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org/Langmuir Article

On Nanobubble Dynamics under an Oscillating Pressure Field

during Salting-out Effects and Its DLVO Potential
Kalyani Agarwal, Mohit Trivedi, Claus-Dieter Ohl, and Neelkanth Nirmalkar*
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ABSTRACT: We have investigated the origin, stability, and

nanobubble dynamics under an oscillating pressure field followed
Downloaded via INDIAN INST OF TECH ROPAR on April 12, 2023 at 19:25:54 (UTC).

by the salting-out effects. The higher solubility ratio (salting-out

parameter) of the dissolved gases and pure solvent nucleates
nanobubbles during the salting-out effect, and the oscillating
pressure field enhances the nanobubble density further as solubility
varies linearly with gas pressure by Henry’s law. A novel method
for refractive index estimation is developed to differentiate
nanobubbles and nanoparticles based on the scattering intensity
of light. The electromagnetic wave equations have been numeri-
cally solved and compared with the Mie scattering theory. The
scattering cross-section of the nanobubbles was estimated to be smaller than the nanoparticles. The DLVO potentials of the
nanobubbles predict the stable colloidal system. The zeta potential of nanobubbles varied by generating nanobubbles in different salt
solutions, and it is characterized by particle tracking, dynamic light scattering, and cryo-TEM. The size of nanobubbles in salt
solutions was reported to be higher than that in pure water. The novel mechanical stability model is proposed by considering both
ionic cloud and electrostatic pressure at the charged interface. The ionic cloud pressure is derived by electric flux balance, and it is
found to be twice the electrostatic pressure. The mechanical stability model for a single nanobubble predicts the existence of stable
nanobubbles in the stability map.

■ INTRODUCTION
Nanobubbles has gained significant attention from both
applied and fundamental research viewpoints in recent
times. 1−3 Nanobubble encompasses a wide range of
applications, particularly toward the 21st century grand
challenges such as water technology,4−6 food sector,7,8 health
technology,9−12 energy sectors, energy efficient aeration,13
surface cleaning,14 disinfection and sanitization,15 mineral
flotation,16 ultrasound contrast agent,17 drag reduction,18 drug
delivery and smart medicine,19,20 tumor hypoxia,21 etc. Despite
numerous applications, the fundamental of the nanobubbles is
under infancy. Broadly, the phase transition or formation of a
new phase via nucleation or mixing is essentially a departure
from the thermodynamic equilibrium. The out-of-equilibrium
conditions give rise to steeper gradients, thereby leading to
interesting colloidal and interfacial phenomena. Indeed, these
nonequilibrium conditions are driven by either one or multiple
influences of phase transfer, external volumetric forces/electric,
magnetic forces, mixing, chemical reaction-driven instabilities,
nonuniform surface tension, etc. Nanobubbles are a two-phase
system that can be created by manipulating such volumetric
driving forces. In this work, we have investigated the
nanobubble generation during the salting-out effect and the
influence of the oscillating pressure field. The term “salting-out
effect” is used interchangeably in salt precipitation by
dissolving the higher soluble compound in the base solution.
Similarly, the gas solubility decreases upon dissolving other
more soluble components in the base solvent, also termed the
salting-out effects.22,23 From a thermodynamic viewpoint, the
dissolved gas in water at a fixed temperature and pressure can
be considered in thermodynamic equilibrium. The Gibbs free
energy of such a multicomponent system is well-defined by the
Gibbs−Duhem equation (combined representation of the first
and second law of thermodynamics). At constant temperature
and pressure, Gibbs free energy solely depends on the chemical
potential of the individual components. Furthermore, the salt
dissolution is expected to increase the chemical potential of the
system [for an ideal solution, μi = μio + RT ln(xi)]. Now, the
new thermodynamic equilibrium state can be achieved by
minimizing the Gibbs free energy of the system, and therefore,
the new interfaces may be created in the form of nanobubbles
due to the dissipation of additional free energy. In other words,
salt mixing/dissolution is the volumetric driving force for the
out-of-equilibrium of the system that gives rise to hetero-
Received: November 11, 2022
Revised: March 27, 2023

© XXXX American Chemical Society https://doi.org/10.1021/acs.langmuir.2c03085

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Figure 1. Schematic of the experimental setup and applied pressure wave.
geneity in the form of nanobubbles. Furthermore, the
volumetric driving force can also be expected to have a
proportional relationship with the new surface creation. The
free energy of the system can also be enhanced by performing
work on the system. For instance, oscillating pressure fields
and ultrasound waves are expected to enhance the free energy
of the system, and therefore, the nanobubble density should
increase when the system undergoes energy minimization. In
this work, we have experimentally verified this fact by
employing the fluctuating pressure field, and our results
show a higher concentration of nanobubbles under the
oscillating pressure field.
Despite the overwhelming application of nanobubbles, the
extraordinary stability of the nanobubbles is still puzzling. The
early speculation was the probability of contamination, such as
active surface molecules, dust, or nanoparticles, etc. For the
nanodroplet generation, diverse emulsification approaches
have been utilized which are similar to bulk nanobubble
formation including high-pressure homogenizer,24 ultrasonica-
tion,25 and light-driven mechanism enveloping porous
membrane.26 Therefore, it is customary to provide strong
scientific evidence of the gas-filled nanobubbles which
differentiate from nanoparticles or nanodroplets. Broadly, the
evidence of the gas-filled nanobubbles is reported by various
methods, for instance, optical methods,27 physical perturbation
techniques,28−30 electron microscopy,31,32 vibrational spectros-
copy,33 surface charge measurement, etc. The advantages and
disadvantages of the various techniques have been critically
examined elsewhere.34 The physical perturbation to the
nanobubble suspension results in the disappearance of
nanobubbles during freezing and thawing, which indicates
the presence of a soft interface. However, it should be
emphasized here that particle aggregation might occur even
when freezing samples in liquid nitrogen.35 Nanoparticles
present with nanobubbles may also agglomerate due to
freezing, and agglomerated nanoparticles can be detected by
NTA, whereas nanobubbles may disappear completely. The
presence of solid particles along with nanobubbles is not very
surprising. During freezing and thawing experiments, the nano-
objects disappear only after the repeated freeze−thaw process.
The size of the nano-object was also reported to be
significantly higher after the thawing process; perhaps the
particle aggregation may be giving rise to the larger size of the
nano-object. Furthermore, if solid particles are present in the
water, they may act as nuclei for heterogeneous nucleation of
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nanobubbles on a particle surface. However, the nanobubble
generation by gas superstation may be a homogeneous
nucleation of nanobubble by virtue of differences in gas
solubility at different pressure or temperature. Furthermore,
electron microscopy emerged as an important method for
determining the structure of nanoscale entities at high
resolution. The ultrahigh-resolution images of individual
particles and their internal structure are used to investigate
the sample properties and behavior. The electron beam as the
imaging radiation source permits for higher spatial resolution
(on the tens of picometers scale) than photons in optical
microscopy (200 nm). Bunkin et al.36 reported a phase
contrast microscopy technique to estimate the refractive index
of nanosized entities. The refractive index of the gas bubble
must lie around RI = 1.000, much lower than that of the water
RI = 1.330. In addition, the refractive index of solid particles
and droplets is expected to bear a refractive index value greater
than 1.330. More recently, off-axis digital holographic
microscopy (DHM) was also utilized to estimate both the
refractive index and the size of nanobubbles.37 In this work, we
have developed a new method to estimate the refractive index
of nanobubbles by measuring the scattering power during
nanobubble tracking analysis. We have estimated the refractive
index of nanobubbles generated during salting out and
oscillating pressure fluctuation to be 1.001, which indicates
that they are indeed gas-filled nanobubbles. Nanobubbles are
reported to be stable for days and months in water; however,
the existence of nanobubbles in liquids other than water is still
an open question. Recently, several stability models for the
nanobubbles have been proposed, namely, the skin model,
dynamic equilibrium model, ion stabilization, etc.38 The most
recent understanding of nanobubble stability is the ion
stabilization.38,39 A mechanical stability model is proposed
based on the force balance around the nanobubble. In general,
the surface tension force is expected to compress the air−water
interface while the electrostatic force between the ions at the
interface acts opposite to the surface tension force. In addition,
the ionic cloud pressure is expected to act opposite to the
electrostatic force.
■ EXPERIMENTAL METHODS
Materials. All experiments were performed using Milli Q collected
from the Milli Q water unit. The pH (6.9) and conductivity (1.357 μS
cm−1) of water referred to as pure water was measured at 20 °C,
employed for the generation of bulk nanobubbles. In addition,
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aluminum chloride (AlCl3, 99.9%), calcium chloride (CaCl2, 99.5%),
sodium sulfate (Na2SO4, 99.5%), and sodium chloride (NaCl, 99.5%)
were procured from Merck Chemicals. The stock solution was
prepared in pure water at room temperature followed by constant
stirring for 45 min. The disposable silicon-free syringes (HSW
NORM-JECT), glass vials, and pipettes were used throughout the
experiments to avoid possible contamination. Preceding the
experimentation, glassware is washed with a cleaning agent (neutral
pH labolene solution) and rinsed with ethanol and water followed by
drying in the oven. Rinsing with ultrapure water is also done multiple
times, and the discharged water is tested for nanoscale entities using
NTA which confirms the absence of nanoscale entities. A 15 mL vial
is used to store the sample for long term stability analysis. The
nanobubble sample prepared in pure water is referred to as 0 mM, i.e.,
without the addition of salt. The nanobubble size distribution and
surface charge were measured by particle tracking and dynamic light
scattering techniques.
Oscillating Pressure Field Setup. Pure water and salt solution
of varying concentration (8 mL), respectively, were poured into a
glass U-tube manometer that was capped with one side and a 50 mL
syringe connected onto the other side of the glass U-tube. An
MPX5700 pressure sensor by NXP, a Freescale Semiconductors, Inc.
subsidiary, is used for the pressure measurement. For better accuracy,
the pressure sensor output is interfaced with the ADS1115-based
ADC (analog-to-digital) converter module, and the built-in ADC
converter of Arduino UNO is avoided. A DS3231 [3] based RTC
(real-time clock) module calculates the sampling interval between
consecutive measurements. The internal temperature sensor of
DS3231 is used to obtain the temperature reading during the
experiment.
Because of the presence of bus voltage in the sensor’s pressure
equation, the bus voltage is also interfaced with the ADS1115 through
a precision resistor voltage divider. Nanobubble generation is carried
out through an oscillating pressure field schematically illustrated in
Figure 1. The operating principle of the setup is the periodic change
in internal pressure in the U-tube induced by the linear motion of the
piston, which is transformed by the eccentric wheel rotating by an
electric motor. Consequently, the pressure field generates the
solubility difference leading to nanobubble generation. The motor
frequency and operating time were set to 500 rpm and 13 min during
the experiment.
Ultrasound Irradiation. The horn-type ultrasound offers a
frequency response of 20 kHz frequency with amplitude variation
from 25% to 98% and delivers 750 W of constant power. The probe
(1/2” dia ≈ 13 mm) is fabricated from high-grade titanium alloy Ti-
6Al-4 V due to its high tensile strength, good acoustical properties,
high resistance to corrosion, low toxicity, and excellent resistance to
cavitation erosion. The 60 mL sample was subjected to ultrasound
irradiation for 5 min and further characterized using NTA and DLS.
Nanobubble Characterization by Particle Tracking and
Dynamic Light Scattering Method. The nanobubble size
distribution and nanobubble concentration were measured by the
particle tracking method. The Brownian motion of the nanobubbles
was recorded by an sCMOS camera and processed by nanoparticle
tracking analysis (NTA) software (NanoSight NS300 and NTA 3.3
Analytical Software, Malvern Instrument, United Kingdom). The
NTA technique tracks the individual nanobubbles to estimate the
mean square displacement and calculates the mean size and
concentration of the nanobubbles using the Einstein-Stoke equation.
The zeta potential is measured by the dynamic light scattering (DLS)
technique (Zetasizer Nano ZSP, Malvern Instruments, UK).
Refractive Index Determination. The light scattering from the
nanobubbles is also measured during particle tracking by NanoSight
NS300. The distribution of scattering power of the nanobubble
sample was recorded. The time and number-averaged value of the
maximum scattering power PS (AU) is selected for the refractive index
calculation. The standard polystyrene nanoparticles are used to
perform the instrument calibration. It is, however, to be noted that
NTA Instruments often suffer from nonuniform illumination, and
also, the distance to optical focus affects the scattering intensity of a
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particle.40,41 This method is inspired by the method reported by van
der Pol et al.40 and de Rond et al.41 The scattering intensity of the
polystyrene nanoparticles of four different sizes (50, 100, 150, and
200 nm) with a refractive index of 1.630 is used to calculate the
scattering cross-section σS (nm2) by comparing with the Mie theory.
The open-source MieConScat software used to calculate the
scattering cross-section requires the particle size, the refractive index
of a given material and medium, and the light source wavelength also
needed for the theoretical scattering cross-section (see the details of
Mie theory in the Supporting Information). Mie scattering is an
analytic solution of the Maxwell equations to the scattering of an
electromagnetic wave with a dielectric spherical object. The solution
is an infinite series of vector spherical harmonics. The measured PS
value is matched with the scattering cross-section σMie calculated from
the Mie theory. The instrument constant σMie/PS = 0.0673 is obtained
by linear regression of the data point. It is also to be noted that the
adopted strategy of using the time average and number-average
maximum intensities of the particles and the maximum scattering
intensity/power of a single particle was found to have a negligible
difference in the calculation of the refractive index for nanobubbles.
Transmission Electron Microscopy Characterization. The
Cryo-TEM imaging of nanobubbles was carried out by an FEI-Tecnai
G2 12 Twin TEM 120 kV equipped with a low-temperature Gatan
unit. A 4 μL nanobubble sample was deposited on a carbon-coated
gold grid, and the vitrification was performed with liquid ethane by
using Vitrobot (FEI Company). Later, the vitrified nanobubble grid
was transferred to the Cryo holder, and images were obtained at an
acceleration voltage of 120 kV and a temperature of −174 °C. The
same procedure is adopted to characterize nanobubbles in the salt
solution. TEM bright-field (BF) mode results in images constructed
by uniform lighting of the whole sample, resulting in a dark picture on
a lighted background. Herein, the contrast is generated by the
absorption of the electron beam in dense areas of the specimen where
the light source angle is subjected to 45 and 90°. Areas with
suspended nanobubbles are expected to appear to be dark in
micrographs obtained by bright-field TEM. The backdrop is bright in
the bright field image, while the objects are dark. Before reaching the
specimen, the electron beam travels directly via an aperture. The
appearance is the consequence of the direct beam being weakened by
its contact with the sample. The ratio of the strength of the signal
from the feature to that of the background is known as a contrast.
Since the features seem dark and the field appears light, the features
are unexpectedly overlooked during analysis and appear to be darker
during the bright-field TEM imaging. Even though the image
resolution in side views is enough to confirm the exact shapes of all
the bubbles, the majority of the observed entities depict a spherical
shape.
■ RESULTS AND DISCUSSION
Salting-out Effects and Oscillatory Pressure Fluctua-
tion on Nanobubble Dynamics. As noted earlier, the
salting-out effect is the decrease in the solubility of gases
during salt dissolution. The dissolution of salt in water
undergoes ion dissociation, which further forms the solvate of
ions with water molecules. The solvation of the ions reduces
the affinity of gaseous molecules with water molecules, and
thus, the solubility of the gas decreases. Recently, it was shown
that the excess gas during the salting-out effect nucleates in the
form of nano-objects.42 These nano-objects were observed to
have similar characteristics, such as extraordinary longevity,
negative zeta potential, etc. The nanobubble density was
reported to correlate positively with the salting-out parameter.
The following expression relates the solubility of gas and the
salting-out parameter:
(1)
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where S0, S, h, and ci are the gas solubility in pure water, gas
solubility in the salt solution, salting-out parameter, and salt
concentration, respectively. The salting-out parameter de-
creases with salt valency; therefore, the bubble number density
in di- and trivalent salts was less than that in monovalent salt.
From the salting-out experiments, it is reasonably clear that the
solubility ratio gives rise to the nucleation of nano-objects. The
solubility ratio can be further increased by employing the
oscillating pressure field as the partial pressure and solubility of
the gas are linearly dependent on Henry’s law (pg = Hcg). The
oscillating pressure field is applied in the pure water and salt
solution filled in the u-tube geometry by the cylinder and
piston system. A pressure sensor records the pressure
fluctuations and varies from +30 kPa to −30 kPa (see Figure
1). The solubility difference created by oscillating pressure is
approximately 30%. The time evolution of the nano-objects
size distribution in pure water and 1 mM NaCl solution is
shown in Figure 2a. The bubble distribution area increases
Figure 2. Effect of cycle time on nanobubble generation by oscillating
pressure method. (a) Bubble size distribution and (b) mean object
diameter and zeta potential.
with the cycle time in pure water and NaCl solution, which
translates into the bubble number density. In other words, the
nano-object density significantly enhances by oscillating
pressure fluctuation due to a higher solubility ratio from ∼9
× 107 bubbles/mL to ∼2 × 108 bubbles/mL (see Figure S2b)
in the case of pure water (0 mM NaCl). On the other hand,
the mean object diameter and zeta potential remain constant
(≈ −20 mV) with the cycle time, as shown in Figure 2b.
Furthermore, the mean object diameter in pure water (180−
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200 nm) is always observed to be smaller than that in the salt
solution (160−350 nm). The mean object diameter of the
nanoscale object exhibits an inverse dependence on the zeta
potential (regardless of the sign). In other words, a higher zeta
potential corresponds to a smaller object diameter. The wide
spectrum of zeta potential at the bubble surface generates such
a strong repulsive force among the neighboring bubbles that
coalescence is successfully prevented, even when the Bjerknes
force is present. The mean object diameter falls as the zeta
potential increases, which signifies the accumulation of surface
charge that tends to shrink the mean size of these nanoscale
objects. In addition, the mean object diameter during the
salting-out effect was also observed to be larger than that
generated under oscillating pressure fluctuation (see Figure
2b). Interestingly, the zeta potential during the salting-out
effect was significantly smaller than that generated by the
oscillating pressure field.
From the preceding discussion, it is reasonably evident that
the nanobubble density positively influences the solubility
ratio. The oscillatory pressure field increases the solubility
difference by 30% in comparison with the salting-out effect.
The zeta potential of nanobubbles in pure water was higher
than that in the salt solution (see Figure 2b). The decrease in
the zeta potential of nanobubbles in the salt solution is
attributed to the screening of an electric double layer around
nanobubbles. The mean object diameter directly relates to the
zeta potential acquired by the bubble. The higher the zeta
potential the lower the size of the nanobubbles. Dynamic light
scattering and the cryo-TEM method have further verified this
claim. The dynamic light scattering method measures the
scattering light intensity in volume, and the average hydro-
dynamic diameter is the volumetric average of individual
bubbles. The mean diameter measured by dynamic light
scattering also confirms that the mean diameter of objects in
the salt solution is higher than in pure water. However, the
mean diameter measured by dynamical light scattering was
slightly higher than the particle tracking method. On the other
hand, the cryo-TEM method predicts a much smaller
nanobubbles size range (12.185 nm is the lowest size) in 0
mM NaCl (see Figure 3d). As expected, the cryo-TEM
method also predicts the mean diameter of objects in pure
water to be higher than in salt solution (see Figure 3a,b).
However, the cryo-TEM method underestimates the bubble
size (Figure 3b) with respect to the dynamic light scattering
and particle tracking method. Note that nanobubbles were
frozen in liquid ethane, and the images were taken by TEM. So
the state of water during the characterization of nanobubbles
by cryo-TEM and the particle tracking method is different.
Despite the different working principles of cryo-TEM, dynamic
light scattering, and particle tracking methods, the mean
diameter of the objects in pure water is measured to be smaller
than in the salt solution. The reasoning behind the behavior of
nanobubbles in the presence of salt has been described by
putting forward a new theoretical model for nanobubble
stability, discussed in the later section. We attempted to
measure the hydrodynamic size of nanobubbles in salt solution
using DLS, and DLS showed an error in the measurement that
the suspension is very dilute. After preparing the stock
solutions, the bubble number density is extremely low
(observed in the NTA) which is further enhanced by
employing generation techniques for nanobubble formation.
The broad size distribution was scattered with a hydrodynamic
diameter above approximately 700 nm in such a polydisperse
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Figure 3. Cryo-TEM micrographs for nanobubble suspension generated in (a) 1 mM NaCl, (b) 0 mM NaCl, (c) nanobubble size distribution (0
mM NaCl), and (d) nanobubble size distribution (0 mM NaCl).
suspension of low concentration. Furthermore, it is important
to compare the bubble number density by NTA and cryo-TEM
techniques. All else being equal, the bubble number density
predicted by NTA and cryo-TEM was ∼108 and ∼1014
bubbles/mL, respectively. The cryo-TEM not only predicts
the significantly higher bubble number density but also
captures the smaller size nanobubbles that are not detected
by NTA because of its inherent limitation.
Light Scattering and Electrical Conductivity of
Nanobubbles. The experimental setup for oscillatory
pressure fluctuation was designed to avoid the possible source
of contamination (see Figure 1). The wet part in this setup was
only the u-tube made of glass. Although the piston and syringe
assembly is not in contact with water in order to make the
experimental protocol uniform, the piston and cylinder system
was also first cleaned with ethanol and water and dried by
sparging with nitrogen gas. A similar cleaning protocol was
followed in each step while transferring the sample from one to
another. Silicon-free syringes were used for the particle
tracking analysis. We have not only followed a strict
experimental protocol but also estimated the refractive index
of nanobubbles to provide experimental evidence of gas-filled
bubbles. As noted earlier, bubbles, particles, and droplets
behave significantly different with light propagation. The
scattered light through the nonoentities contains information
about the phase of the electromagnetic waves.
The light scattering from a nano-object strongly depends on
its refractive index; the scattering cross-section increases with
the refractive index.40,41 On the basis of the measured intensity
of scattered light, the refractive index of the nanosuspension
can be determined by Mie scattering theory (see details in
Figure S1). The scattering intensity of polystyrene nano-
particles (d = 100 nm) was used as a reference material. The
scattering cross section by polystyrene nanoparticles has been
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compared with Mie scattering and electromagnetic wave
simulation (see Figure S3a). A close match between theory
and numerical simulation was observed. The corresponding
simulation for nanobubbles in salt solution was performed and
compared with Mie scattering theory as shown in Figure S3b.
The far-field radiation of electromagnetic waves was gauged by
the norm of the far electric field in the x−z plane. Clearly, the
scattering of electromagnetic waves (λ = 405 nm) is
significantly higher for polystyrene nanoparticles in compar-
ison with nanobubbles in NaCl solution (see Figure 4a). The
experimentally measured scattering intensity of laser light (405
nm) confirms the finding as shown in Figure 4b, which shows
the overlap between particles and bubbles. It seems that the
solid particle may also be present along with the nanobubbles.
However, the fraction of nanobubbles may be significantly
higher than solid particles as the sample’s refractive index is
estimated to be 1.002 ± 0.02, which is closer to the air
nanobubbles. It is reasonable to argue that the filtration
process surely may not be able to eliminate the solid particles
of the order of 100 nm. The particle tracking system is
calibrated with the known refractive index of the particles, as
shown in Figure 5a, which shows the refractive index of
nanobubbles generated by oscillating pressure fluctuation in
different salt solutions after salting out (see Figure 5b). In both
cases, the refractive index of nanobubbles was estimated to be
close to 1. The ultrasound probe may generate nanoparticles
depending on the tip quality and total operational time.43
However, the ultrasound probe can be safely used in the 130−
750 W power range and for a shorter operational time (≈ 5
min). We have estimated the refractive index of nanobubble
treated by probe ultrasound as shown in Table 1.
The electric conductivity of the nanosuspension has also
been measured. For instance, the conductivity of the Milli Q
water and nanobubble water was measured to be 1.639 μS
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Figure 4. (a) Numerical comparison of the scattered electric field (E)

and (b) comparison of the scattering intensities of 100 nm
monodispersed polystyrene latex beads and the NBs generated by
the salting-out effect using NaCl and AlCl3 measured by NTA. Figure 5. Refractive index estimation. (a) Variation of scattering
cross-section with the size of polystyrene nanoparticle. (b) Refractive
cm−1 and 1.214 μS cm−1, respectively. The electrical index of different salt valency.
conductivity of nanobubbles drops by ∼25%. The drastic
decrease in electric conductivity can also be considered as one Table 1. Refractive Index Variation with Ultrasound
evidence of nanobubbles. Usually, the electrical conductivity of Amplitude
the nanoparticle suspension increases with the fraction of the amplitude (%) 0 mM NaCl 1 mM NaCl
nanoparticle. Since nanobubbles are gas-filled entities, the 0 1.002 1.003
effective conductivity drops as gaseous molecules are poor 25 1.005 1.006
conductors of electricity. In a nutshell, the electrical 40 1.006 1.003
conductivity of the nanosuspension can be used to differentiate 55 1.004 1.003
nanobubbles from nanoparticles. However, the refractive index 60 1.004 1.001
method provides a piece of robust scientific evidence for the 70 1.005 1.002
nanobubbles. The maximum error in RI was estimated to be 85 1.004 1.002
0.045, where the minimum error was 0.001. The average error 98 1.003 1.005
in the RI was evaluated to be 0.02, and the average refractive
index of nanobubbles can be expressed as 1.002 ± 0.02,
irrespective of the salt solution. Furthermore, the presence of characteristics such as negligible buoyancy and a steep rise in
dissolved gas is shown to have a substantial influence on mass transfer efficiency compared to macro or microbubbles.
electrical conductivity at a lower salt as compared to higher However, the puzzling stability of the nanobubbles is still in a
concentrations. Though ionic effects dominate in changing the paradoxical state.
electrical conductivity, removing dissolved gases also contrib- Despite the enormous Laplace pressure at the nanosized
utes to this property. The high polarizability gas volume tends bubble, the lifetime of the nanobubble has been measured to
to destabilize the water structure and reduce electrical be days and weeks. A set of experiments was carried out in the
conductivity to a great extent. Helium, for example, has the presence of various salts in order to understand the
least effect on decreasing the electrical conductivity of water nanobubble dynamics. It is widely known that salt exhibits
while having the lowest solubility and polarizability volume of screening of the electric double, and it is also expected that
all gases. Electrical conductivity was also shown to be screening of the electric double layer strengthens with salt
temperature-dependent, with conductivity increasing with valency. Furthermore, charge reversal is also expected in the
increasing temperature with a slight tapering off at 60 °C.44 charged colloidal suspension, depending on the salt valency.
Nanobubble Dynamics in the Presence of Charged Nanobubble in pure water was measured to have a negative
Ions. Indeed, nanobubbles (NBs) in bulk liquid offer enticing zeta potential.
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The magnitude of the zeta potential on nanobubble
decreases with the salt concentration (see Figure 7) for
NaCl and CaCl2. This is perhaps attributed to screening an
electrical double layer around the nanobubbles. On the other
hand, the density of nanobubbles more or less decreases with
salt concentration (see Figure 6b) for NaCl and CaCl2,
Figure 6. Nanobubbles dynamics in aqueous solutions of NaCl,
CaCl2, and AlCl3 of varying concentration. (a) Mean bubble diameter
and (b) bubble number density.
whereas AlCl3 exhibits the opposite trend. The mean size of
the nanobubbles was observed to be higher in the presence of
salt (see Figure 6a). The mean diameter is also measured with
dynamic light scattering, confirming this trend. In other words,
the equilibrium size of nanobubbles increases with a decrease
in the magnitude of the zeta potential. A similar set of
experiments were carried out for the divalent (CaCl2) and
trivalent salts (AlCl3) (see Figure 6). The nanobubble behavior
in divalent salt is typically similar to that of monovalent.
However, as expected, the drop in zeta potential is much
steeper, as shown in Figure 7. In other words, lower zeta
potential nanobubbles are generated in the divalent salt. The
higher mean diameter of the nanobubbles is generated for a
given salt concentration (DLS data shown in Figure S4). Some
experiments were also conducted on symmetric divalent
(Na2SO4) salt. However, all else being equal, the steepness
of the zeta potential with salt concentration was somewhat
similar to the monovalent salt (see Figure S4). On the other
hand, a positive charge nanobubble was generated in the
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Figure 7. DLS measurement of the zeta potentials of NBs aqueous
solutions of NaCl, CaCl2, and AlCl3 of varying salt concentration.
trivalent salt, even at a lower concentration. Trivalent salt
exhibits the charge reversal at a very small salt concentration
(see Figure 7) with respect to the nanobubbles in pure water.
It is also to be noted that AlCl3 forms HCl by a hydrolysis
reaction; therefore, the medium already becomes acidic for
nanobubble generation. This is similar to the zeta potential
variation with pH, where an acidic medium gives rise to the
charge reversal. In addition, the proton released during the
hydrolysis reaction also enhances the polarization of water
molecules. Furthermore, the magnitude of the zeta potential is
observed to decrease with AlCl3 concentration. Interestingly,
the zeta potential again exhibits an inverse correlation with the
equilibrium size of nanobubbles. It is also seen that the
maximum size of the nanobubbles monotonically increases
with the salt valency. In a nutshell, the zeta potential seems to
govern the nanobubble dynamics, and the size of nanobubbles
grows in the presence of the salts. The theoretical under-
standing of the behavior of nanobubbles in the salt solution is
explained in the later section. The zeta potential of the
nanobubbles seems to play a vital role in determining their
stability. It is interesting to examine the charge acquired by the
nanobubbles. The property of the water at the gas−water
interface and in bulk differ significantly; the libration frequency
at the gas−water interface and in bulk was estimated by sum-
frequency vibrational spectroscopy (SFVS) to be 834 and 670
cm−1, respectively.45 Although, time-averaged structure, OH−
stretch, and pico-second structural dynamics do not differ
between the gas−water interface and the bulk water. Indeed,
the libration frequency has a direct correlation with the
stiffness of the rotational potential of water, and the increase in
the liberation frequency may, as a result of the termination of
the hydrogen bonding network at the gas−water interface.
This effect may lead to the retardation of the rotation of water
around intact hydrogen bonds.45 The electrical properties
(dielectric permittivity, dipole moment) of the water at the
interface differ from their bulk water values within more or less
a nanometer. Similarly, the solvation and dissociation proper-
ties of the water also change at the interface, the gas molecules,
rather than the ions and hydrophilic solutes, prone to
dissolving. This phenomenon perhaps directly affects the
surface tension, and the drop in the surface tension is the so-
called Jones-Ray effect.46 The ions inherently abundant in the
water, such as hydrogen and hydroxide ions, also exhibit
differently at the air−water interface than the bulk water. Both
OH− and H3O+ can adsorb at the gas/water interfaces, but
certainly, they cannot absorb simultaneously because of their
rapid association and dissociation to form water. From the
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experimental zeta potential, the gas−water interface prefers
OH− ions over the H3O+ ions. In addition, other gases, such as
carbon dioxide, may form the carbonate and bicarbonate ions,
further enhancing the negative zeta potential.47 On the other
hand, strong acids like HCl may undergo reassociation at the
gas−water interface48
Nanobubble Charging by Ultrasound Waves. From
the preceding discussion, it is pretty clear that the zeta
potential acquired by the nanobubbles is one contributor to
the extraordinary stability of the nanobubbles. We also
examined the presence of ions on nanobubble generation
and concluded that the nanobubbles grow with the
concentration of the ions. Now, it will be equally interesting
if we revert the process and if we can start charging the
nanobubbles. Hydrodynamic and ultrasound cavitating waves
have been shown to form reactive oxygen species and free
radicals together with enhanced dissociation of OH− and H3O+
ions without the addition of foreign materials. Ultrasonic
irradiation was performed in the bulk nanobubble suspension
both in the presence and absence of the salt ions. The bubble
number density, mean diameter, and zeta potential were
measured with an increasing amplitude percentage (increasing
power) for a fixed period. The molar concentration of
monovalent salt (NaCl) was chosen to be 1 mM, on which
the nanobubble was generated by oscillating pressure
fluctuation. The nanobubble sample of 60 mL volume was
subjected to the 20 kHz ultrasound for 5 min. The same
procedure is adopted for pure water nanobubble samples. The
bubble size distribution was observed to be shifted toward the
left, leading to the narrow bubble size distribution. This narrow
size distribution is reflected in the mean bubble diameter. This
trend has been verified further by the dynamic light scattering
(DLS) method in addition to the particle tracking technique.
Furthermore, the zeta potential of the nanobubble was
observed to be enhanced with the increase in the ultrasound
amplitude (see Figure 9a). However, this effect was observed
to be more pronounced in pure water than in the presence of
ions. Similar experiments were performed for pure water (see
Figure S5). In summary, the mean bubble diameter of the
nanobubbles decreases with the zeta potential during the
charging of the nanobubbles by ultrasound waves.
The long-term stability of the nanobubbles was measured by
monitoring the bubble size distribution over 2 to 3 weeks. The
nanobubbles in the presence of salt ions are observed to die
out much faster in comparison to the nanobubbles in pure
water. Nanobubbles in pure water were observed to survive for
more than 2 weeks, while nanobubbles in the presence of salt
ions decay in a week. The plausible reason is that perhaps the
screening of the electric double layer may be responsible for
the rapid decay of the nanobubbles in the presence of ions. In
addition, the weak zeta potential on the nanobubbles also
results in less colloidal stability of the system, and therefore, it
can also be speculated that nanobubbles should disappear
relatively faster in the presence of salt ions rather than in pure
water. On the other hand, nanobubbles treated with ultrasound
waves were observed to have the highest stability due to the
strong zeta potential. The refractive index of the nanobubbles
was also estimated during the charging of the nanobubbles by
ultrasound waves to avoid contamination. The refractive index
of oil droplets in water and nanoparticles was reported to be
more than 1.330. For nanobubbles in pure water and
electrolyte solution, the refractive index value was evaluated
to be in the range of 1.020−1.030, which affirmed the absence
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of contamination during the charging of nanobubbles. Long-
term monitoring of the nanobubble suspensions over more
than 2 weeks shows that the bubble size distribution retains its
shape, but the peak gradually steeps down over time. There is
no such substantial difference in the mean diameter, suggesting
the absence of significant bubble coalescence, bubble breakage,
or Ostwald ripening effects due to the zeta potential. In a
nutshell, the electrically charged liquid−gas interface provides
a repulsive force to prevent bubble coalescence and the high
dissolved gas content in the water. This highly contributes to
nanobubble stability over a period of time. The surface
potential of particles or bubbles is one of the most important
aspects used to describe them. The charged layer allows the
nanobubbles to resist one another and remain suspended
indefinitely. Depending on the overall ionic concentration of
the surrounding solution, the surface layer can be constricted
or extended.49 The variation in electrokinetic surface charge
with electrolyte concentration would imply that ions are
adsorbed on the surface of the nanobubbles. Precise adsorption
would entail the ion losing its hydration shell and being
adsorbed or the hydrated ion being adsorbed on the particle
surface, with the latter being more thermodynamically
advantageous.50
Single Nanobubble Stability theory. Nanobubbles have
various peculiar characteristics discussed in the preceding
section, extraordinary longevity, negative zeta potential, strong
DLVO potential, etc. However, the mechanical stability of the
nanobubbles is still a puzzling question. Considering the
electrostatic pressure provides stability to the nanobubbles,
which acts opposite to the surface tension force. On the other
hand, the ionic forces are expected to act against the
electrostatic and Laplace pressure. Recently, Tan et al.38
considered these ionic forces derived from the solution of the
spherical Poisson−Boltzmann equation. We have adopted this
term in the force balance in the stability model. Consider a
charged spherical nanobubble experiencing an electrostatic
expanding pressure due to the zeta potential. The surface
tension force acts tangential at the interface of the bubble. On
the other hand, the liquid and the gas pressure are expected to
exert opposite to each other. Let us consider the ionic pressure
arising from the Coulombic force between opposite ions at the
interface. The Poisson equation around the nanobubble for
potential distribution can be written as follows:
(2)
where ρe is the local electric charge density in C/m3, ϵr is the
relative dielectric constant, and ϵ0 is the permittivity of the free
space. On the basis of the assumption of axial symmetry, the
Poisson equation can be written as follows:
(3)
The boundary conditions can be written as follows:
(4)
where σ is the surface charge density and n is normal to the
surface at the sphere. For any conservative force field, the force
field can be written as follows:
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Langmuir pubs.acs.org/Langmuir
Figure 8. Nanobubble mechanical stability map comprising the contour value of ϕ−1 obtained from the eq 12 for various values of β and ξ and for a
fixed α = 1. The values obtained using the experiment are shown with the solid lines, and the corresponding theoretical values of β and ξ are
estimated from the relation of eq 13.
(5)
where Fionic = qE. The pressure can be written as follows:
or
On the other hand, the electrostatic pressure acts opposite
to the ionic pressure. The electrostatic pressure can be derived
by assuming two hemispheres, and the force is acting to
expand these hemispheres. The following expression can be
written for electrostatic pressure:
The thickness of the first layer of the opposite ion can be
assumed to be much smaller than the radius of the
nanobubble. The ions can be considered to be the point
charge. We can assume the validity of the local electro-
neutrality condition near the surface of the nanobubble. With
this reasoning, the surface charge density can be approximated
σe ≈ σi = σ. Therefore, the force balance around nanobubbles
can be given as follows:
(6)
(7)
or
(8)
The equation of the state for the real gas can be expressed as
follows:
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Article
(9)
where PBO is the gas pressure at R0. From the charge
conservation, the surface charge density can be written as
follows:
(10)
Upon substitution eq 7 can be rewritten as follows:
(11)
or
(12)
where
(13)
The inverse of the roots of the cubic equation (eq 12) for a
range of value of α, β, and ζ have been plotted in Figure 8 for a
fixed value of α and range of values of β and ξ. The surface
charge density is calculated by the zeta potential and size of
nanobubbles using the Debye−Huckel approximation (
). Sample calculations were also performed using
the complete analytical solutions of the Possion-Boltzman
equation reported by Makino and Ohshima.50 No significant
differences were observed between these two methods. The
theoretical value of ϕ−1 was estimated and compared with the
experimental results for a given value of zeta potential and
surface tension. The difference between the two values
indicates the experimental deviation from the proposed theory.
The nanobubble stability map predicts the existence of stable
nanobubbles. Our results fall in the stable regime of the
nanobubbles. However, the theoretical and experimental
results deviate significantly as we compared the stability of
the single nanobubble with the nanobubble cloud from the
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experiments. The present model does not predict the actual
behavior of nanobubble clouds. However, the theory is
important to understand the effect of surface charge and
surface tension on nanobubble dynamics. Furthermore, it is to
be noted that the relation between the surface charge density
and surface potential was approximated by the Debye−Huckel
approximation. However, a more accurate approximate
expression for the surface potential and surface charge density
relationship offers to express the variation of surface charge at
different locations of the nanobubble surface.50 The parameter
ζ corresponds to the zeta potential on the nanobubbles, the
critical size of the nanobubbles increases with an increase in ζ,
and for a fixed value of β and α, a decrease in charge of the
nanobubble reaches toward the unstable regime of nano-
bubbles. On the other hand, β corresponds to the surface
tension and leads to the collapse of the nanobubbles system in
an unstable regime. In a nutshell, nanobubbles are not stable
for all values of ζ and β but is only stable when the zeta
potential and surface tension of the nanobubbles are balanced
with gas pressure inside the bubble.
DLVO Interaction Potential of Nanobubbles. In the
preceding discussion, it was noted that the long-term stability
of the nanobubbles strongly depends on the zeta potential. For
instance, the nanobubbles treated with ultrasound waves
acquired the highest zeta potential, and the nanobubbles in
the presence of salt ions were measured to be the lowest zeta
potential. The long-term stability was observed to be highest
for the nanobubbles with higher zeta potential. The zeta
potential also contributes to the colloidal stability of the
nanosuspension. The nanobubbles suspended in the water can
be considered a nanosuspension, and the DLVO interaction
potential may be used to gain insight into the long-term
stability of the nanobubbles. Undoubtedly, any charge interface
undergoes the formation of an electric double layer
characterized by the Debye length. The salt valency and the
concentration determines the Debye length. Debye length
exponentially decreases with salt concentration. The classical
DLVO theory has been used to evaluate the total interaction
potential of the nanobubbles. The classical DLVO theory
includes van der Waal and electrostatic potentials. The total
interaction potential (wT(D)) between nanobubbles consist of
the van der Waals and electrostatic potentials that can be
written as follows:
(14)
i.e.,
(15)
where wR(D), wA(D), R, D, and A are, respectively, the
electrostatic potential, van der Waals potential, mean radius of
the nanobubbles, the interspacing distance between nano-
bubbles, and the Hamaker constant. The interaction constant
(Z) is stated by the following expression:51
(16)
where ψ0 is the surface potential. According to Lifshitz theory,
the Hamaker constant A132 between material 1 and material 2
interacting over material 3 can be calculated from the
frequency dependence of the dielectric function ϵ using the
following equation:52
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Article
(17)
where kB is the Boltzmann constant, T is the absolute
temperature, and h is Planck’s constant. Eq 16 is the
approximated formula for eq 15 that is often used for organic
and inorganic materials.
(18)
The prime symbol that refers to the first summation indicates
that the value is multiplied by 0.5 when n = 0 (the static
contribution). Each parameter in eq 16 is calculated employing
eqs 17−19.
(19)
(20)
(21)
By this approach, the Hamaker constant for an air−water
system is estimated based on Lifshitz theory and is given by −7
mm
(22)
where ϵ1, ϵ2, h, νe, n1, and n2 are permittivity of air and water,
Planck’s constant, absorption frequency of water, and refractive
indexes of air and water. The values of these constants are as
follows: ϵ0 = 8.854187 × 10−12 m−3 kg−1 s4A2; kB = 1.380 ×
10−23 m−2 kgs−2 K−1; νe = 3 × 1015 s−1; h = 6.626 × 10−34 J.
Based on the eq 17, the estimated value of the Hamaker
constant for bulk nanobubbles in pure water is 3.679 × 10−20 J.
The total interaction potential is normalized by the
microscopic kinetic energy of the molecules (kBT), and it is
plotted against the dimensionless interspacing distance (κD) as
shown in Figure 9b.
The energy barrier in the potential curve denotes the
strength of the colloidal stability. The energy barrier decreases
from the monovalent ions to the trivalent (from 785 kBT to
720 kBT). This suggests that the higher valency of the salt is
more prone to destabilize than the monovalent salts.
Furthermore, the energy barrier also decreases with ion
concentration in the water (see Figure 9b). The lower zeta
potential may be the reason behind the reduced energy barrier.
Similarly, the total interaction potential has also been
calculated for the charging of the nanobubbles by ultrasound
waves.
Evidently, the energy barrier enhances with the amplitude
due to the fact that the charging of the nanobubbles gives rise
to higher zeta potential on the nanobubble interface. The
colloidal behavior of the nanobubbles is also seen to be in
agreement with the long-term stability measurement. In
summary, nanobubbles in the presence of salt ions deteriorate
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Langmuir pubs.acs.org/Langmuir
Figure 9. Nanobubble dynamics in terms of (a) mean bubble
diameter under the effect of ultrasound amplitude and (b) DLVO
interaction potentials of bulk nanobubbles generated in aqueous salt
solution varying NaCl concentration.
the colloidal stability of the nanobubbles, while nanobubble
charging promotes the colloidal stability of the nanobubbles.
■ CONCLUSIONS
In this work, we have examined the evidence of nanobubble
generation during salting-out effects. The influence of an
oscillating pressure field on nanobubble dynamics during
salting-out effects has been extensively discussed. The
refractive index calculation and the electrical conductivity of
the nanobubbles confirmed the evidence for the gas-filled
nanobubbles. A novel method for the refractive index of
nanobubble is proposed based on the measured scattering
power during particle tracking, where the Mie theory of light
scattering is employed for scattering cross-section calculation.
The screening of the electric double layer decreases the zeta
potential of the nanobubbles depending on the valency of the
salt. Therefore, the equilibrium size of nanobubbles was
observed to be higher in the presence of salts. The mean
diameter of nanobubbles exhibits the inverse dependence on
the zeta potential. Our experimental findings agree well with
the theoretical prediction based on the mechanical stability
model. The presence of an oscillating pressure field enhances
the concentration of nanobubbles compared to solely due to
salting-out effects. The behavior of nanobubbles under the
ultrasound field has also been investigated, and it is observed
that the presence of the ultrasound field further enhances the
nanobubble concentration and zeta potential. The colloidal
stability of nanobubbles in the presence of an ultrasound field
K https://doi.org/10.1021/acs.langmuir.2c03085
Article
is investigated, and it is reported that the energy barrier for
colloidal stability of nanobubbles under an ultrasound field is
significantly higher than both nanobubbles by the salting-out
and oscillating pressure field. A novel mechanical stability
model for nanobubbles has been proposed by considering the
ion cloud pressure, and it is shown to be twice the electrostatic
pressure. The present nanobubble stability model not only
predicts the existence of stable nanobubbles but is also in line
with the experimental results obtained in this work. The
following are the major outcome of the present work: (i) The
refractive measurement gives a precise distinction between
nanobubbles and nanoparticles. (ii) Nanobubbles were
observed to be a stable colloidal system despite the screening
of a double layer in the presence of salt ions. (iii) Numerical
simulation of electromagnetic waves around nanobubbles and
nanoparticles confirms the scattering behavior of the nano-
bubble and nanoparticles.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.langmuir.2c03085.
Optical configuration of NS-300, nanobubble dynamics
in terms of bubble size distribution and zeta potential,
steps to estimate the refractive index, and estimation of
the scaling factor (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Neelkanth Nirmalkar − Department of Chemical Engineering,
Indian Institute of Technology, Ropar 140001, India;
orcid.org/0000-0002-1602-3843; Email: n.nirmalkar@
iitrpr.ac.in
Authors
Kalyani Agarwal − Department of Chemical Engineering,
Indian Institute of Technology, Ropar 140001, India
Mohit Trivedi − Department of Chemical Engineering, Indian
Institute of Technology, Ropar 140001, India
Claus-Dieter Ohl − Otto-von-Guericke University Magdeburg,
Faculty of Natural Sciences, Institute for Physics, Department
Soft Matter, Magdeburg 39106, Germany; orcid.org/
0000-0001-5333-4723
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.langmuir.2c03085
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge the DST Inspire scheme (DST/
INSPIRE/04/2016/001163) under DST for the funding of
this work.
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