J Nanopart Res (2019) 21: 173

https://doi.org/10.1007/s11051-019-4618-y

RESEARCH PAPER

Average size and zeta potential of nanobubbles in different

reagent solutions
Thi Thuy Bui & Duc Canh Nguyen & Mooyoung Han

Received: 24 January 2019 / Accepted: 22 July 2019 / Published online: 7 August 2019
# Springer Nature B.V. 2019

Abstract In the present study, we analyzed the average charge and the size of NBs, allowing them to be appli-
size and zeta potential of nanobubbles (NBs) in chem- cable in many treatment processes for water treatment.
ical reagent solutions. Here, we proposed the possible
mechanisms for the size growth and for negative and Keywords Adsorption . Chemical reagents .
positive NB creation. NBs were produced by dispersing Nanobubble coalescence . Nanobubble size . Zeta
a supersaturated air-water mixture in a mixing chamber, potential . Water treatment
and then causing the breakup of microbubbles in a
Teflon hose. The size and zeta potential of the NBs were
measured by dynamic light scattering. The NB size had Introduction
no dependency on pH and grew over time. The pro-
posed mechanism of the NBs’ size growth related to Macro- and microbubbles have been observed repeat-
their coalescence in the solutions. The bubbles were edly in solutions. Recently, nanobubbles (NBs) have
charged negatively in the presence of glucose, ethylene- drawn more attention in the field of water treatment. A
diaminetetraacetic acid, and Na+, while they were previous work (Agarwal et al. 2011) reported that NBs
charged positively in the addition of have a role in the catalysis of chemical reactions, used
dimethyldioctadecylammonium bromide, Al3+, and for the purification of contaminated water and the im-
Fe3+. The NB zeta potential decreased in all solutions, provement of chemical treatment efficiency. Several
while their pH increased from 2 to 12. Zeta potential papers have focused on the application of NBs to flota-
values remained stable for 150 min, proving the long- tion processes: substances like oil, grease, powder, met-
term permanence of bubbles in the bulk solutions. The al ions, and organic matter (Galvin et al. 1994) can be
charged NBs were created from the adsorbed species separated from the rest of the solution based on the
such as OH− and DODA+ and possible aqueous speci- floatability of bubble-pollutant aggregates (Haarhoff
ation (through the addition of metal ions) on its surface. and Edzwald 2001; Tsai et al. 2007; Fan et al. 2010).
Our results indicate that the type of chemical reagent Recently, Temesgen et al. (2017) reported that the sur-
solution can influence both the sign of the surface face charge of bubbles and contaminants should be

T. T. Bui : M. Han (*) D. C. Nguyen (*)

Department of Civil and Environmental Engineering, Seoul Sustainable Management of Natural Resources and Environment
National University, Gwanak-ro 1, Gwanak-gu, Seoul 08826, Research Group, Faculty of Environment and Labour Safety, Ton
South Korea Duc Thang University, 19 Nguyen Huu Tho Street, Tan Phong
e-mail: [email protected] Ward, District 7, Ho Chi Minh City, Vietnam
e-mail: [email protected]

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173 Page 2 of 11 J Nanopart Res (2019) 21: 173

opposed to enhance treatment efficiency. In addition, monovalent ion (Na+ and K+) solutions. From a litera-
most of the contaminants in the natural water has shown ture review (Uchida et al. 2016), it was concluded that
their negative charge (Han et al. 2006), allowing the the presence of 100 mM NaCl in the solution improves
application of positive bubble technology for the high the stability of O2 micro- and nanobubbles (MNBs) for
efficacy. In more detail, the performance of NB technol- at least 1 week; on the other hand, a larger amount of
ogies is affected by the physical properties of gas-liquid NaCl could shorten the permanence time of the MNBs,
phases and of contaminants (Tsai et al. 2007; Temesgen accelerating their coalescence. In Wu et al. (2012), the
et al. 2017). Moreover, the characteristics of NBs can be air captured in the NBs remained there for up to 5 h in
adapted to the chosen design and operational conditions the presence of another monovalent metal ion (i.e.,
(Najafi et al. 2007; Ushikubo et al. 2010). The size and 1 mM KCl solution). Overall, the appearance of a sur-
zeta potential are key surface properties of bubbles, face charge, improving the stability of NBs in the solu-
which have been measured under various conditions: a tion, was attributed to the relative arrangement of the
number of studies have focused on the influences of water structure at the bubble interface (Ushikubo et al.
surfactants and/or salt concentration (Saulnier et al. 2010). The mentioned studies agreed on a critical mag-
1996; Kim et al. 2000; Cho et al. 2005; Quinn et al. nitude of zeta potential (30 mV), which can produce a
2014; Arturo et al. 2015), frother-electrolyte solutions great repulsion force, avoiding coalescence and contrib-
(Elmahdy et al. 2008; Castro et al. 2013; Sovechles et al. uting to the persistence of NBs.
2016), and electrolytes (Botello-Álvarez et al. 2011), In order to identify possible mechanisms at the base
paralleled with variations in pH. Controlling zeta poten- of NBs’ size growth, and understand the dependence of
tial of NBs (i.e., negative and positive) plays a major this parameter on the properties of additives in the
role in bubble-mineral contaminant interaction and solution, it can be useful to study the temporal evolution
bubble-oil aggregates; meanwhile, bubble coalescence of several parameters. In this paper, we proposed the
significantly influences several treatment and separation possible mechanisms explaining the size growth of
processes, such as flotation, oil sand separation, organic NBs: coalescence of NBs and the negative and positive
reduction, and membrane defouling (Calgaroto et al. NB creation, adsorption of adsorbed species in the so-
2014). lution. In this study, NBs were generated by adding
In most cases, the adsorption of the OH− group 1 mM of chemical reagents. The NBs were generated
(caused by the enthalpy difference in hydration between by dispersing microbubbles (MBs) in a narrow, long
OH− and H+ ions) was dominant at the interface of the Teflon hose; their physical properties (i.e., size and zeta
bubbles and determined the negative sign of the bubble potential) were measured by dynamic light scattering, in
zeta potential in deionized water (Najafi et al. 2007; the entire pH 2~12 and over a period of 150 min (at 30-
Elmahdy et al. 2008). In addition, the bubble zeta po- min increments). The findings of this study contribute to
tential has been used to calculate the pH of solutions the understanding of NBs’ fundamental characteristics,
(Najafi et al. 2007; Wu et al. 2012). Recent studies which can play an important role in bubble-mineral
focused on modifying the charge of air bubbles, by pollutant interactions; furthermore, they might be ap-
varying the pH and ionic strength of aqueous solutions: plied to other types of mineral flotations and water
acidic/basic solutions were buffered adding several treatment processes.
types of chemicals at different concentrations (Cho
et al. 2005; Najafi et al. 2007; Wu et al. 2012). However,
there has been little investigation on the stability of NBs Methodology
(Ushikubo et al. 2010) and the adapting mechanisms
related to NBs’ size growth in surfactant solutions (es- NB generation
pecially in those containing trivalent metal ions). Bubble
stability could be encouraged by the repulsion process, The NBs were prepared by injecting a supersaturat-
which is caused by electrical charges at the air-water ed liquid-gas dispersion in a mixing chamber and
interface and affects bubble coalescence. The stability of then causing the breakup of MBs in a splitter
bubbles in the presence of trivalent metal ions (i.e., Al3+ (Teflon hose). This breakage was related to the
and Fe3+) has not been studied sufficiently. However, surface tension of the aqueous system, known as
several studies have discussed the occurrence of NBs in “local stress” on the bubble interface. In bulk

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J Nanopart Res (2019) 21: 173 Page 3 of 11 173

solutions, surfactants and frothers induce a surface NB size and zeta potential measurement
tension gradient which increases the instability of
the MB interface (Chu et al. 2016). As shown in Dissolved oxygen (DO) concentration was measured
Fig. 1, the NB formation system consisted of a 10- using an optical DO meter (ProODO YSI Inc., USA),
L acrylic reactor, a motor (TM90-A0553, output in order to check the quantity of supersaturated of gas in
120 W, voltage AC 220 V, current 0.65 A, rota- the NB generation system. In this study, the DO con-
tional speed 3000 rpm), a pump (Yongwon centration was ~ 20.0–20.5 mg/L: much higher than the
980 kPa, external diameter = 12 mm, flow rate = maximum DO saturation concentration at 25 °C
15 L/min), a 5-L mixing chamber, and two Teflon (8.24 mg/L). All experiments were conducted in tripli-
hoses (10 m length, 3 mm and 10 mm diameter, cate. The bubble size and zeta potential were measured
respectively). A compressor was used to inject air using a zeta potential-particle size analyzer (ELSZ-
at the Teflon hose at a pressure of 6 bars and at a 1000, Otsuka Electronics Co., Ltd., Japan). The instru-
flow rate of 50 mL/min; then, this air was mixed ment detects the particle with the size range of
with additive-containing water. A milky aqueous 0.6~10,000 nm and zeta potential value of − 200~+
suspension of MBs was produced in the mixing 200 mV under concentration of 0.1~400,000 ppm
chamber and then broken up into NBs within the (Najafi et al. 2007; Stetefeld et al. 2016). Due to
narrow Teflon hose, before it returned to the electro-osmosis measurement and plot analysis, this
reactor. instrument enables to provide high-precision analysis
The physical properties of the bubble were observed of zeta potential and size using micro-volume flow cell
after the addition of different reagents such as glucose and disposal cell, respectively. This instrument mea-
(≥ 98%), ethylenediaminetetraacetic acid (EDTA) (≥ sured the size of NBs by dynamic light scattering
98.5%), dimethyldioctadecylammonium bromide (DLS). The size of NBs was obtained using polystyrene
(DODAB) (≥ 98%), Al3+ in Al2(SO4)3 (98%), Fe3+ in cuvettes (single use). It is confirmed that the DLS meth-
FeCl3·6H2O (98%), and Na+ in NaCl (≥ 98%). All od can be used to observe nano-sized bubbles, which
chemicals were purchased from Daejung Chemicals & ranged between ~ 30–250 nm (Kikuchi et al. 2009) and
Metals Co., Ltd. (South Korea) and used after dilution in > 290 nm (Najafi et al. 2007). In this study, measured
5 L of filtered water in the acrylic reactor, at a concen- concentration of NBs at which the measurements were
tration of 1 mM, as summarized in Table 1. Solution carried out was ~ 1.62 × 106 ± 1.2 × 105 particles per
samples were collected from the reactor after 10 min of minute. Due to advanced backscatter system, zeta
operation. potential-particle analyzer greatly offsets multiple

Fig. 1 Schematic diagram of the experimental facility used to generate NBs: volume (V), diameter (D), flow rate (Q), and pressure (P)

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173 Page 4 of 11 J Nanopart Res (2019) 21: 173

Table 1 Summary of used chemicals in the experiments

Ionic
Chemicals Structure Role in water treatment
strength

Crystallization: purification
Glucose
- technique
(Alves 2007)

EDTA Chelator: Heavy metal

6.47 x 10-3
removal (WHO 1998)

Antimicrobial activity:
Biological process and
DODAB 1.00 x 10-3
disinfection (Carmona-
Ribeiro 2017)

Most widely-used
Al2(SO4)3
3.19 x 10-3 coagulant: coagulation and
– 18.H2O
flocculation process

Widely-used coagulant:
FeCl3 –
4.14 x 10-3 coagulation and flocculation
6.H2O
process

Common electrolyte to
NaCl Na-Cl 1.00 x 10-3 characterize zeta potential of
bubbles (Uchida 2016)

scattering influences from the calculation near the cell Before the zeta potential measurements, the sam-
wall (Stetefeld et al. 2016). In addition, backscatter ples were transferred into a flow cell (high concen-
system significantly boosts the measured concentration tration cell, made of glass with a path length of
for single scattering (Stetefeld et al. 2016), so that it is 1.5 mm, between two platinum electrodes). The mea-
not suffered from multiple scattering. sured zeta potential was converted using

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J Nanopart Res (2019) 21: 173 Page 5 of 11 173

Smoluchowski’s equation, considering a viscosity of Figure 2 shows NB size for different types of solu-
8.83 × 10−4 Pa s, a dielectric constant of 1.783, a tions. As seen, the bubbles in the presence of glucose,
refractive index of 1.3328, and a base frequency of EDTA, and Na+ remained nano-sized, whereas bubbles
123.8 Hz. The signs of the zeta potentials were ob- in the DODAB and trivalent metal ions became
tained from the pH (oscillating between 2 and 12) submicron-sized after 90 min. Glucose, EDTA, and
and measured within a timeframe of 150 min, at 30- Na+ had little effect on the NB size, due to the insignif-
min increments. Hereafter, we proposed the possible icant adsorption of possible species at the air-water
mechanisms of size growth and negative and positive interface. In the presence of Na+, the stability of NBs
NB creation in such solutions. Due to Brownian supports the results of a previous study (Uchida et al.
motion and low rising velocity (Temesgen et al. 2016), in which NBs were maintained for 2 weeks when
2017), the NB convection and buoyancy can be con- adding 1 mM Na+. The NBs observed in our study
sidered negligible for these samples. Possible aque- showed a similar trend to that described in Uchida
ous speciation, ionic strength, and adsorbed species et al. (2016). We found that the accumulation of ions
were obtained from the calculation of charge and from glucose, EDTA, and Na+ near NB surfaces
mass balance at 25 °C, using Visual Minteq 3.1. inhibited their coalescence, resulting in very stable
NBs in such solutions.
An increase in size obtained in the presence of
Experimental results and discussions DODAB, Al3+, and Fe3+ after 90 min confirms that
several NBs would coalesce (expressed by the number
Creation and average size of NBs of coalesced bubbles), creating MBs in such solutions.
Here, we suggest a simple equation to express the num-
Creation of NBs ber of NBs that came in contact with each other over
time (the bubbles were assumed to be spherical):
During the production of bubbles in the presence
of chemical additives, > 83% of the bubbles were 4 4
nano-sized (diameter ≤ 1 μm; Temesgen et al. πðD=2Þ3 ¼ n πðd=2Þ3 ð1Þ
3 3
2017). The initial bubbles produced in filtered
tap water had instead an average diameter of
490 nm. Overall, the NBs in the metal ion solu- where D is the size of coalesced NBs at a specific time
tions were slightly smaller than those in the or- (nm), n is the number of coalesced NBs, and d is the
ganic chemical solutions, having average diameters initial size of coalesced NBs (nm). The number of
of 450–600 nm and 500–680 nm, respectively. The coalesced bubbles in the solutions, during the 150-min
results were obtained through DLS, which detects observation period, is indicated in Table 3. Overall, a
the Brownian motion of particles with diameters larger number of NBs coalesced in the presence of
between 0.6 nm and 6 μm (Ushikubo et al. 2010). DODAB, Al3+, and Fe3+, rather than in the presence of
Our results indicate a significantly high generation glucose, EDTA, and Na+.
of NBs in the presence of additives in the Teflon It is still challenging to explain the bubble coalescence
hose (using a special splitter). mechanism because of its rapid evolution. In an earlier
report (Kracht and Finch 2009), bubble coalescence was
Average size of NBs estimated to occur within milliseconds. The basic process
seems to involve the creation of a small region of orga-
Table 2 shows that solution pH effects on NB size are nized water and with a single NB, through the diffusion
relatively small. When looking at NB size variation with and adsorption of surfactants; this region would then affect
pH, Cho et al. (2005) reported that bubble size stayed bubble contacts (Finch et al. 2006). Similar mechanisms
similarly at ~ 750 nm in the entire pH 2–12. In addition, have been discussed concerning the presence of inorganic
Meegoda et al. (2018) confirmed that the gas pressure salts, like NaCl (Finch et al. 2008, Kracht and Finch 2009):
and gas flow rate are major contributors to bubble size. the total stress model of the solution (with viscoelastic
Hence, it is concluded NB size had no dependency on properties and dilation viscosity) would be related to the
solution pH. mechanism of bubble coalescence. Here, the numbers

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173 Page 6 of 11 J Nanopart Res (2019) 21: 173

Table 2 Average size of NBs in various solution pH

pH of solution

2 4 7 9 12

Average size of NBs in the addition of Glucose 650 643 658 652 656
EDTA 665 649 653 670 674
DODAB 552 524 513 542 552
Al3+ 543 552 532 537 527
3+
Fe 592 574 583 590 569
Na+ 465 452 459 465 455

referring to the quantity of coalesced bubbles are not Zeta potential of NBs
integers: n = 3.9 for Fe3+, n = 13.6 for DODAB, and n =
15.1 for Al3+ at the end of the observation time (after Changes under variable pH
150 min; Table 3). Our calculation relates the volume (V)
and diameter (D and d) of the bubble, assuming that the The solution had a neutral pH in the presence of glucose,
number of coalesced bubbles is a function of the bubble DODAB, and Na+, but an acidic pH in the presence of
shape (S) and chemical properties (p) (n = f(S, p)). More- EDTA, Fe3+, and Al3+. Figure 3 (left panel) indicates
over, we assumed that the shape of bubbles was spherical, that bubbles in the 1 mM glucose and in the 1 mM
in order to obtain an ideal shape coefficient (S = 1); in fact, EDTA solutions yielded similar negative charges for
for S = 1, the effect of bubble shape on the calculations is pH values between 4 and 12. A low positive value
negligible. The properties of the reagents added to the (~+ 5 ± 0.5 mV) was observed in the presence of
solution (p) (e.g., ionic strength, surface tension, concen- 1 mM EDTA under strong acidic conditions (pH < 4).
tration, activity) may have additional effects on NB coa- The zeta potential generally reflects the adsorption of
lescence. However, our main objective in this work was to ions in the bulk solutions, a phenomenon which induces
investigate the possible mechanisms behind the growth of an electrical charge on the bubble surface. Previous
NBs in the bulk solutions. More detailed investigations on studies suggested that the zeta potential results from
the effects of p could help to bring the application of the the combination of ion adsorption on the bubble surface
number of NBs contacted (n) to predict other systems gain and the creation of counterions on the internal surface
more attention in the further researches. (Usui 1984; Saulnier et al. 1996). The preferential

Fig. 2 Temporal changes in the average NB diameter (size), in the presence of different chemical reagents. The data were obtained in
triplicate and the error bars show the standard deviation

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J Nanopart Res (2019) 21: 173 Page 7 of 11 173

Table 3 Number of coalesced bubbles during the observation period (at pH 7)

Reagent solutions Observation time (min)

30 60 90 120 150

Number of coalesced bubbles Glucose 1.1 1.2 1.2 1.2 1.2

EDTA 2.1 2.7 2.4 2.4 2.6
DODAB 1.6 3.2 5.8 8.3 13.6
Al3+ 1.1 1.2 2.0 4.7 15.1
3+
Fe 1.2 1.8 2.1 3.2 3.9
Na+ 1.0 1.1 1.8 2.2 2.2

adsorption of H+ ions (hydration energy = − 1127 kJ/ adsorption of DODA+ was dominant, while the effect of
mol; Takahashi 2005) at pH < 4 was greater than that H+ on the zeta potential was negligible for pH > 7;
of OH− groups in the EDTA solution, resulting in a resulting in a drop of zeta potential from + 35 ± 2 to +
positive zeta potential. A higher amount of OH− groups 20 ± 3 mV. At pH > 9, the zeta potential values remained
(hydration energy = − 489 kJ/mol; Takahashi 2005) at stable (~+ 20 ± 5 mV) for pH > 9. The positive charge
pH > 4, resulted instead in a negative zeta potential. resulted from the positivity of the adsorption layer that is
When 1 mM DODAB was added in the solution, the greater than negativity of the bubble inner surface.
NBs were charged positively over a pH range of 2–12. Figure 3 (right panel) shows the zeta potential of
Figure 2 (left panel) shows a decrease in the positive bubbles in the presence of 1 mM metal ions: the NBs
zeta potential value with increasing pH (~+ 40 ± 2 mV were charged negatively and the absolute value of their
for pH = 2, and ~+ 20 ± 5 mV for pH = 12). Similar zeta potential decreased following the addition of Na+;
trends have been reported in earlier studies. For exam- no significant differences were observed in relation to
ple, the surface charge of NBs dropped from ~+ 50 to NBs in tap water (pH > 2). A previous work (Li and
~+ 35 mV increasing the pH from 3 to 12 in a Somasundaran 1991), which tested NaCl solutions at
cetyltrimethylammonium bromide (CTAB) solution concentrations of 100, 10, and 0.01 mM, reported a
(Kim et al. 2000), and from ~+ 18 to ~ 0 mV increasing similar trend of bubble zeta potential: its negative values
the pH from 3.5 to 10.5 in a dodecyltrimethyl ammoni- dropped with increasing NaCl concentration. The pres-
um chloride (DTAC) solution (Jia et al. 2013). The ence of Na+ ions likely did not affect the preferential
DODAB, which is a double-chain cationic surfactant, adsorption of OH− (from the aqueous solution) at the
could induce a bilayer adsorption of gas-liquid interface. Furthermore, an exponential in-
dioctadecyldimethylammonium (DODA+ or crease in the concentration of selective adsorptive
C30H80N+) at the air-water interface. In our case, the groups (e.g., OH− at high pH) has been suggested to

Fig. 3 Zeta potential of bubbles as a function of pH, in the presence of different chemical reagents

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173 Page 8 of 11 J Nanopart Res (2019) 21: 173

Fig. 4 Aqueous speciation of 1 mM Al3+ (left) and 1 mM Fe3+ (right) at various pH levels

cause a higher density of negative charges: ~− Al3+ in an aqueous solution can influence signifi-
18.18 mV for pH = 9, and ~− 23.03 mV for pH = 12. cantly NB zeta potential values. Figure 4 illustrates
Our results show a positive zeta potential in the presence the species which can be formed in Al3+ and Fe3+
of metal ions for pH = 2, proving that when H+ concen- solutions in relation to pH: [Al3+] and [Fe3+] were
tration is increased considerably under very low pH, it predominant at low pH, and their adsorption caused
can cause a drop in the density of negative charges and higher positive zeta potential values.
even change the sign of the NB surface charge. Negative and positive potentials resulted from the
Over the entire studied pH range, positively balance between the charges of the adsorbed group
charged NBs were obtained after the addition of (ions) and those on the inner surface of the NB; in most
trivalent metal ions (i.e., Al3+ and Fe3+) at a con- cases, the potentials reflect the adsorption of additives at
centration of 1 mM. Figure 3 (right panel) shows the air-water interface. Table 4 indicates the adsorbed
that NBs were positively charged in similar ways in species from the analysis using Visual MINTEQ (ver-
the Fe3+ and Al3+ solutions. Overall, the absolute sion 3.1) when adding chemicals into NBs generation
value of their charges decreased with increasing pH. system. Specifically, glucose could not form any
Specifically, in the presence of Al3+, the charge of adsorbed specie at NBs interface so that negative NBs
NBs dropped from ~+ 25 ± 1 to ~+ 9.5 ± 4 mV, while creation was due to the adsorption of OH− from water. In
the pH increased from 2 to 12. These findings indi- other solutions, mechanism of negative (a, b) and pos-
cate that the adsorption of the speciation of Fe3+ and itive (c) NB creation is exemplified in Fig. 5.
In Fig. 5(a, b), the proposed mechanism for negative
Table 4 Dominant adsorbed species of used chemicals on the NB NB creation could be related to OH− (from EDTA) or to
surface (chemicals concentration = 1 mM, solution pH = 7) Na+ added into the solution. Negative NBs seemed to
Chemicals added Adsorbed species undergo OH− adsorption at higher negative charges
(total charge of the inner surface and adsorption layer)
Glucose No adsorbed specie than for Na+ adsorption (balance between inner surface
EDTA OH− (0.51 mM) charges and those of Na+ adsorbed onto the NB surface).
DODAB C30H80N+ (1 mM) In Fig. 5(c), the R+ symbols indicate the cations from the
Al2(SO4)3 Al3+ (0.52 mM) cationic surfactants or trivalent metal ions adsorbed onto
Al (OH)++ (0.06 mM) the surface of the NB, which are partly balanced by the
FeCl3–6H2O Fe3+ (0.01 mM) negatively charged inner surface. In particular, the sum
Fe (OH)2+ (0.012 mM) of the adsorbed cations positive charges was greater than
Fe (OH)++ (0.08 mM) the sum of negative charges on the inner surface. At the
NaCl Na+ (1 mM) end of the process, the zeta potential of the NB shifted
positively.

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J Nanopart Res (2019) 21: 173 Page 9 of 11 173

OH- OH- _
_ _
OH- - -
OHOH _ _ _ __ a
OH-
OH-
__ _ _ _
_ _
OH-
OH- OH-
OH-
_ __ _ _ _ _
_ _ _ _
_
OH-
- _ __ _ _ __ _ _
__ _
OHOH __
- OH-
OH- _ _ _ _ _ _ __ _
OH- adsorption ∑ (-) charge =
Negative NB
onto NB surface ∑ (inner surface + OH- adsorbed)
_
_ _ __
Na+
_ _ _
_
_ _ __ Na+ _ _
_ _ _ + _
_ _ Na+ _ _ Na+
_ _ _ _ _ _
Na+ _ _
_ _ Na+ _ _
_ _ b
_ _ _ _ _
_ _ Na+ +
Na _ _ +
__ _ _ _
__ _ __
_ _ _ Na+ _ _ _ Na+
_ +
Na+
Na+ + _ _ _
Initial NB (negative
charge on inner surface) Na+ adsorption ∑ negative charges > Negative NB
onto NBs surface ∑ positive charges
+ _+
+ _ _ _+ _ + + + +
+_ _ _ _+ +_
R+ R+ _+
R+ + + _ _ + +
+
R+ +R _ _ + +
R + _ _ +
R+ +_ + c
R+ R+ R+ _ _ +
+ _
+ _ _ _ __ + + _+
R+R +R+ + +
R + + + + + + + + +
Cations adsorption ∑ negative charges < Positive NB
onto NBs surface ∑ positive charges
Fig. 5 Proposed mechanism of negatively and positively charged positive NB (with a bilayer of DODA+, species of Al3+, Al
NB generation (a) for negative NB (with OH− adsorption from (OH)2+, Fe3+, Fe (OH)2+, and Fe (OH)2+)
EDTA); (b) for negative NB (with Na+ adsorption); and (c) for

Fig. 6 Evolution of bubble zeta potentials over time, in the presence of different chemical reagents at pH = 7. The graphs show the averaged
values obtained from triplicate measurements; the error bars indicate the correspondent standard deviations

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173 Page 10 of 11 J Nanopart Res (2019) 21: 173

Temporal changes ions, another common trivalent metal ion: the positive
charges were lower in the Fe3+ solution than in the Al3+
In order to observe the behavior of NBs over time, all solution (~+ 8 ± 0.5 mV at the initial measurement and ~+
samples were maintained at a pH of 7. The zeta potential 12 ± 0.5 mVat the end of the 150-min observation period).
of initially formed NBs (in filtered water) was negative Based on the zeta potential analysis, we confirmed that the
(~− 25 ± 3 mV). Negative zeta potential values were presence of metal ions (Na+, Fe3+, and Al3+) improves NB
registered in the glucose solution and EDTA solution, stability in a solution: the zeta potential affected NB size,
whereas positive values were registered in the DODAB which is related to the accumulation rate of metal (positive)
solution (Fig. 6, left panel). In the 1 mM glucose solu- ions on the NB surface (Temesgen et al. 2017). In this
tion, a stable zeta potential would be a desirable out- study, the remaining bubble surface charges (~− 12 ±
come; however, a reduction in zeta potential (from ~− 0.5 mV in the Na+ solution, ~+ 12 ± 0.5 to + 20 ± 1 mV
10 ± 1 to ~− 21 ± 1 mV) was observed during the obser- in Al3+ solution, and ~+ 8 ± 0.5 to ~+ 12 ± 0.5 mV in the
vational period. The negative charge of NBs slightly Fe3+ solution) support that idea that zeta potential values <
dropped in the presence of 1 mM EDTA, during the first 30 mV could inhibit bubble coalescence after the addition
120 min, but remained stable after reaching − 24 ± of metal ions.
2 mV. In contrast, the zeta potential of NBs in the
1 mM DODAB solution was ~+ 40 ± 2 mV with a
fluctuation around 0 mV for the whole 150-min period Conclusions
(Fig. 6, left panel). These results prove the stability of
bubbles in the bulk solution for at least the first 150 min. Remain of NBs in the presence of different chemical
Prior works have documented bubble stability in several reagents was discussed in relation to evolution of their
surfactant solutions via zeta potential analysis: there, the size and zeta potential. Coalescence of NBs was the
bubbles remained stable for a period of 60 min or up to proposed mechanism of the size growth. Moreover, we
> 24 h (Saulnier et al. 1996; Kim et al. 2000; Wu et al. suggested that the adsorbed species created an adsorp-
2012). These studies agree with the results of our work: tion layer on the surface of NB, resulting in negative or
the ion adsorption carried out by additive head groups positive NB creation. Our results demonstrated that the
can not only influence the sign of the bubble surface zeta potential was remained over time, confirming the
charge but also create a protective layer around the stability of NBs. Behaviors of the NB size and zeta
bubble and inhibit the dissolution of NBs in surfactant potential are all important factors affecting bubble-
solutions. mineral pollutant interactions and mineral flotation
Figure 6 (right panel) illustrates the surface charge of processes.
NBs observed in metal ion solutions: monovalent metal
ions (Na+) yielded negative zeta potentials, which
Funding information This work was supported by Korea En-
remained quite stable for the whole studied period (~− vironment Industry & Technology Institute (KEITI) through Pub-
12 ± 0.5 mV, similar to the NB charge values in tap water). lic Technology Program based on Environmental Policy, funded
The observed negative charges agree with previously re- by Korea Ministry of Environment (MOE) (2018000200001).
ported results (Li and Somasundaran 1991; Cho et al.
2005; Arturo et al. 2015), suggesting that positive mono- Compliance with ethical standards
valent metal ions (Na+) are poorly attracted to NB surfaces.
Conflict of interest The authors declare that they have no con-
The invariability of the zeta potential confirmed the stabil- flict of interest.
ity of negatively charged bubbles for at least the first
150 min in the 1 mM Na+ solution. In contrast, positively
charged bubbles were formed in trivalent metal ion solu-
tions (i.e., Al3+ and Fe3+). We observed changes in the
charges of NBs after the addition of a small amount of Al3+ References
ions. The value of the zeta potential gradually increased
with time, from ~+ 12 ± 0.5 mV (initial measurement) to + Agarwal A, Ng WJ, Liu Y (2011) Principle and applications of
20 ± 1 mV (at the end of the 150-min period). We also microbubble and nanobubble technology for water treatment.
investigated the charges of NBs in the presence of Fe3+ Chemosphere 84(9):1175–1180

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