Journal of Membrane Science 281 (2006) 386396

Size control of nanobubbles generated from

Shirasu-porous-glass (SPG) membranes
Masato Kukizaki a, , Masahiro Goto b
a

Miyazaki Prefecture Industrial Technology Center, 16500-2 Higashi-kaminaka, Sadowara, Miyazaki 880-0303, Japan
Department of Applied Chemistry, Graduate School of Engineering, Kyushu University, 744 Moto-oka, Fukuoka 819-0395, Japan
Received 18 November 2005; received in revised form 7 April 2006; accepted 8 April 2006
Available online 25 April 2006

Abstract
We recently discovered that monodispersed nanobubbles/microbubbles could be generated from Shirasu-porous-glass (SPG) membranes with
uniform pores in a system composed of dispersed gaseous and continuous water phases containing a surfactant. In the present study, size control of
the nanobubbles generated was examined using SPG membranes with less than submicron-size pores. Air was pressurized into a sodium dodecyl
sulfate (SDS) solution ranging from 0.05 to 0.5 wt.% flowing through a SPG membrane with a transmembrane/bubble point pressure ratio of
1.12.0. Under these conditions, monodispersed nanobubbles with a mean bubble diameter of 360720 nm were stably produced from membranes
with mean pore diameters of 4385 nm. The mean bubble diameter was shown to be 8.6 times larger than the mean pore diameter; therefore, the
nanobubble diameter could be controlled by the membrane pore size. Mean bubble diameter was barely affected by a flow velocity of 0.53.7 m s1
or by the surface tension between air and 0.050.5 wt.% SDS solution.
2006 Elsevier B.V. All rights reserved.
Keywords: Monodispersed nanobubbles; Bubble size control; Shirasu-porous-glass membrane; Bubble point pressure; Surfactant

1. Introduction
Shirasu-porous-glass (SPG) membranes [1,2], which are
prepared by phase separation of the mother glass in the
Na2 OCaOMgOAl2 O3 B2 O3 SiO2 system and subsequent
acid leaching, have uniform pores with mean diameters ranging
from 40 to 20 m. The mean diameter size can be determined by
the phase-separation conditions, that is, the temperature and the
time of thermal treatment. SPG membranes, despite their high
porosity, have high water resistance due to their relatively high
Al2 O3 content and a sufficiently high mechanical strength for
practical use [3]. These membranes are used as the liquid/liquid
dispersion medium in membrane emulsification, which we previously proposed as a novel method for preparing monodispersed emulsions [4]. During membrane emulsification, the dispersed phase is pressed through the membrane pores forming
droplets on the permeate side, while the continuous phase flows
along the membrane surface. A distinguishing feature is that the

Corresponding author. Tel.: +81 985 74 4311; fax: +81 985 74 4488.
E-mail address: kukizaki@iri.pref.miyazaki.jp (M. Kukizaki).

0376-7388/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2006.04.007

resulting droplet size can be controlled primarily by varying the

membrane pore size. Many researchers have attempted to control
the size distribution of emulsions through membrane design and
control of the operating parameters; for example, the emulsification pressure, velocity of the continuous flow and emulsifier, and
so on [517]. The membrane emulsification technique is used
in various processes such as the development of low-calorie fat
spreads, spacer material for liquid crystal displays, and carriers
for drug delivery systems [2,6,10,11,18].
We recently proposed a new method for generating monodispersed nanobubbles and microbubbles using SPG membranes
as the gasliquid dispersion medium [19]. In this method, the
gaseous phase is pressed through the SPG membrane into a flowing continuous liquid phase containing a surfactant. The biggest
advantage of this technique is that the resultant bubble size can be
controlled by varying the pore size of the membrane employed,
as with droplet size control during membrane emulsification.
Nanobubbles and microbubbles have many potential applications in fields such as the pharmaceutical, food, chemical,
and cosmetic industries. In the field of medicine, nanobubbles
and microbubbles are expected to be applicable to areas such as
developments of ultrasound contrast agents [20], targeted drug

M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

delivery, thrombus destruction, and tumor destruction, while in

the food industry, the density and texture of, for example, gel
and cream-based foods could be controlled by the uniform and
fine dispersal of gas into these materials [21]. In the chemical
industry, nanobubble and microbubble generation is expected
to be applicable to developments of porous materials such as
microcellular plastic foam [22]. Thus size control of nano- and
micro-bubbles is crucial in all these applications.
In addition to the above, formation of nanobubbles and
microbubbles is also applicable to developments of highly efficient gasliquid contactors because of the creation of a large
interfacial area between the gas and liquid. Thus, in designing gasliquid contactors; for example, a bubble column, gas
absorbers, chemical reactors, and fermenters, the estimation and
control of the size and distribution of bubbles generated using
a nozzle, orifice, porous plate or porous membrane is essential.
Monodispersed nanobubbles and microbubbles are also useful in
fundamental studies on their characterization, because interpretation of their experimental results is much simpler than those of
polydispersed nanobubbles and microbubbles. That is, they are
useful system for measurements of important properties such as
bubble stability, gas-dissolution rate, and the bubble-rising rate.
Kim et al. [23] showed that nanobubbles with a mean diameter of 300500 nm were stably generated by ultrasonication
using a palladium electrode. Moreover, Oeffinger and Wheatly
[24] demonstrated that nanobubbles with a mean diameter of
400700 nm could be produced by ultrasonication of a surfactant mixture solution with constant purging using a steady stream
of octafluoropropane gas and subsequent centrifugation of the
resultant bubbles, and also showed that the generated nanobubbles were applicable in a nano-scale contrast agent. However,
it is difficult to generate monodispersed nanobubbles with the
above methods. A few papers have documented the formation of
monodispersed microbubbles [19,21,25]. For example, GananCalvo and Gordillo [21] reported the formation of monodispersed microbubbles with a mean diameter of 5120 m on
the basis of a self-excited breakup phenomenon (which locks
at a certain frequency) of a short gas microligament coflowing in a focused liquid stream. Moreover, Yasuno et al. [25]
showed that monodispersed microbubbles with a mean diameter of 3550 m could be generated using a microfabricated
silicon microchannel. However, there has been no investigation
reported regarding the size control of nanobubbles.
In the present study, size control of nanobubbles was investigated using SPG membranes, newly developed in our laboratory,
with mean pore diameters of less than submicron size [26]. The
effects of nanobubble generation on the applied transmembrane
pressure, wall shear stress at the membrane surface and surface
tension between air and the water phase were also studied.

387

Table 1
Chemical composition of Shirasu and the mother glass used for preparation of
SPG membranes (wt.%)
Component

Shirasu

Mother glass

Na2 O
K2 O
CaO
MgO
A12 O3
Fe2 O3
B2 O 3
SiO2

4.20
4.02
1.00
0.15
12.15
1.50

76.98

5.74
2.57
12.54
4.82
7.77
0.96
16.40
49.20

used as raw materials. Shirasu is a volcanic ash widely available in the southern part of Kyushu Island, Japan. As shown
in Table 1, Shirasu is a source of SiO2 and Al2 O3 , and contains Na2 O, K2 O, CaO, MgO and Fe2 O3 as impurities. The
mixture was melted at 1623 K for 3 h in a platinum crucible.
After cooling to 1473 K, a glass sample was formed by blowing into a tube 5.6 mm in outer diameter, 0.3 mm in thickness
and 100 mm in length. The chemical composition of the mother
glass tube is listed in Table 1. The glass tubes were thermally
treated at 933953 K for 20 h in an electric furnace. The phaseseparated glass tubes were then leached out with the hydrochloric acid solution of 0.5 mol dm3 at 278 K resulting in SPG
membranes with four different pore diameters (43, 55, 64 and
85 nm). SPG membranes with mean pore diameters of 550 nm
and 2.23 m were also prepared for examining the effect of the
shear stress at the membrane wall caused by the continuous
water phase on the monodispersed microbubble formation (see
Section 3.5). The mean pore diameter and porosity of the membranes were determined using the mercury penetration method
with a mercury porosimeter (Poresizer 9320, Micromeritics
Co. Ltd., USA). Mean pore diameter was expressed as 50 Dm ;
that is, the diameter corresponding to 50 vol.% on a relative
cumulative pore diameter distribution curve. The microstructure of the membranes was also observed by a scanning electron
microscope (SEM; S-800M, Hitachi High Technology Co. Ltd.,
Tokyo, Japan). The membrane samples were sputter-coated with
platinumpalladium alloy (8:2) using an ion sputter coater (E1030, Hitachi High Technology Co. Ltd.).
The contact angle between the membrane surface and the
water phase was calculated using the liquid-capillary-rising
method [27] at 293 K. This method is based on the Washburns
equation, which has the advantage that the contact angle can be
directly measured for hydrophilic membranes.
Shirasu (KP#60F) was obtained from Kyushu Pumice Co.
Ltd. (Miyazaki, Japan). Na2 CO3 , CaCO3 , MgO, H3 BO3 and
HCl (all reagent grade) were all purchased from Wako Pure
Chemical Industries Co. Ltd. (Tokyo, Japan).

2. Experimental
2.2. Nanobubble formation
2.1. Preparation and characterization of SPG membranes
Tubular SPG membranes with four different mean pore diameters from 43 to 85 nm were prepared in our laboratory [26]. A
mixture of Shirasu, Na2 CO3 , CaCO3 , MgO and H3 BO3 were

The experimental apparatus used for the bubble formation

experiments is shown in Fig. 1. The gasliquid dispersion
system consisted of air as the dispersed gaseous phase and
distilled water containing sodium dodecyl sulfate (SDS) as

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M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

Fig. 1. Schematic diagram of the experimental apparatus.

the continuous water phase. The SDS concentration of the

water phase ranged from 0.01 to 0.5 wt.%. A continuous water
phase (SDS aqueous solution) of 3.0 dm3 was flowed inside
the membrane using a pump, while air was introduced on the
outside and forced through the membrane pores. The gaseous
phase flux, Jd , was calculated using the following:
Jd =

Q
A

(1)

where Q is the volumetric flow rate of the air measured

using a flow meter (Fig. 1) and expressed as atmospheric
pressure (101.3 kPa), and A is the effective membrane area
(1.57 103 m2 in this study). Transmembrane pressure was
calculated as the difference between the dispersed phase
pressure and mean pressure of the continuous water phase.
Bubble point pressure is defined as the transmembrane pressure
at which bubbles first appear in a water phase from a membrane
surface. In this study, when bubbles began to be formed from
SPG membranes, a light diffraction/scattering peak began to
be detected using a laser diffraction particle size analyzer (see
Section 2.3). Thus, the bubble point pressure was determined
by measuring the transmembrane pressure at which light
diffraction/scattering peak began to be detected.
Mean water phase flow velocity, u, in the membrane tube
ranged from 0.5 to 3.7 m s1 , corresponding to a Reynolds number, Re, of 280021,000. Thus, under these conditions, the flow
was turbulent. The shear stress at the membrane wall, , was
calculated using:
=

di Pfr
4 L

(2)

where di is the inner diameter of the membrane tube and Pfr is

the pressure drop necessary for overcoming friction resistance
in the membrane tube over length L. In the case of turbulent flow,
Eq. (2) is as follows:
=

c u2
8

(3)

where c is the density of the water phase and is the

Moody friction factor, 2500 < Re < 100,000, given by the Blasius

equation:
= 0.3164Re0.25

(4)

By substituting Re of 280021,000 into Eq. (4) and the resultant Eq. (4) into Eq. (3), = 1.447.2 Pa. All bubble formation
experiments were carried out at 293 K.
The surface tension between the air and water phase was
measured using the drop volume method at 293 K. SDS (purity
> 97%) and the air cylinder (synthetic air, purity > 99.999%)
were purchased from Wako Pure Chemical Industries Co. Ltd.
and Japan Fine Products Co. Ltd. (Tochigi, Japan), respectively.
2.3. Mean bubble diameter and diameter distribution
Diameter distributions of the generated bubbles were immediately measured using a laser diffraction particle size analyzer
(SALD2100, Shimadzu Co. Ltd., Kyoto, Japan) with the refraction index of air (1.0) [19,24], as shown in Fig. 1. This analyzer
allowed the detection of bubbles in the range of 0.031000 m.
The monodispersity of the bubbles generated was determined
using the particle size dispersal coefficient [19]:
=

90 D

b
50 D

10 D

(5)

where 90 Db , 50 Db and 10 Db are the diameters corresponding to

90, 50, and 10 vol.% on the relative cumulative bubble size distribution curve, respectively; 50 Db represents the mean bubble
diameter.
3. Results and discussion
3.1. Characterization of SPG membranes
Figs. 2 and 3 show SEM images and the cumulative pore
diameter distributions of SPG membranes with mean pore diameters of 43, 55, 64 and 85 nm. All the SPG membranes have
cylindrical tortuous pores that form a three-dimensional network, reflecting the phase-separated structure of the mother
glass [1,26]. As shown in Table 2, the membrane porosity measured by the mercury penetration method, and the contact angle

M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

389

Fig. 2. SEM images of SPG membranes with mean pore diameters of (a) 43 nm, (b) 55 nm, (c) 64 nm and (d) 85 nm.

between the membrane surface and water phase calculated using

the liquid-capillary-rising method were 0.560.58 and 2327 ,
respectively, irrespective of pore size.
3.2. Bubble point pressure
Bubble point pressure was measured using SPG membranes
with different mean pore diameters. Fig. 4 shows the relationship
between the membrane pore diameter, 50 Dm , and bubble point
pressure, PBP . Bubble point pressure increased with decreasing membrane diameter. The bubble point pressure at which air
Table 2
Characteristics of the SPG membranes used in this study

Fig. 3. Cumulative pore diameter distributions of SPG membranes with mean

pore diameters of (a) 43 nm, (b) 55 nm, (c) 64 nm and (d) 85 nm.

Mean pore diameter 50 Dm (nm)

Porosity

Contact angle ( )

43
55
64
85

0.58
0.56
0.57
0.56

25
23
27
25

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M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

Fig. 4. Relationship between bubble point pressure, PBP , and mean pore size,
50 D . The dotted line shows the bubble point pressure calculated from Eq. (6).
m
SDS concentration was 0.3 wt.% and water phase flow velocity was maintained
at 0.7 m s1 .

began to permeate through the membrane into 0.3 wt.% SDS

solution can be calculated from the following equation for capillary pressure [19]:
PBP =

4 cos
50 D
m

(6)

where is the surface tension between air and the water phase
and is the contact angle between the membrane surface and
the water phase. Substitution of the measured values shown
in Table 2 and = 36.8 mN m1 (see Fig. 10) into Eq. (6) gives
the dotted line shown in Fig. 4. From the experimental data,
PBP was shown to be inversely proportional to 50 Dm , and these
results were in good agreement with the theoretical line.

Fig. 5. Cumulative size distributions of nanobubbles generated from SPG membranes with mean pore diameters of (a) 43 nm, (b) 55 nm, (c) 64 nm and (d)
85 nm. No light diffraction/scattering peak of the water phase was detected
before bubble formation (e). SDS concentration was 0.3 wt.% and water phase
flow velocity and transmembrane/bubble point ratio were maintained at 0.7 and
1.1 m s1 , respectively.

results show that the mean bubble diameter can be controlled by

membrane pore size.
Bubble formation from a pore mainly consists of bubble growth (bubble expansion) and bubble detachment [28,29]
(Fig. 7). In the nanobubble formation process using SPG membranes, the various forces act on a nanobubble formed at a
pore opening: the airwater surface tension acts mainly on the
nanobubble as a force holding the nanobubble at the pore opening. Contrarily, the drag force caused by the water-phase flow
acts mainly on the nanobubble as a force detaching the nanobubble from the pore opening. The nanobubble exuding from the
pore into the flowing water phase would initially have the same

3.3. Relationship between bubble diameter and membrane

pore diameter
Fig. 5 shows the cumulative diameter distributions of
monodispersed nanobubbles generated using SPG membranes
with diameters of 43, 55, 64 and 85 nm, respectively, at a transmembrane pressure 1.1 times higher than each bubble point
pressure. The flow velocity and concentration of SDS solution
were kept at 0.7 m s1 and 0.3 wt.%, respectively. Under these
conditions, monodispersed nanobubbles with a mean bubble
diameter of 360720 nm were stably generated from membranes
with mean pore diameters of 4385 nm, reflecting the uniformity of the SPG membrane pores. No light diffraction/scattering
peak of the water phase before bubble formation was detected,
as shown in Fig. 5(e). Fig. 6 shows the relationship between the
mean bubble diameter and mean pore diameter of the membrane.
The mean bubble diameter increased linearly with increasing
mean pore diameter with a correlation slope of 8.6 (correlation
coefficient: 0.995). The slope was close to the value of 8.8 that
has been previously reported for microbubble formation [19].
The particle size dispersal coefficient of the nanobubbles formed
was in the range of 0.450.48; and was almost independent of the
membrane pore diameter, as shown in Fig. 6. The experimental

Fig. 6. Relationships among the mean pore diameter, 50 Dm , mean bubble diameter, 50 Db , and the particle size dispersal coefficient, . SDS concentration was
0.3 wt.% and water phase flow velocity and transmembrane/bubble point ratio
were maintained at 0.7 and 1.1 m s1 , respectively.

M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

391

Fig. 7. Schematic representation of bubble formation process from a pore.

diameter as the pore. The nanobubble would form a hemisphere

shape, and the internal pressure of the nanobubble would reach
to its maximum value. But then, due to the nanobubble expansion
the nanobubble has to grow to reduce its internal pressure. On the
other hand, as the nanobubble grows (expands) at the membrane
surface, and thus the diameter of the bubbles increases, the drag
force caused by the water-phase flow increases [28,29]. When
the detaching force becomes larger than the holding force due to
the nanobubble expansion, the nanobubble would detach from
the pore opening. As a result, the monodispersed nanobubbles
with a diameter larger than the pore diameter are formed from
the membrane.

has been found with droplet formation from SPG membranes

[10,1214,17]. Yasuno et al. [14] observed in situ formation of
individual emulsion droplets from the pores of a plate-type SPG
membrane with a mean diameter of 15 m using microscope
video systems, and showed that the increase in the dispersed oil
phase flux with increasing transmembrane pressure resulted in
the formation of a polydispersed emulsion. They also explained
that, at a high dispersed oil phase flux, the oil phase flowed out
continuously like a laminar flow into the water phase, and thus,

3.4. Effect of transmembrane pressure on bubble diameter

Fig. 8 shows the effect of the transmembrane/bubble point
pressure ratio, Pr , on the gaseous phase flux, Jd , mean bubble
diameter, 50 Dm , and particle size dispersal coefficient, , with a
55-nm membrane and SDS concentration of 0.3 wt.%. The water
phase flow velocity was set at 0.7 m s1 . At Pr < 1, no bubbles
were observed; however, in a range of 1 Pr 2 monodispersed
nanobubbles were stably generated. In addition, the gaseous
phase flux linearly increased with increasing transmembrane
pressure, while both mean bubble diameters and particle size
dispersal coefficients were nearly constant, independent of the
transmembrane/bubble point pressure ratio. Contrarily, at Pr > 2,
larger bubbles with a broad diameter distribution were generated and the particle size dispersal coefficient increased with
increasing transmembrane pressure. With increasing transmembrane pressure, the dispersed phase flux increased compared to
in the range of 1 Pr 2.
These results can be explained as follows: in a range of
1 Pr 2, monodispersed nanobubbles grow at pore openings
until they reach a certain size and then detach by necking. At
Pr > 2, probably because of the effect of the inertial force of
the gaseous phase, the dispersed gaseous phase flows out continuously through the membrane into the water phase forming
larger bubbles. Similar transmembrane pressure dependency

Fig. 8. Effect of transmembrane/bubble point pressure ratio, Pr , on the dispersed

gaseous phase flux, Jd , mean bubble diameter, 50 Db , and particle size dispersal coefficient, . Results of a SPG membrane with a mean pore diameter of
55 nm are shown. The SDS concentration was 0.3 wt.% and the water phase
flow velocity was maintained at 0.7 m s1 .

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M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

larger droplets were formed because of the effect of the inertial force of the oil phase, which was enough to cause dispersed
phase outflow through the membrane.
A number of reports have described the dispersed gaseous
phase flux in relation to bubble formation from a porous nozzle
[e.g. 3032]. According to Anagbo and Brimacombe [31], the
dispersion patterns of bubbles generated from a round porous
nozzle in a water bath can be classified into three types with
respect to the gaseous phase flux; namely, low, middle, and high
gas flow rate regimes. Under a low gas flow rate, small bubbles of a few millimeters in diameter were generated without
coalescence or disintegration, while under a middle flow rate
some bubbles clustered and coalesced into a large bubble. Further, under a high gas flow rate, bubbles forming at the nozzle
exit merged into one large packet. These results are similar to
our results; however, further detailed discussion cannot be made
because Anagbo and Brimacombe dealt mostly with bubbles of
submillimeters to millimeters in diameter at rather high flow
rates. In this study, on the other hand, bubbles of less than 1 m
in diameter (nanobubbles) were formed from SPG membranes
with pore diameters of less than submicron size at a very low
gaseous phase flux.
3.5. Effect of shear stress at the membrane surface on
bubble diameter
Bubbles formed on the membrane surface are thought to
detach due to the shear force caused by the water phase flow.
Fig. 9 shows the effect of shear stress at the membrane wall,
, on bubble diameter using SPG membranes with mean pore
diameters of 55 nm, 550 nm and 2.23 m and an SDS concentration of 0.3 wt.%. The transmembrane/bubble point pressure
ratio was set at 1.1. With the 550-nm a and 2.23-m membranes,
the mean bubble diameter decreased as the shear stress increased
until reaching a certain diameter at which the bubbles became
more or less independent of the shear stress. The largest change
in bubble diameter occurred at a small shear stress. On the con-

Fig. 9. Effect of shear stress at the membrane wall, , on the mean bubble
diameter, 50 Db . SPG membranes had a mean pore diameter of 55 nm (circles),
550 nm (triangles) and 2.23 m (squares). SDS concentration and transmembrane/bubble point ratio were 0.3 and 1.1 wt.%, respectively.

trary, with the 55-nm membrane, there was little change in the
mean bubble diameter. This result shows that the mean diameter of the nanobubbles generated was little affected by the shear
force of the water phase flow velocity.
A number of reports have described bubble formation with
a liquid crossflow [e.g. 3344]. The findings show that the bubble diameter decreases with increasing liquid crossflow velocity
until reaching a certain diameter at which the bubbles become
more or less independent of the flow velocity. However, the
above reports dealt mostly with bubbles of submillimeters to
millimeters in diameter.
On the other hand, several reports have documented the effect
of wall shear stress at the membrane surface on droplet formation using porous membranes such as SPG [10,14,16,17],
ceramic [45], polycarbonate [46], and micro-engineered silicon
nitride membranes [47]. Schroder et al. [45] prepared oil-inwater (O/W) emulsions using ceramic membranes and showed
that the smaller the membrane pore size the smaller the minimum droplet size and the smaller the shear stress needed to
reach a certain droplet size. For instance, a wall shear stress of
more than 2 Pa was required for a 100-nm membrane and more
than 30 Pa for an 800-nm membrane. Using SPG membranes
with a mean pore diameter of 570 nm, Katoh et al. [10] found
that a minimum wall shear stress of 0.5 Pa, which corresponded
to a mean continuous water phase flow velocity of 0.2 m s1 ,
was needed for formation of monodispersed oil droplets with a
mean diameter of 2.6 m. As an explanation for this, Schroder
et al. [45] suggested that droplet size decreases with increasing
continuous water phase flow rate because of the increased drag
force caused by the water phase flow at relatively low wall shear
stress. However, the further decrease in mean droplet size at high
wall shear stress is prevented by the forming droplets hindering
each other in detaching from the pores; Droplets forming at the
pore openings are therefore surrounded by other droplets, and
therefore, the continuous phase fluid cannot flow freely around
them, but rather it flows above them. A similar effect is observed
with a rough membrane surface. On the other hand, Joscelyne
and Tragardh [48], and Peng and Williams [49] suggested that
with very small droplets the sublayer thickness might start to
limit the effect of crossflow velocity. That is, within a laminar
sublayer existing near the membrane surface the flow velocity of
the water phase is relatively small, despite the fact that outside
this sublayer the flow velocity can be very high and turbulent.
With small droplets, the droplet diameter is always smaller than
the laminar sublayer thickness, so the flow velocity around the
droplets is always small and laminar, irrespective of the total
flow rate of the continuous phase.
Fine bubble formation from SPG membranes seems to be
almost identical to droplet formation. Therefore, it is suggested
that the diameter of very small bubbles (nanobubbles) is barely
affected by the shear stress of the water phase due to the rough
membrane surface effect and/or sublayer thickness.
3.6. Effect of surface tension on mean bubble diameter
First, surface tension between air and the water phase
was measured with SDS concentrations of 0.010.5 wt.%.

M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

393

tension within a range of 58.067.4 mN m1 (SDS concentration of 0.010.05 wt.%). This was probably due to unsaturated
adsorption of SDS molecules at the newly formed airwater
interface during bubble formation with decreasing SDS concentration. Consequently, the probability of bubble coalescence at
the membrane surface increases, and thus, large bubbles with a
broad diameter distribution are formed.
3.7. Effect of operating parameters on void fraction

Fig. 10. Relationship between SDS concentration and surface tension, ,

between air and the water phases.

Fig. 10 shows that the critical micelle concentration (cmc) was

0.20 wt.% SDS. Next, the effect of surface tension between air
and the water phase on bubble diameter was investigated using
a membrane with 55-nm pores at a water phase flow velocity of 0.7 m s1 . Fig. 11 shows the effect of surface tension
on mean bubble diameter and particle size dispersal coefficient
with an SDS concentration of 0.010.5 wt.%, which corresponds
to a surface tension of 67.436.5 mN m1 . Monodispersed
nanobubbles were stably generated in a surface tension range
of 58.036.5 mN m1 (SDS concentration of 0.050.5 wt.%);
that is, even at an SDS concentration below the cmc. However,
an increase in the mean bubble size diameter and particle size
dispersal coefficient was observed with an increase in surface

For practical applications of nanobubble formation using

SPG membranes, the volume of gaseous phase (air) permeated
through the membrane is as important as the bubble diameter
and the diameter distribution. The void fraction, , is defined as
the ratio of the volume occupied by the dispersed gaseous phase
(air), Vd to that of the two-phase mixture (the air and water
phase):
=

1
Vd
=
Vd + V c
1 + (Vc /Vd )

(7)

where Vc is the volume of continuous water phase. The gaseous

phase volume is expressed using the gaseous phase flux as following:
Vd = Qt = Jd At

(8)

where t is the time. By substituting Eq. (8) into Eq. (7), the void
fraction becomes
=

1
Vd
=
Vd + V c
1 + (Vc /Jd At)

(9)

and it can be seen that the void fraction increases with increasing
gaseous phase flux and/or membrane area.
For laminar viscous air flow through the membrane pores
(see the Appendix A), the gaseous phase flux may be described
by the HagenPoiseuille equation as follows:
2

Jd =

k(50 Dm ) Peff
32d
x

(10)

where k is the proportion of active pores (the proportion of the

pores taking part in bubble formation to all the pores), Peff
the effective transmembrane pressure, d the viscosity of the
dispersed gaseous phase, the pore tortuosity, and x is the
membrane thickness. The effective transmembrane pressure is
given by
Peff = P PBP

Fig. 11. Effect of surface tension, , on the mean bubble diameter, 50 Db ,

and particle dispersal coefficient, . Results of a SPG membrane with a mean
pore diameter of 55 nm are shown. Water phase flow velocity and transmembrane/bubble point ratio were maintained at 0.7 and 1.1 m s1 , respectively. The
dotted line shows the critical micelle concentration (cmc) of SDS.

(11)

At a transmembrane pressure larger than the bubble point pressure (i.e. at a transmembrane pressure equal to 0), bubble formation at the membrane surface starts. In this study, monodispersed
nanobubbles were formed in a range of 1 Pr 2. By substituting P = PBP Pr and Eq. (6) into Eq. (11), the effective
transmembrane pressure is given by
Peff = PBP (Pr 1) =

4 cos
(Pr 1)
50 D
m

(12)

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M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

By substituting Eq. (12) into Eq. (10), the gaseous phase flux
becomes
Jd =

k cos (50 Dm )
(Pr 1)
8d
x

(13)

and it can be seen that with increasing transmembrane pressure

in a range of 1 Pr 2, the gaseous phase flux increases (Fig. 8)
and thus the void fraction increases. However, the gaseous phase
flux is independent of the water phase velocity and thus the void
fraction is not at all influenced of the water phase velocity. In
Eq. (13), , , 50 Dm , , and x are related to the membrane characteristics. For SPG membranes, , (Table 2), [50], and x
are almost constant, irrespective of the membrane pore diameter. Hence, with increasing the pore diameter the gaseous phase
flux increases, and therefore the void fraction increases.
4. Conclusions
In this study, our newly developed SPG membranes with uniform pore diameters of less than submicron size were used to
generate nanobubbles with a narrow diameter distribution. The
applied transmembrane pressure, shear stress at the membrane
wall caused by water phase flow, and surface tension between
the gaseous phase and water phase were also investigated. The
gasliquid dispersion system consisted of air as the dispersed
gaseous phase and pure water containing SDS as the continuous
water phase. Monodispersed nanobubbles with a mean bubble
diameter of 360720 nm were stably generated by pressing air
through SPG membranes with mean pore diameters of 4385 nm
at a transmembrane/bubble point pressure ratio of 1.02.0 while
0.050.5 wt.% SDS solution was flowed along the inner surface of the membrane. Mean bubble diameter was found to be
8.6 times larger than mean pore diameter: therefore, nanobubble
diameter could be controlled by varying the membrane pore size.
Larger bubbles with a broad diameter distribution were generated above a transmembrane/bubble point pressure ratio of 2.0
or below an SDS concentration of 0.03 wt.%. Moreover, mean
bubble diameter was barely affected by an SDS solution flow
velocity of 0.503.70 m s1 .
Acknowledgment
We thank Dr. G.T. Vladisavljevic of the University of
Massachusetts-Amherst for valuable discussion.
Appendix A. Gas ow regime through the pores of SPG
membranes
The Knudsens number, Kn is the dimensionless parameter
used to define the gas flow regime through a pore, and is given
by
Kn =

p
Dm

(14)

where p is the mean free path of the gas molecules, and Dm is

the pore diameter. The mean free path, which is defined as the

average distance traversed by a molecule between collisions, can

be written as:
p =

kB T

dg2 P 2

(15)

where kB is the Boltzmann constant, T the absolute temperature,

dg the diameter of the gas molecule, and P is the gas pressure.
This equation indicates that as the pressure decreases, the mean
free path increases.
If Kn is significantly smaller than unity, the gas flow is purely
viscous. In laminar viscous flow, the flow is driven by a pressure difference and the viscosity of the gas opposes the flow,
as described by the HagenPoiseuille equation. If Kn is significantly larger than unity, the gas flow is mainly by molecular
diffusion, in which the gas molecules colloid elastically with
the wall of the pores, and a concentration difference provides
the motive force for the flow by diffusion.
For air at 293 K, the mean free path is approximately given
by
p

6.7
P

(16)

where p is expressed in nm and P in MPa. In this study, the

gas pressure (the applied transmembrane pressure) and the pore
diameter of the SPG membranes were in the range of approximately 1.53.5 MPa (Fig. 4), and 4385 nm. Substituting P of
1.53.5 MPa into Eq. (16) and the resultant p of 1.94.5 and Dm
of 4385 nm into Eq. (14) gave Kn of 0.0440.053, which were
significantly less than unity. Therefore, the air flow through the
pores of SPG membranes should be viscous.

Nomenclature
A
dg
di
nD
b
50 D

Dm
50 D
m
Jd
k
kB
L
N
P
PBP
Pr
P
Peff
Pfr

effective membrane area (m2 )

diameter of gas molecule (m)
inner diameter of the membrane tube (m)
bubble diameter at n% of the cumulative volume
(m)
mean bubble diameter (m)
pore diameter (m)
mean pore diameter (m)
gaseous phase flux at atmospheric pressure and
293 K (m3 m2 s1 )
proportion of active pores (%)
Boltzmann constant (J K1 )
length of the membrane tube (m)
number of pores
gas pressure (Pa)
bubble point pressure (Pa)
ratio of transmembrane pressure to bubble point
pressure
transmembrane pressure (Pa)
effective transmembrane pressure (Pa)
pressure drop required for overcoming friction
resistance in the membrane tube (Pa)

M. Kukizaki, M. Goto / Journal of Membrane Science 281 (2006) 386396

Q
Re
T
u
Vc
Vd
x

volumetric flow rate of the gaseous phase (m3 s1 )

Reynolds number in the membrane tube
absolute temperature (K)
mean flow velocity of the water phase in the membrane tube (m s1 )
volume of continuous water phase (m3 )
volume of dispersed gaseous phase (m3 )
membrane thickness (m)

Greek letters

void fraction

surface tension between the gaseous phase and

water phase (N m1 )

particle size dispersal coefficient

membrane porosity
d
viscosity of dispersed gaseous phase (Pa s)

contact angle between the membrane surface and

water phase ( )

Moody friction factor

p
mean free path of gas molecules (m)
density of the continuous water phase (kg m3 )
c

wall shear stress at the membrane surface (Pa)

pore tortuosity
Subscripts
b
bubble
c
continuous water phase
d
dispersed gaseous phase
g
gas
m
membrane pore

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