrated
In addition the effectiveness
to the mechanical of NB-assisted
flotation cells, flotation
column flotation technol-
experiments performed
ogy mostly on coal and phosphate
by some researchersparticles. Figure 11 the
have demonstrated displays most ofofthese
effectiveness works.flotation
NB-assisted For tech-
example, it was shown that ultrafine bubbles increased P2O5 and coal flotation recoveries
nology mostly on coal and phosphate particles. Figure 11 displays most of these works.
by 10–30% and 8–27%, respectively,
For example, at different
it was shown particle
that ultrafine size fractions
bubbles increased[24,131].
P2 O5 andLicoal
et al.
flotation re-
[203] conducted coveries by 10–30% and 8–27%, respectively, at different particle size fractions [24,131].
the flotation of siliceous phosphate ore using NBs, but no specific infor-
Li et al. [203] conducted the flotation of siliceous phosphate ore using NBs, but no specific
mation was reported on the bubble size. Xiong et al. [55] reported such tendencies (about
information was reported on the bubble size. Xiong et al. [55] reported such tendencies
14%) in the presence
(aboutof14%)
NBsinfortheP2presence
O5 particles.
of NBs for P2 O5 particles.

Figure 11. Studies about 11.

Figure NBs-assisted flotation
Studies about in NBs-assisted
column flotation cells, in2008–2021
flotation column [24,53–
flotation cells,
56,83,101,107,146,202,203].
2008–2021 [24,53–56,83,101,102,107,108,146,202–204].

NBs were formed bywere

NBs a self-aerating
formed by abubble generator
self-aerating bubble ingenerator
a cycloneinflotation
a cyclonecolumn.
flotation column.
Recovery of fine particles (<10 µm) reached 86%, which was increased by 5% compared
Recovery of fine particles (<10 µm) reached 86%, which was increased by 5% compared
with that of direct flow circulation [203]. In another work, Sobhy and Tao [53] investigated
with that of direct flow circulation [203]. In another work, Sobhy and Tao [53] investigated
the recovery of coal particles in a column flotation in the presence/absence of NBs, where
the recovery of coal particles in a column flotation in the presence/absence of NBs, where
the bubbles were formed through dissolved air (DAF) in coal slurry. Results showed an
the bubbles wereenhancement
formed through dissolved
of about 50% (from air47(DAF)
to 97%)inincoal slurry. Results
the combustible showed
recovery of −an
150 µm coal
enhancement of about 50% (from 47 to 97%) in the combustible recovery of −150 µm coal
particles. Fan et al. [54] indicated that in coal particles with coarse sizes of −355 + 600 µm,
the recovery was enhanced from 13 to 22% using NBs, while the corresponding improve-
ments were 8%, 28%, and 46% in fine particles of −38 + 45, −20 + 38, and −20 µm, respec-
Minerals 2022, 12, 462 21 of 31

particles. Fan et al. [54] indicated that in coal particles with coarse sizes of −355 + 600 µm,
the recovery was enhanced from 13 to 22% using NBs, while the corresponding improve-
ments were 8%, 28%, and 46% in fine particles of −38 + 45, −20 + 38, and −20 µm,
respectively. Experimental results reported by Ma et al. [56] showed that coal recovery in
the presence of ultrafine bubbles increased by 10–39%, halved frother and collector dosages,
reduced the required air consumption, and increased the capacity of the flotation column
to some degree.
Table 4 presents the scale and the level of recovery improvement of coal and mineral
flotation assisted with NBs. Considering the results given in the cases studies, it was
recognized that the most attention was paid to proving an improvement in recovering only
some typical minerals and coal particles in the presence of ultrafine bubbles. Almost all of
them were performed under different experimental setups, reagent regimes, and operating
conditions, leading to the creation of slight differences among the results. Thus, the role of
NBs on the grade and selective separation was relatively overlooked and still needs to be
understood and explained. Another challenge in these studies is rescaling the laboratory
results to industrial applications. As can be seen in Table 4, efforts in the industrial use of
NBs are very limited and constrained to coal flotation on a semi-industrial scale. The reason
for this comes from the simplicity of the coal flotation process compared to complex ores
such as sulfides. Therefore, the development of investigations in the field of exploration
of mechanisms and the interaction of NBs with particles in complex systems (no single-
mineral system) will be the first step to find industrialization solutions for the application
of NBs in the mineral processing industry. Additionally, according to Table 4, the method
used on the largest scale is of cavitation type. This method is currently used on a large
scale in spargers used in flotation columns. For this reason, the efficiency of this method
has been evaluated and approved on an industrial scale. Therefore, it seems that the main
challenge in large-scale applications of NBs does not arise from mechanical aspects.
Flotation kinetics include several sub-processes that take place in the pulp and froth
phases, including particle–bubble collision and attachment, transport of the particle–
bubble aggregate to the froth phase, and recovery of the particle from the froth phase
to a concentrate launder. The bubble size and froth stability significantly affect these sub-
processes [204]. The flotation rate constant depends on the particle hydrophobicity, particle
size, solids content, feed rate, froth depth, reagent type, reagent dosage, gas flow rate,
and bubble diameter (bubble generators) [205].
Two factors that contribute to the increased flotation rate constant are (i) NBs formed
on hydrophobic particles may cause agglomeration by a bubble-bridging mechanism
resulting in an enhancement of the collision efficiency; and (ii) particles frosted with the
bubbles may present a surface favorable to attachment to CBs. In this regard, several
case studies addressed an improvement in the flotation kinetics rate (k) of minerals in
the presence of NBs (Table 5). For instance, Nazari et al. [51] showed that k of quartz
coarse particles improved by 21% in the presence of DDA-NBs. Han et al. [35] reported an
endearment of 37% in coal flotation kinetics, attributing it to an increase in collision and
attachment probabilities and a reduction in detachment probability. In another work, the
flotation kinetics rate of hematite was reduced from 3 to less than 1 min [133]. Farrokhpay
et al. [201] focused on the kinetics of fine particles in the presence of MBs and CBs, reporting
higher values when the NBs were applied. One main reason for higher kinetic rates in
the presence of ultrafine bubbles is related to the increased hydrophobicity expressed by
the water contact angle. For instance, the water contact angle on quartz measured by the
sessile drop technique increased from 18◦ (standard deviation = 3.6◦ ) to 46◦ (standard
deviation = 7◦ ) in the presence of NBs [61].
Minerals 2022, 12, 462 22 of 31

Table 4. Summary of observed change in the flotation recovery for mechanical and column flotation cases. UN: unknown or not mentioned in the manuscript.

Flotation Cell Materials Scale NBs Size (nm) Equipment Relative Change (%) Refs.
Silica Laboratory UN Venturi tube 23 [5]
ZnS Laboratory UN Venturi tube 13 [5]
Quartz Laboratory 171 Venturi tube 21 [34]
Quartz Laboratory 150–200 Depressurization of DI water 23 [63]
Quartz Laboratory 200–720 Steel needle valve 13 [61]
Mechanical flotation Chalcopyrite Laboratory 358 Venturi tube 21 [64]
P2 O 5 Laboratory 150–200 Depressurization of DI water 30 [63]
Coal Laboratory ~300 Hydrodynamic cavitation 35 [134]
Kaolinite Laboratory <120 Decompression 8 [136]
Diaspore/kaolinite Laboratory 100–300 Venturi tube 14 [14]
Coal Laboratory 100–200 Ultrasonic cavitation 13 [67]
Scheelite Laboratory UN Venturi tube 17 [32]
Muscovite Laboratory 100 Venturi tube 18 [13]
Hematite Laboratory 150–280 Venturi tube 16 [133]
P2 O 5 Laboratory <1 µm Venturi tube 30 [24]
Coal Pilot <1 µm Venturi tube 27 [131]
Column
P2 O 5 Laboratory 150–240 Venturi tube 14 [55]
flotation
Coal Laboratory <1 µm Venturi tube 50 [53]
Coal Pilot 700 Hydrodynamic cavitation 46 [54]
Coal Laboratory 160–250 Venturi tube 39 [56]
Minerals 2022, 12, 462 23 of 31

Table 5. Summary of observed changes in the flotation rate constant for mechanical and column
flotation cases.

Flotation Cell Materials Relative Change (%) Refs.

Silica 40 [5]
Zns 65 [5]
Coal 98.4 [131]
PGM 61 [148]
Quartz 36 [51]
Mechanical flotation Muscovite 26 [13]
Coal 33.6 [35]
Quartz 75 [200]
Apatite ore 10.4 [153]
Coal 14.4 [135]
Rutile 42.7 [150]
Coal 40 [97]
Column flotation Phosphate 109 [24]
Coal 160 [54]

6. Conclusions and Future Works

Efficient recovery of fine, ultrafine, and coarse particles has been a long-standing
challenge in flotation processes for over a century. A wide diversity of research investi-
gations have been undertaken to overcome this, and recently, NB-assisted flotation has
appeared as a promising technique. To this end, the present review addresses the key
opportunities and challenges regarding the generation and detection of ultrafine bubbles
as well as the effectiveness in recovering particles and flotation kinetics. The following
findings were highlighted.
• Evaluating literature data showed that while CB analyzers are used to detect ultrafine
bubble sizes and distributions, the most commonly used methods are LPSA and NTA
instruments, which may include a reasonable amount of bias.
• Alkaline environments lead to the formation of smaller and stable bubbles because
highly negatively charged bubbles tend to repel each other, which prevents inter-
bubble aggregation and coalescence.
• Hydrodynamic cavitation was found to be the most popular technique for producing
NBs, which can be likely extended to industrial applications in the future.
• An integrated separation of minerals in flotation using ultrafine bubbles reduces col-
lector and frother consumption and improves not only recovery but also the flotation
rate constant of fine, ultrafine, and coarse particles.
• Flotation in the presence of NBs can elevate the recoverability of mono-minerals
by approximately 15% and 20% on average using mechanical and column flotation
cells, respectively.
• Most of the focus in the last two decades has been on approving the existence, stability,
and impact of single-mineral flotation, and little attention and few reports have been
on bulk and actual ores.
Considering the above conclusions and given information in the literature, the follow-
ing future works are recommended:
• There are no solid comparative results concerning generating and observing ultrafine
bubbles using commonly used apparatus. Thus, such information can help in better
quantitative judgment among common techniques.
• Although some basic principles about how to generate and apply NBs to flotation
research and operations are known, challenges remain in quantifying and mathemati-
cally describing their role in flotation.
• Future research should be focused on understanding the stabilization mechanisms of
bubbles generated by different methods, optimizing their size ranges for maximized
Minerals 2022, 12, 462 24 of 31

flotation recovery, minimizing wear and damage in industrial operations, and intensi-
fying the role of in situ NB nucleation on particles in flotation.
• From an economic point of view, there is no information in the literature about total
costs versus metallurgical beneficiations.
• Although a reasonable degree of recovery improvement has been widely reported in
the literature, researchers have rarely reported the impact of NBs on grade, separation
efficiency, and selectivity of separation. Thus, further studies are recommended in
this sense.
• The synergy of chemical, physical, and hydrodynamic features for NB generation in
an energy-efficient, technically effective, and user-friendly manner, with controlled
sizes of generated bubbles, are also important goals in the future.

Author Contributions: Conceptualization, S.N. and A.H.; methodology, S.N. and A.H.; investigation,
S.N., A.H., H.K. and P.B.K.; validation, S.N. and A.H.; data collection, S.N., A.H. and H.K.; writing—
original draft preparation, S.N., A.H. and H.K.; writing—review and editing, S.N., A.H., H.K., Y.H.
and P.B.K.; visualization, A.H., P.B.K. and Y.H.; and supervision, A.H., Y.H. and P.B.K. All authors
have read and agreed to the published version of the manuscript.
Funding: This work was supported by the Fundamental Research Funds for the Central Univer-
sities (2022QN1072).
Conflicts of Interest: The authors declare no conflict of interest.

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