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A Henry’s law method for generating bulk

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Cite this: Nanoscale, 2020, 12, 15869

nanobubbles†
Open Access Article. Published on 22 July 2020. Downloaded on 8/28/2022 2:37:23 AM.

Gianluca Ferraro, Ananda J. Jadhav and Mostafa Barigou *

A new technique for generating bulk nanobubble suspensions has been developed based on Henry’s law
which states that the amount of dissolved gas in a liquid is proportional to its partial pressure above the
liquid. This principle which forms the basis of vacuum degasification has been exploited here to produce
stable bulk nanobubbles in excess of 109 bubble mL−1 in pure water, through successive expansion/com-
pression strokes inside a sealed syringe. We provide evidence that the observed nano-entities must be
gas-filled nanobubbles by showing that: (i) they cannot be attributed to organic or inorganic impurities;
(ii) they disappear gradually over time whilst their mean size remains unchanged; (iii) their number density
depends on the concentration of dissolved gas in water and its solubility; and (iv) added sparging of gas
Received 28th April 2020, enhances process yield. We study the properties of these nanobubbles including the effects of type of
Accepted 8th July 2020
dissolved gas, water pH and the presence of different valence salts on their number density and stability.
DOI: 10.1039/d0nr03332d Given the potential of the technique for large scale production of nanobubble suspensions, we describe a
rsc.li/nanoscale successfully tested automated model and outline the basis for process scale-up.

1. Introduction action between two charged surfaces. Thus, it would seem

plausible that the surface charge might govern the stability of
Bulk nanobubbles (BNBs) are a fascinating bubble system BNBs, and there is mounting evidence in support of such an
which challenges conventional understanding and theories of argument.10 Nonetheless, a complete physical model is still
bubble physics. The most peculiar characteristic of this class missing.
of bubbles is their extraordinary longevity, having been Bulk nanobubbles have been reported in numerous papers
reported to last for days, weeks and months.1–7 Classical (>150) and several patents. Despite this multitude of scientific
physics suggests that BNBs should have a very high Laplace reports, the mystery behind the longevity of BNBs is still
pressure, e.g. about 30 bar inside a nanobubble of 100 nm dia- causing some scepticism about their existence, leading to
meter. However, the Epstein and Plesset theory predicts that speculation and controversy about the nature of BNBs and
such nanobubbles should dissolve and vanish on a timescale their origin. The small minority of works which dispute the
of microseconds.8,9 There are three aspects associated with the existence of BNBs have tended to attribute them to solvent/oil
long-term stability of BNBs: (i) their negligible buoyancy force contamination, solid impurities, mesoscale aggregates or
which prevents them from rising to the free surface, their supramolecular structures.12–19 Whilst direct evidence is still
movement being solely dominated by Brownian motion; (ii) missing, recently, however, a significant body of indirect corro-
their colloidal stability, as recently demonstrated;10 and (iii) borative evidence has been reported that BNBs do exist and
their interfacial stability against dissolution. The physical they are stable in pure water as well as in aqueous organic
chemistry of this interfacial stability is an observational solvent solutions.1,3,4,10,20–23
mystery that is attracting considerable interest.1,5,10,11 Whilst research in this area is still in its infancy, already a
However, it appears that such stability may be related to wide range of potential BNB applications have been suggested
another peculiar property which is the existence of a negative or have indeed been industrially implemented, including drag
charge on the BNB interface.1,4,10 From a theoretical point of reduction,24 enhanced germination rate of seeds,25,26 froth
view, the stability of nano-entities depends on the strength of flotation,27–31 improved engine efficacy using hydrogen
their surface charge, as borne out by the electrostatic inter- nanobubbles,32,33 nanobubbles as ultrasound contrast
agent,34–39 promotion of the physiological activity of living
organisms,6 sterilisation of bacteria,40 surface cleaning,41–43
School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham
wastewater treatment44 and medical applications such as
B15 2TT, UK. E-mail: [email protected]
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ improved blood oxygenation,45 therapeutic drug
38,39,46,47
d0nr03332d delivery, reversal of hypoxic conditions,48,49 and use in

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diagnostics and gene therapy.50 Thus, it appears that there is amounts of ultrapure water, drying in a microwave oven and
immense scope for nanobubbles to impact and perhaps revo- flushing with a stream of high-purity dry nitrogen gas.
lutionise many current industrial and medical processes. Polypropylene plastic syringes used for BNB generation were
A number of techniques have been reported for the gene- thoroughly cleaned, and all traces of lubricating silicone oil
ration of BNBs including single nanobubble electrolysis,51–55 removed, by immersion for 30 min in a 10% aqueous solution
acoustic cavitation,1,3,22 hydrodynamic cavitation,56,57 fluidic of analytical grade ethanol (99.9% pure, Fisher Scientific, UK),
oscillation,58 nano-membrane filtration,59 water-solvent followed by thorough rinsing with ultrapure water and drying
mixing,3,21,60,61 laser,62,63 periodic pressure changes,23 com- with a stream of high-purity dry nitrogen gas. Prior to exper-
pression and decompression of gas,64–66 and chemical reac- imentation, the purified water and all stock solutions were
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tions.67 Each method has its own advantages and shortcom- examined using the Nanosight instrument (described further
ings. For example, electrochemical and chemical reaction below) employed for the measurement of BNBs, to ascertain
Open Access Article. Published on 22 July 2020. Downloaded on 8/28/2022 2:37:23 AM.

methods are limited to specific gases, for instance, electrolysis that no significant levels of nanoscale impurities could be
of water can only produce hydrogen and oxygen nanobubbles. detected. In all cases, the BNB suspensions formed were
On the other hand, hydrodynamic cavitation, ultrasound cavi- stored in 20 mL air-tight glass vials for further analysis.
tation and membrane filtration are more general and can be
utilized with a wide range of gases. These methods, however, if
2.2. Henry’s law method of bulk nanobubble generation
used in an uncontrolled fashion, are prone to contamination,
they have low resistance to corrosive chemicals, which restricts According to Henry’s law, at constant temperature, the satur-
the use of reactive gases and solutions, and they tend to be ation concentration of gas in a given liquid, i.e. the amount of
energy intensive. Therefore, to serve industrial and medical dissolved gas, is directly proportional to the partial pressure of
needs, the search continues for BNB generation techniques the gas above the liquid, thus:
which can produce large concentrations of BNBs, are ‘clean’,
C ¼ H  Pg ð1Þ
cost effective and amenable to scale-up and process control.
In this paper, we present a new technique based on Henry’s where, C is the gas solubility at a given temperature in a par-
law’s principle of vacuum degasification, for generating bulk ticular solvent, Pg is the partial pressure of gas and H is
nanobubble suspensions by means of successive expansion/ Henry’s law constant. Therefore, subjecting the liquid to
compression strokes inside a sealed syringe, and provide mul- reduced pressure makes the dissolved gas less soluble and,
tiple evidence that the observed nano-entities must be gas- hence, leads to gas molecules being released. This principle
filled nanobubbles. We study the influence of the number of forms the basis of the technique of vacuum degasification.68
expansion–compression cycles, the type and concentration of We show that subjecting water to vacuum pressure at con-
dissolved gas in water and its solubility on the formation of stant temperature inside a syringe creates gas undersaturation
BNBs, and we demonstrate how sparging of added gas which, when followed by vacuum release, leads to the for-
enhances process yield. We also investigate systematically the mation of BNBs; we call this an expansion–compression
effects of water pH as well as the presence of different valence method, as schematically illustrated in Fig. 1. Initially, a
salts on the number density of BNBs formed and their stabi- syringe is filled with pure water and after expelling any air
lity. Finally, we propose a tested automated model of the tech- trapped within, the syringe tip is sealed using a Luer lock cap.
nique and outline the basis for process scale-up. The water is then depressurised by quickly pulling the syringe
plunger out and then repressurised by instant release of the
plunger which travels at a relatively high velocity under the
2. Experimental action of vacuum pressure (typically ∼7 cm s−1); these two
steps represent one full cycle of the BNB generation process. It
2.1. Materials should be noted that a sufficient amount of vacuum needs to
Ultrapure water (Type 1), henceforth referred to as pure water be created inside the syringe in order to cause enough dis-
or simply water, from a Millipore purification system (Avidity solved gas to be released as well as have enough pressure
Science, UK), of electrical conductivity 0.055 μS cm−1 and pH differential during the compression stage to enable the for-
6.7 at a temperature of 20 °C, was used in all experiments. mation of BNBs. In other words, the pressure inside the
Sodium chloride (NaCl, ≥99.5%), calcium chloride (CaCl2, syringe during the expansion stroke needs to be as low as poss-
≥99%) and aluminium chloride (AlCl3, 99.9%) were obtained ible. Many successive cycles are required to produce a
from Sigma Aldrich. Potassium hydroxide (KOH, 98%) and sufficiently large number of BNBs. The process is demon-
hydrochloric acid (37% HCl AR grade) were purchased from strated in a video provided in ESI.†
VMR Chemicals (UK). Dry air, nitrogen and Argon gases of It should be noted, however, that if the absolute pressure of
purity >99.5%, were supplied by BOC (UK). All solvents and water is reduced to its vapour pressure at the prevailing temp-
reagents used were of the highest purity grade available on the erature, it boils and vapour bubbles develop, a process com-
market. Prior to use, all glassware was cleaned by immersion monly known as cavitation. The vast majority of our experi-
for 30 min in a 10% aqueous solution of potassium hydroxide ments were conducted at a temperature of 20 °C with a
inside an ultrasound bath, followed by rinsing with copious minimum absolute pressure of ∼0.048 atm inside the water-

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Fig. 1 Schematic representation of BNB generation process by means of successive expansion–compression cycles of pure water in a syringe.

filled syringe, which is well above the water vapour pressure of were discounted because glass syringes tended to release silica
0.023 atm at the same temperature.69 Hence, cavitation did impurities, whilst stainless steel syringes generated too much
not play a role in the process of BNB generation. Some limited friction for manual operation. Polypropylene plastic syringes
experiments were performed at temperatures of 5, 15, 25 and with a latex-free elastomer seal are highly resistant to most sol-
35 °C to investigate the effects of air solubility in water. As vents and chemicals70 as well as being abrasion resistant.71
shown in Table 1, the operating vacuum pressure in the They generated no significant levels of impurities and were
syringe was marginally below vapour pressure (0.056 atm) only found to be the most appropriate for manual handling. We
at 35 °C where air solubility was least. Any amount of cavita- also established that the optimum syringe size and water
tion which might have occurred in this case, however, would volume were ∼10 mL and ∼6 mL, respectively, for ease of
have been insignificant and did not affect the results of the manual operation, i.e. for generating sufficient but manage-
temperature experiment, as discussed further below. In con- able pressures, as well as providing adequate samples of BNB
clusion, whilst the method described here has been tested suspension for analysis.
solely on the basis of Henry’s law effects, in practice any occur- It should be emphasised that successful operation of the
rence of cavitation can only assist the process of BNB gene- technique relies on ensuring that the syringe is air-tight and
ration. However, it is unlikely that cavitation will play any sig- the right level of vacuum pressure is generated; any leakage
nificant role even if the pressure inside the syringe falls below would affect the internal pressure and, hence, the performance
vapour pressure, because the time available for cavitation to of the BNB formation process. Prior to experiments, therefore,
take effect towards the end of the expansion stroke is very we used a calibrated absolute pressure sensor (MPX5700AP,
short. 15–700 kPa, 0.2–4.7 V output; NXP Eindhoven, Netherlands) to
The choice of syringe material and size, as well as the measure the pressure online inside the syringe and ensure
volume of water used for the generation of BNBs are impor- that the right level of vacuum was achieved consistently and
tant. After a series of tests, glass and stainless steel syringes precisely to ensure the reproducibility of results, as depicted in
Fig. 2a. The pressure transducer was controlled by a microcon-
troller device (Arduino Uno Rev3 MCU) driven by a code
written in LabVIEW software.72 The pressure sensor was cali-
Table 1 Values of water vapour pressure67 and minimum operating
absolute pressure inside water-filled syringe at different temperatures
brated following the manufacturer’s datasheet and implement-
ing the transducer’s transfer function in the driver code
Minimum written in LabVIEW, thus:
Temperature Water vapour operating pressure
(°C) pressure (atm) (atm) Cavitation
V out ¼ V S  ð0:0012858  P þ 0:04Þ + δ ð2Þ
5 0.0087 0.048 None
15 0.0170 0.048 None where, Vout is the signal received from the microcontroller and
20 0.0234 0.048 None
25 0.0316 0.048 None detected by the pressure transducer, VS is the voltage required
35 0.0562 0.048 Insignificant by the transducer (VS = 5 V), that is the voltage the microcon-

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using a water-filled syringe is schematically illustrated in

Fig. 2c, showing typical cyclic pressure variations inside the
syringe.

2.3. Characterisation of bulk nanobubble suspensions

The size distribution and the number density of BNBs were
measured using a nanoparticle tracking analysis (NTA) instru-
ment (NanoSight NS300, Malvern, UK). NTA tracks the
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Brownian motion of nanoparticles and is well suited for real-

time analysis of polydisperse systems ranging from 10 to
2000 nm in size and 107 to 109 particles per mL in concen-
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tration. We recently established that, in this context, NTA is

superior to dynamic light scattering (DLS) whose measure-
ments are based on the intensity of scattered light and is con-
sequently biased towards large particles and, hence, tends to
overestimate the size of nanoparticles.1 Prior to the analysis of
bulk nanobubble samples, standard suspensions of solid latex
nanospheres were used to verify the accuracy and precision of
the NTA system and to adjust the instrument settings accord-
ingly. The zeta potential of the nanobubbles was measured
using a Zetasizer Nano ZSP instrument (ZEN5600, Malvern,
UK). These measurement techniques and their protocols as
well as their theoretical foundations are discussed in more
Fig. 2 Online pressure measurements inside a syringe: (a) pressure detail in our recent papers.1,10
sensor setup; (b) accuracy of pressure measurement as a function of
initial air volume V0 inside air-filled syringe; (c) typical pressure variations
inside water-filled syringe during generation of bulk nanobubbles.
3. Results and discussion
3.1. Generation of BNBs in pure water
troller provides by default to an external A/D sensor; P is the The formation of BNBs by this method can probably be
pressure registered by the transducer and δ = 0.025Vout is the divided into two stages: (i) as the syringe plunger is pulled out,
measurement error. the water pressure reduces substantially much below atmos-
To test the accuracy of the pressure sensor, a Pressure– pheric (∼0.048 atm) which results in a decrease in air solubility
Volume (or P–V) curve was constructed using a 10 cc empty and creates local gas undersaturation in the form of micro-
plastic syringe. Initially at time t = 0, the tip of the syringe is scopic gas packets. Since this is a closed system, the released
sealed and the plunger is in its initial arbitrary position x0 air molecules form thousands of microbubbles which expand
corresponding to a certain amount of air V0 inside the syringe, by virtue of Boyle’s law and manifest themselves in the form of
which is at initial pressure P0 equal to atmospheric pressure a visible milky cloud; and (ii) as the plunger is instantly
(Patm = 1 atm = 101.325 kPa). By pulling out the plunger from released, it travels at high velocity and the compression from
x0 to x, as depicted in Fig. 2a, the volume of air inside the vacuum back to atmospheric pressure results in the conversion
barrel expands from V0 to V, and the internal pressure of microbubbles into BNBs, presumably either through micro-
decreases according to the ideal gas law: bubble collapse or gas diffusion and shrinkage. Successive
cycles lead to more and more BNBs being formed. Similar
PV ¼ nRT ð3Þ observations of microbubbles being transformed into BNBs
through pressure variations have been recently reported.23,64,65
where, P, V and T are the pressure, volume and temperature; n The characteristics, in terms of bubble size distribution,
is the number of moles and R is the ideal gas constant mean bubble diameter, bubble number density and zeta
(8.31441 J K−1 mol−1). By running the experiment at constant potential, of the BNB suspensions generated by expansion and
room temperature (20 °C) and fixing the initial volume of air compression of pure water at 20 °C are presented in Fig. 3, as a
present inside the syringe V0, it is possible to estimate the function of number of cycles. The bubble size distributions at
number of moles of air. Thus, the readings of the sensor could different cycles are similar and the mean bubble diameter is
be checked against theoretical values. The most accurate approximately the same. Initially, the bubble number density
experimental results with the least deviation from the ideal gas rises considerably as the number of cycles increases, but the
law predictions were obtained for values of V0 ≥ ∼5 mL which rate of increase starts to slow down as the number of cycles
delineate the optimum operating range of the pressure sensor, exceeds the first decade, and tends towards a plateau above
as shown in Fig. 2b. The actual process of generating BNBs about 25 cycles. The zeta potential of the nanobubbles, as

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entities were gradually disappearing whilst their average dia-

meter and zeta potential retained their initial values shown in
Fig. 3.
On the basis of these observations, we can safely discount
the possibility of solid nanoparticles disappearing through
growth in size by aggregation (constant mean diameter) and
sedimentation (samples were stirred before NTA analysis). The
gradual depletion of nano-entities over time, therefore, sup-
ports the hypothesis that they are gas-filled bubbles. Such a
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behaviour is characteristic of stable bubbles disappearing over

time through no apparent breakage, coalescence or Ostwald
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ripening. We had recently argued that BNBs which we pro-

duced by other BNB generation methods probably disappeared
by interaction with the free surface or the solid container
surfaces;1,4,10 such a conjecture has been experimentally corro-
borated in a more recent paper.73
3.2.2. Effects of dissolved air content on generation of
BNBs
3.2.2.1. Effects of water degassing. BNB generation experi-
ments were performed, as depicted in Fig. 5a, using pure water
which had been partially degassed at 15 mbar. The effects of
Fig. 3 Characteristics of bulk nanobubbles in pure water generated by degassing time on the formation of BNBs after 30 expansion–
different numbers of expansion-compression cycles: (a) bubble size dis- compression cycles are presented in Fig. 5b.
tribution; (b) mean bubble diameter; (c) bubble number density; (d) zeta Whilst, the mean diameter remains more or less unaffected
potential. throughout, results show that the longer the water degassing
time, i.e. the less the dissolved air content, the fewer the nano-
entities observed per unit volume. After a degassing time of
expected, remains unchanged within experimental error at 5 h, there is about 50% reduction in the number density of
about −36 mV. nano-entities generated compared to undegassed water. The
considerable dependence of the number of nano-entities
3.2. Bulk nanobubbles or not nanobubbles?
formed on the amount of dissolved air is another strong indi-
Our hypothesis is that the nano-entities produced by this cation that they must be gas-filled nanobubbles.
expansion–compression method are nanobubbles suspended 3.2.2.2. Effects of air solubility. The quantity of dissolved air
in water. We investigate a number of physical aspects and use is affected by the solvent temperature; the lower the water
various analytical techniques to prove this hypothesis, as temperature the higher is the air solubility. Using water at
follows. different temperatures, BNBs were generated employing
3.2.1. Gradual disappearance of BNBs over time. We different numbers of expansion–compression cycles. Results
observed the long-term behaviour of the BNB suspensions and plotted in Fig. 6a show that the number of BNBs increases
monitored their bubble number density, size distribution,
mean bubble diameter and zeta potential. The bubble concen-
tration slowly declined as the bubble size distribution col-
lapsed over time, as shown in Fig. 4, indicating that the nano-

Fig. 5 Effects of water degassing on generation of bulk nanobubbles:

(a) schematic representation of BNB generation process using water
Fig. 4 Long-term evolution of BNB suspension: (a) bubble size distri- degassed inside vacuum cell at 15 mbar; (b) BNB measurements after 30
bution; (b) bubble number density. expansion–compression cycles.

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in Fig. 7 show that sparging enables water to be resaturated

with air, thus, allowing the concentration of BNBs to increase
linearly, well above the bubble concentration obtained from
dissolved air only. Therefore, repeated sparging of air might
provide a mechanism for producing significantly higher con-
centrations of BNBs, which has so far been elusive.
Furthermore, these findings represent further evidence that,
the number of nano-entities being significantly augmented by
the supply of additional air, must be bubbles.
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3.2.4. Spectroscopy analysis of BNB suspensions. Following

Fig. 6 Effects of air solubility on generation of bulk nanobubbles in our recent work,4 we adopted a range of chemical analytical
Open Access Article. Published on 22 July 2020. Downloaded on 8/28/2022 2:37:23 AM.

pure water: (a) effects of number of expansion–compression cycles at techniques, details of which are given in ESI,† to show that the
constant temperature; (b) effects of temperature at constant number of observed nano-entities are not due to the presence of nano-
expansion–compression cycles. scale organic or inorganic impurities or contamination includ-
ing oil nanodroplets, solid nanoparticles and supramolecules.
We used Fourier transform infrared spectroscopy (FT-IR) and
with the number of generation cycles. At temperatures of 25 °C Raman spectroscopy analysis and compared the functional
and higher, the bubble number density levels off after about groups present in pure water and in the BNB suspensions. We
40 cycles as the available released gas is depleted. However, at also analysed pure water and BNB suspensions using gas
lower temperatures, the curve does not reach a plateau even chromatography (GC) to examine for any organic contami-
after 90 cycles and continues to increase, albeit at a slower nation. The measured spectra are presented in Fig. 8, and they
rate, which implies that more released air is still available in show that water is the only chemical species being detected by
the water which requires more cycles to convert into BNBs. As these three different analytical techniques in the BNB
expected for gas-filled bubbles, the number density is much suspensions.
higher at lower temperatures and declines steeply at higher Additionally, we used inductive coupled plasma mass spec-
temperatures, as depicted in Fig. 6b. In conclusion, these find- troscopy (ICP-MS) to analyse for the presence of 20 common
ings provide further corroboration for the assumption that the metal/nonmetal elements. Results summarised in Table S3 in
observed nano-entities are indeed gas-filled bubbles. ESI,† show that the BNB suspensions contained extremely low
3.2.3. Effects of air sparging on generation of BNBs. More levels of metal traces mostly similar to pure water. The concen-
experiments were conducted by sparging additional air in pure tration of Si in the nanobubble suspension is higher than in
water for 20 min using the setup depicted in Fig. 7, and then pure water, which suggests the existence of some syringe
using such air-saturated water to produce BNBs over 30 expan- abrasion effects. It should be pointed out that the sample ana-
sion–compression cycles. After each sparging operation, a lysed by ICP-MS represents a probably worst-case scenario
sample of the BNB suspension was withdrawn for NTA analysis
and the remainder was sparged again with air for 2 min,
before being subjected to another 30 expansion–compression
cycles. The process was repeated four time. Results displayed

Fig. 7 Effects of repeated additional air sparging on generation of bulk Fig. 8 Spectroscopy analysis of pure ware and bulk nanobubble sus-
nanobubbles. pensions: (a) FT-IR spectra; (b) Raman spectra; (c) gas chromatogram.

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where the syringe was deliberately overused (>400 cycles) to of magnitude) higher and the absolute value of the zeta poten-
assess the amount of potential impurities that can be gener- tial increases steadily with pH to reach −63 mV at pH 12.
ated and, hence, the usability of the syringe. In reality, the Whilst the acidic BNB suspensions are short-lived, these alka-
amount of such impurities can be controlled at much lower line BNBs enjoy more long-term stability and the vast majority
levels by generally restricting the number of syringe cycles to were still in suspension after several weeks, while the mean
less than ∼200. Nonetheless, the concentration of these impu- bubble size remains approximately constant.
rities is still far too low and the observed nano-entities cannot, A plausible reason for the relatively weak stability of BNBs
therefore, be attributed to the presence of metal/nonmetal in acidic solutions may be advanced as follows. During pro-
contamination. In conclusion, these analyses combined duction of BNBs the auto-ionisation process of water which in
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strongly suggest that the observed nano-entities must be gas- a neutral pH environment, produces an equal number of
filled bubbles. hydroxyl ions (OH−) and hydronium ions (H3O+). In an acidic
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solution, such a process becomes heavily biased towards the

3.3. Properties of BNBs generated by expansion–compression production of the latter positive ions.74 Since there is a short-
method age in hydroxyl ions which normally attach to bubble inter-
faces to stabilise them, the H+ ions emanating from the added
3.3.1. Effect of water pH on generation and stability of HCl take over and attach to the bubble interfaces causing
BNBs. Nanobubble suspensions were generated in pure water instead a positive surface potential,75,76 as shown in Fig. 9b.
with the pH pre-adjusted in the range 2–12 by addition of HCl Above the isoelectric point, the nanobubble interfaces are
to make acidic solutions and KOH to make basic solutions. negatively charged (Fig. 9b). Thus, an electric double layer is
Results are plotted in Fig. 9 showing the effects on bubble expected to form around the nanobubbles, similar to that
number density, mean bubble diameter and zeta potential. observed around solid nanoparticles.10 According to the pre-
The bubble number density increases sharply as a function of viously postulated ion-stabilisation model, the charged nano-
pH (Fig. 9a). A large bubble number density can be achieved bubble interface gives rise to an external electrostatic pressure
in acidic solutions but these BNBs which have a relatively which balances the internal Laplace pressure and, hence, no
small positive zeta potential (∼+10 mV; Fig. 9b) are relatively net diffusion of gas occurs at equilibrium. We previously
short-lived and generally disappear within a day or two. Their derived expressions for these counterbalancing pressure forces
disappearance is preceded by a substantial increase in the from which, at equilibrium, the radius R of the nanobubble is
mean bubble diameter (Fig. 9c). The zeta potential changes to given by:10
negative at a pH between 4 and 5, which is expected to corres-
pond to the isoelectric point of the solution. In these basic γε
R¼ ð4Þ
solutions, the bubble number density is much (up to an order πσ 2
where, ε is the permittivity of the suspending medium, γ is the
surface tension and σ is the density of surface charge which is
related to the surface potential ψo via the Grahame equation,
thus:77
 
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi zeψ 0
σ ¼ 8kB Tεε0 c1 sin h ð5Þ
2kB T

where, kB, T, ε0, c∞, z, e and ψ0 are, respectively, the Boltzmann

constant, temperature, permittivity of vacuum, concentration
of co-ions in the bulk, the charge on ion or valence of the
ionic species, elementary charge and surface potential.
It can be inferred from eqn (4) that a lower surface charge
density, caused by a lower surface potential (eqn (5)), will
cause the nanobubble to expand to maintain equilibrium
between the inner and outer counterbalancing pressures,
which probably explains why at low pH values the mean nano-
bubble diameter increases with time (Fig. 9c). Furthermore,
beyond some critical nanobubble diameter, further reduction
in electrostatic pressure at low pH may promote outward gas
diffusion and, hence, disappearance of the BNBs, which could
explain the sharp drop as a function of time in bubble number
density observed in Fig. 9a.
Fig. 9 Effects of pre-adjustment of water pH on generation and stabi-
Very recently, using various sets of experimental data from
lity of bulk nanobubbles: (a) bubble number density; (b) zeta potential; the literature, other authors have tested the above ion-stabilis-
(c) mean bubble diameter. ation model.78 They showed that the excess surface charge is

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indeed responsible for the stability of bulk nanobubbles as the could not be measured due to the conductivity of the solution
electrostatic effect acts as a restoring force to stabilize nano- exceeding the instrument’s limit). The addition of AlCl3 led to
bubbles, which prevents nanobubbles in equilibrium from a very acidic solution ( pH ∼2.0) due to the formation of
shrinking and growing. We previously studied the effects of aqueous solution of hydrogen halide (HCl) which made it
adding surfactants on the stability of BNBs. The presence of impossible to generate BNB suspensions that are sufficiently
such impurities tends to affect the stability of BNBs afforded stable for further analysis.
by surface ions depending on the type of surfactant polarity.10 As pointed out above and as discussed in our recent
Those results further corroborate the idea of the ion-stabilis- works,10 owing to the presence of counter-ions (OH−) and co-
ation mechanism. ions (H+), charged BNBs in water may form an electric double
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3.3.2. Generation and stability of BNBs in salt solutions. layer, the thickness of which is the Debye length k−1 which can
The effects of pre-addition of varying concentrations of salts of be estimated from:
Open Access Article. Published on 22 July 2020. Downloaded on 8/28/2022 2:37:23 AM.

different valence to pure water, namely NaCl (monovalent), sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

CaCl2 (divalent) and AlCl3 (trivalent), on the generation and 1 εε0 kB T
k ¼ ð6Þ
stability of BNBs was investigated. Results for NaCl and CaCl2 2zi 2 e2 c1
are presented in Fig. 10. In both cases, the presence of salt
where, ε0 is the permittivity of vacuum, zi, is the salt valence
leads to a sharp drop in bubble number density which is
and C∞ is the concentration of co-ions in the bulk. In pure
accompanied by a considerable rise in mean bubble diameter
water, k−1 = 961 nm and, according to eqn (6), it will reduce
with increasing salt concentration. In addition, the presence of
with increasing co-ion concentration and salt valence, leading
either salt dramatically reduces the lifetime of BNBs.
to so-called screening of the electric double layer. Due to such
The magnitude of the negative zeta potential decreases con-
screening of the electric double layer, the external negative
siderably but stays negative in the case of NaCl, as shown in
electrostatic pressure, as discussed above, would decrease
Fig. 10. In the presence of CaCl2, however, the zeta potential is
leading to a pressure imbalance across the nanobubble inter-
positive and increases in magnitude with salt concentration
faces which would then expand, possibly explaining the
(note zeta potential for concentrations greater than 50 mM
observed growth in mean bubble diameter.
The observed dramatic impact of the divalent salt on the
zeta potential compared to the monovalent salt could, there-
fore, be plausibly explained by a deterioration of the electric
double layer around the BNBs (i.e. k−1 decreases) in case of the
divalent salt. This is reflected in the comparatively much less
stable BNBs generated in the CaCl2 solutions compared to the
NaCl solutions (Fig. 10a and d) at any concentration; the rate
of BNB disappearance being at least an order of magnitude
faster in the divalent salt solution.
3.3.3. Effects of type of dissolved gas on the formation of
BNBs. The effects of type of dissolved gas on the formation of
BNBs in the syringe, were explored by pre-sparging air, nitro-
gen or Argon in pure water for 20 min at a controlled tempera-
ture in the range 5–35 °C. Results plotted in Fig. 11 show that
increasingly more BNBs are generated with Argon than with
air than with N2. The difference in bubble number density can
be qualitatively explained by the differences in water solubility
of these gases, i.e. Argon > air > N2.

3.4. Automation of BNB generation process

Given the potentially large number of BNBs per unit volume
that this expansion–compression method may be able to gene-
rate, especially with additional gas sparging (Fig. 6), we con-
sidered automating the technique to enable easy operation as
well as scale-up of the BNB production process. A schematic
diagram of an automated model is depicted in Fig. 12a. We
used a scale which is identical to that of the manual process
used in this study, i.e. a 10 mL syringe, to illustrate the auto-
mation of the system but the design can be readily scaled up
Fig. 10 Effects of pre-addition of salts on generation and stability of using the same design concept. The syringe is housed inside a
bulk nanobubbles: (a)–(c) NaCl solution; (d)–(f ) CaCl2 solution. cylinder whilst the plunger is attached to a reciprocating pneu-

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matic 16 × 30 twin-piston driven by a two-position solenoid

valve operating in the pressure range 0.15–0.8 MPa in conjunc-
tion with silencer valves, actuated by a 12 V trigger cycle timer
delay switch.
A series of tests were conducted to establish the most
efficient operating conditions for an automated 1 : 1 scale
syringe model. First, the best operating gas pressure (2.5 bar)
had to be selected within the operating range of the solenoid
valve to yield the maximum bubble number density without
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causing mechanical damage to the syringe. Then, by keeping

this gas pressure constant, the linear piston velocity was
Open Access Article. Published on 22 July 2020. Downloaded on 8/28/2022 2:37:23 AM.

varied, as shown in Fig. 12b. The most effective piston velocity

was 6 cm s−1. Higher velocities did not improve the bubble
number density but caused instead increasingly more friction
and mechanical stresses leading ultimately to mechanical
damage of the syringe.

4. Conclusions
Fig. 11 Effects of type of gas on formation of BNBs: (a) bubble number A new technique based on Henry’s law’s principle of vacuum
density; (b) mean bubble diameter; (c) zeta potential.
degasification has been developed to generate concentrations
in excess of 109 bubble mL−1 of stable bulk nanobubbles in
pure water, through successive expansion/compression strokes
inside a sealed syringe. We have shown that the observed
nano-entities must be gas-filled domains as: (i) they cannot be
attributed, as proven by various spectroscopy analyses, to the
presence of organic or inorganic impurities; (ii) they gradually
disappear over time whilst their mean size remains
unchanged; (iii) the amount of dissolved gas and its solubility
have a direct bearing on their number density; and (iv) added
sparging of gas enhances their number density.
The number of bubbles generated increases as a function
of the number of expansion–compression cycles up to a point
and then levels off as the available dissolved gas is depleted.
However, sparging additional gas allows improved yield to be
achieved.
Results on the pre-adjustment of water pH show that BNBs
enjoy much higher stability in alkaline solutions than acidic
ones. The mean size of nanobubbles increases with a decrease
in pH whereas the bubble number density decreases. We con-
jecture that in pure water, due to the adsorption of OH− ions,
an electric double layer similar to that observed around solid
nanoparticles, forms around the negatively charged nanobub-
bles. The charged nanobubble interface is postulated to create
an external negative electrostatic pressure which balances the
internal Laplace pressure so that, at equilibrium, no net gas
diffusion occurs. The disruption of this equilibrium due to a
lower surface potential at low pH, is believed to be behind the
expansion and destabilisation of BNBs in acidic environments.
The presence of even small amounts of salt of any valence
causes a drastic reduction in bubble number density and a
sharp increase in mean bubble size, as it leads to screening of
Fig. 12 Automated 1 : 1 scale BNB generation process: (a) schematic
the electric double layer formed by the co-ions. As a result, the
diagram of process setup; (b) effects of linear piston velocity at constant external negative electrostatic pressure decreases leading to a
optimum operating gas pressure of 2.5 atm. pressure imbalance across the interface of nanobubbles which

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then expand and grow in size; this situation is exacerbated in 16 D. Rak, M. Ovadová and M. Sedlák, J. Phys. Chem. Lett.,
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cessfully developed and tested an automated 1 : 1 scale model E. P. Favvas, J. Colloid Interface Sci., 2020, 564, 371–380.
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Conflicts of interest 22 K. Yasuda, H. Matsushima and Y. Asakura, Chem. Eng. Sci.,
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