Documente Academic
Documente Profesional
Documente Cultură
by
Palaniappan Arumugam
Palaniappan Arumugam
Master of Applied Science
Department of Mechanical and Industrial Engineering
University of Toronto
2015
Abstract
The micro-bubble technology in water is widely known and effectively used, but the
fundamental mechanisms of the micro-bubble generation and characteristics are not clearly
established. To better the understanding, extensive literature survey coupled with theoretical and
experimental bubble size estimations and volumetric mass transfer rate calculations were carried
out. Observed multitude of increase in the volumetric mass transfer rate is essentially due to the
specific interfacial area rather than the liquid mass transfer co-efficient. This signifies the
effectiveness of pressurized dissolution type over its counterparts. A second set of experiments
were focussed on particle size analysis using Bluewave particle size analyzer. Measurements for
bubble size distribution were made alongside two cases of surfactant addition, tween20 at
concentrations of 10mM and 1mM. The effect of surfactant on bubble dynamics and stabilization
is interpreted and the axial rise distance hence the rise velocity are computed for both
experimental and theoretical data.
ii
Acknowledgments
iii
Table of Contents
Abstract .......................................................................................................................................... ii
Acknowledgments ........................................................................................................................ iii
List of Tables ............................................................................................................................... vii
List of Figures............................................................................................................................. viii
iv
References.. ...........71
Appendix A. ..........79
vi
List of Tables
CHAPTER 3:
Table 3.1: Theoretical bubble size estimation ...............................................................................32
Table 3.2: Comparison of D.O levels ............................................................................................35
Table 3.3: D.O variation as a function of time...............................................................................36
Table 3.4: Volumetric mass transfer co-efficient...........................................................................37
Table 3.5: Specific Interfacial Area and Liquid phase mass transfer co-efficient .........................39
CHAPTER 4
Table 4.1: Bubble Size Distribution at 3 Bar Pressure ..................................................................47
Table 4.2: Experimental Cases.......................................................................................................56
Table 4.3: Bubble Size Distribution: Case1: 10 -4M Tween20 .......................................................57
Table 4.4: Bubble Size Distribution: Case2: 10 -3M Tween20 .......................................................59
vii
List of Figures
CHAPTER 1
Figure 1.1: Components of a microbubble.......................................................................................3
Figure 1.2: Bubble Rise Velocity.....................................................................................................4
Figure 1.3: Young Laplace law ........................................................................................................5
Figure 1.4: Macro and Micro Bubbles .............................................................................................7
Figure 1.5: Bubble Shrinkage ..........................................................................................................9
Figure 1.6: Zeta Potential Variation.................................................................................................9
CHAPTER 2
Figure 2.1: Pressurized dissolution type micro-bubble generator..................................................13
Figure 2.2: Venturi flow combined with De laval nozzle condition..............................................14
Figure 2.3: Swirl liquid flow type micro-bubble generator ...........................................................16
Figure 2.4: MBG systems (a) Venturi-type micro-bubble generator (b) Ejector-type
micro-bubble generator ..............................................................................................16
Figure 2.5: Sadatomi Model of MBG ............................................................................................17
Figure 2.6: Effect of gas distributors on gas hold up .....................................................................18
Figure 2.7: Bubble size distributions for floatation process ..........................................................20
Figure 2.8: Mechanism of Ozone generation .................................................................................24
CHAPTER 3
Figure 3.1: MBG Schematic ..........................................................................................................26
viii
CHAPTER 4
Figure 4.1: Comparison of Refractive index..................................................................................42
Figure 4.2: Particle Size Analyzer .................................................................................................43
Figure 4.3: Particle image analyzer................................................................................................43
Figure 2.4: Experimental Set-up ....................................................................................................45
Figure 4.5: Understanding Volume and Number based distribution .............................................46
Figure 4.6: Volume based size distribution (top), Number based size distribution (bottom) ........46
Figure 4.7: Bubble size distribution at 3 bar ..................................................................................48
Figure 4.8: Bubble Coalescence Phenomenon...............................................................................49
ix
CHAPTER 5:
Figure 5.1: Deposits on an OLED Processing Glass .....................................................................66
Figure 5.2: Ozone microbubble generation assembly....................................................................67
Figure 5.3: Cleaning Procedure (a) Hot bath, (b) Initial Brushing, (c) MBG Ozonation Cleaning,
(d) Fine Brushing, (e) 2nd Ozonation ...........................................................................68
Figure 5.4: Rubber Coupling Attachment ......................................................................................70
Figure 5.5: Optical chamber...........................................................................................................70
Chapter 1
INTRODUCTION
Surface tension effect can be demonstrated by the meniscus formation on a water surface
where the cohesive forces between the water molecules cause an inward pull on the surface of
the water. On the other hand interfacial tension in an air-water system can be visualized as a
balance of forces at the interface of an air bubble in water. To attain a perfect balance, the
cohesive forces of water molecules should be nullified by the internal pressure of the air bubble
[1].
S= (1/18)*(l- g)*g*d2/
(1-1)
where l is the density of liquid, g is the density of the gas, g is the acceleration due to gravity, d
is the equivalent bubble diameter and is the dynamic viscosity of the liquid. However the
formulation is characterized by assumption which considers every bubble to be an isolated
sphere devoid of collisions and coalescence during its ascension. Conformable similarity was
observed in the theoretical and experimental rise velocities.
The low rising speed can also be realized in terms of two kinds of forces, namely
the body force, Fb, which is a long range force and the surface force which is a short range force.
(1-2)
(1-3)
(1-4)
(1-5)
The term (water- air)/(3K) R loses significance as R decreases. Therefore, Eq (1-5) is reduced to:
Faxial Fs = K*4**R2
(1-6)
As the bubbles decrease in size, their volumes decrease and hence the magnitude of the
body force, compared to the surface force, decreases - a low body force implies a low rising
speed. Though the local surface force decreases, the cumulative surface force tends to be high
due to the enlarged surface area, and hence, the surface force plays the predominant role and
effects the change in rising velocity.
Besides the increased surface to volume characteristic, micro-bubble encompass several
other significance as to follow.
where PB(t) and P(t) represent the pressure inside the bubble and ambient liquid pressure
respectively, R is the bubble size, S is the surface tension of the liquid, L is the liquid density
and vL is the kinematic viscosity of the liquid. With water being inviscid, the pressure force
should counteract the interface force to account for the stability of the bubble in the ambient
liquid. For microbubbles residing in water, the pressure difference across the interface is many
folds greater than macro-bubbles and the bubbles present a self-pressurizing effect due to
combined effect of low rising velocity and shrinkage due to increased dissolution [18].
(1-8)
Volume=4/3**r3
(1-9)
(1-10)
This relation lays emphasis on the fact that as the bubbles decrease in size, an increased
surface area is made available for the same volume as represented in Figure 1.4. This way, sites
for mass transfer are promoted and froth flotation is a classic example that makes effective usage
of this characteristic of micro and nano-bubbles [19].
values of the solution used along with addition of different surfactants. The negative values are
related to the ionic concentrations. Literature [21] reports a detailed study on zeta potential
variations for an air and water microbubble system evaluated through different techniques with
varying experimental conditions.
Figure 1.5:
ii.
iii.
iv.
11
Chapter 2
LITERATURE REVIEW AND BACKGROUND
p = khc
(2-1)
12
where p is the partial pressure of the gas, c is the concentration and kh is the henrys constant. In
other words, henrys law states more gas can be dissolved into a solution at a higher pressure.
This empirical practice is utilized in a pressurized dissolution microbubble generator where
pressurized air is introduced into a water tank. Due to the subsequent drastic drop in pressure of
the supersaturated air, air is expelled as microbubbles in to the water stream. Figure 2.1
illustrates this principle.
traverse the remaining section of the venture tube where bubbles are generated due to the shear
forces encountered in the diverging part.
However this method is only effective in producing bubbles of the order of millimeter
and not micro or nano-sized bubbles. In addition to the cavitation or gas injection principles,
acoustic characteristics of the fluid flow given by the de laval nozzle underlies the phenomenon.
Despite water being incompressible, the two phase flow adds compressibility parameters to be
taken into account.
(a)
(b)
Figure 2.4: (a) Venturi-type micro-bubble generator (b) Ejector-type micro-bubble generator [3]
16
(2-2)
where C* is the saturation concentration of oxygen in the liquid usually gathered from published
data, Cf and Ci are the final initial concentration of dissolved oxygen measured using a dynamic
Dissolved Oxygen meter and t, the time of operation of the experiment. This equation is used as
such when the initial dissolved oxygen is different from ambient conditions as in cases where
nitrogen is removed from air. However this can be simplified further, which will be discussed in
subsequent chapters.
17
With reference to the fundamental microbubble generators discussed, it has been reported
that the Swirl liquid flow type and pressurized dissolution types show significant gas hold-up at
lower superficial gas velocities meanwhile the significance diminishes at relatively higher flow
rates [3]. The linear proportionality between gas hold-up and superficial gas velocity is obvious
and due to the higher gas flow rates and the efficiency of the microbubble generators are best
The volumetric oxygen transfer co-efficient plot follows a similar trend as it is a function
of gas hold-up. Spiral flow type is evaluated to be the most effective in terms of mass transfer.
However, due to more operating parts enlisted in case of microbubble generators
compared to stationary spargers or sprayers, power requirement has been estimated to exceed the
macro-bubble generators.
Ultrasonic cavitation is another unique technique used in the field of microbubble
generation and ubiquitous in drug delivery applications. They are advantageous when precision
18
is required however applicability to industrial scale is dubious owing to the cost involved in
operation. A comparison between a microbubble generator operated based on sonication and a
similar driven my mechanical agitation was carried out [30] to evaluate the performance.
Sonication operated equipment generated bubbles of very fine sizes, large interfacial area
and especially lower critical radius which meant the bubbles are more stable and procrastinate
immediate shrinkage. The experimentation also involved selection of kinds of surfactants but
predominant focus was on the type of bubble generation mechanism rather than the surface
active agents.
2.3 Flotation
Flotation is a separation treatment process that uses small bubbles to remove low -density
particulates from potable water and wastewater. Flotation is used as an alternative to
sedimentation for removing low-density materials like clays or algae. Flotation, based on the
method of bubble generation, can be classified as:
Electro-flotation
Microbubble generation using technologies like electro-flotation and electrostaticspraying are industrially favored due to continuous operation where electricity is used to produce
bubbles inside the surface of water. Bubbles of H2, are formed at the cathode and bubbles of O2
at the anode. This method generates bubble diameters ranging from 22 to 50 um, depending on
the experimental conditions and follows the reaction:
19
H2O
2H20 + 2e
(2-3)
(2-4)
20
(2-5)
We = v2d /
(2-6)
where is the density of the liquid, u is the liquid velocity and the exit, d is the size of the
bubble, is the dynamic viscosity of the liquid and is the surface tension.
21
To give a furthermore insight to Weber number, [39] puts into words what Weber
number means and their significance on monodisperse microbubble jets. A stable bubble
distribution is hard to attain at very low Weber numbers and a nominal range of 1< We < 40
ensures a stable dispersion. Also, this is complimented by [40] which reports that no stable
microbubble conditions is observed at a Weber number less than 8 and the maximum can go to
few hundreds, in regards to microjets. These conclusions throw light on the fact that the inertial
forces shall always govern the fluid dynamics relative to the surface tension.
For microbubbles in water, the particle Reynolds number, Re p which uses the bubble size
in the Reynolds number formulation in place of the water outlet diameter, has to be low enough
for assumptions used in flow modelling to hold good.
In addition to the basic dimensionless numbers in fluid dynamics, two dimensionless
numbers namely Morton Number and Eotvos Number are grouped together in simulation
experiments to characterize the structural significance of bubbles in a liquid medium.
Morton number is given by:
Mo = gc4/c23
(2-7)
(2-8)
The Bond number is a very slight variation of the Eotvos number but used interchangeably.
Bond Number is given by:
Bo=
a L2 /
(2-9)
In simulation experiments, it has been observed that bubbles coalesce readily in liquids
with low Morton number and cluster in liquid with high Morton number [41] and can be
visualized directly in terms of viscosity and surface tension forces. Conclusion that high Morton
number liquid is more favorable for effective mass transfer compared to low Morton number
liquids is proposed.
ii.
iii.
iv.
v.
Pollution control: prevent growth of blue-green algae in water bodies [11] absorption of
CO2 gas [12].
vi.
Separation process: treatment of oil/water emulsion [13]; gas liquid contactors and algal
separation [14].
In addition, for free radical generation [15] and they fit in specific applications such as
23
24
50% inactivation using a bubble contactor in addition multifold increase in Total and Soluble
Chemical Oxygen demands (SCOD).
Also Zimmerman et al. [17] recently came up with a novel design that incorporates an
oscillating air lift technology into the bio-reactor system to effectively generate ozone
microbubbles with appreciable mass transfer rates.
Reports on effective removal of different strains of bacteria have been published and
finds intense practice in food processing sector [43-45].
An Electro-static ozonation reactor based on Electrostatic spraying was developed [31]
and evaluated for mass transfer of ozone but at higher voltage levels the results failed to conform
owing to pressure fluctuations and poor controllability of the system.
25
Chapter 3
3. Experimental Approach: Part 1
3.1
Experimental set-up:
The microbubble generation technology used in our study is of the pressurized
As a general base, water from the city of toronto is used, delivered through internal
plumbing to the pump incorporated in the micro-bubble generator. Compressed air is also
supplied to the system from internal gas lines. The micro-bubble generation system is of a
dynamic nature where we have two mobile phases compared to single mobile phase. The main
aspect that separates the micro-bubble generator from other counterparts is the bubble number
density characterized by a bubble swarm.
presence of innumerous bubbles and this can be realised in Figure 3.8 as discussed in later part of
this section. For this very reason, characterization of the system using optical imaging isnt
pursued rather a dynamic particle size analysis is carried out.
3.1.1 Micro-bubble generation break-down:
Step 1: Process water is sent into the mixing chamber through a pump assembly
26
Step 2: Gas (i.e) air compressed at 100 psi is dissolved in the water inside the mixing chamber at
different gas flow rates.
Step 3: The air-water mixture enters a pressure reducing valve which can be viewed as a
convergent nozzle and exits as air micro-bubbles in water.
Step 4: The final two phase flow is collected in a custom-built water column for further
observations.
Flow meters to regulate the water and gas flow rates are added to the system in addition
to an emergency stop switch and a pressure gauge which gives the pressure inside the system
before its released to ambient conditions.
An experimental system of micro-bubble generator (MBG) has been set up with the
assistance of the KIMM. All the components of the micro-bubble generator were manufactured
by the EMT Plus, Korea (Jong-Gu Yim, emt4466@naver.com, +82-10-4466-0173) but all the
electronic and electric systems were replaced by Canadian ones to satisfy the CSA approval.
Figure 3.2, 3.3 and 3.4 show images of the MBG system-front view, internal assembly and outlet
part design respectively.
27
Figure 3.3: a: Connections inside the MBG, b: Mixing chamber part design
28
Stokes equation:
2
(3-1)
Hadamard-Rybczynski equation:
2
(3-2)
The deviation of stokes equation from the latter is by a constant of 18/12 which is 1.5.
For simplicity purpose and to have a referential comparison to similar works, stokes equation is
used going forward.
29
Water quality:
Industrial water constitutes numerous dissolved solids which influence its quality.
Salinity is a measure of the mass of dissolved salts in a given mass of solution. Salinity is to be
known to effectively determine the dissolved oxygen saturation limit of the water being used. At
a temperature of 20 C and a conductivity of 318 micro-Siemens/cm,
Salinity = 0.17 ppt ~0.20 ppt
(3-3)
The acrylic column shown in figure 3.6 was custom built with a 22x22 cm2base standing
80 cm tall sealed at the edges using acrylic cement. Acrylic was preferred over glass for their
30
promote the viewing reducing the travel time through the medium.
31
2. By varying the mass flow rate of the gas. This way, more fluid is forced to exit for the
same operating conditions thereby increasing the pressure or vice versa.
In our experimentations for bubble size estimations, gas flow rate was fixed and the
pressure variations where brought about in the former way. Whereas for dissolved oxygen
measurements where mass flow rate of gas becomes a variable, the pressure variations were
based on this.
Table 3.1: Theoretical bubble size estimation
No
Pressure (bar)
Bubble Superficial
Rising Velocity (mm/s)
2.6
34
1.617
54.481
3.8
65
0.846
39.403
4.4
85
0.647
34.456
5.2
111
0.495
30.152
(3-4)
D.O. varies inversely with the temperature, salt concentration and altitude implying the
colder the water, the higher is its capacity to hold gas. In the field of aquaculture, D.O. levels are
of prime importance [5] as plant and animals breeding in water require appropriate amounts of
32
Oxygen for their very survival. A more common and relatable example is the monitoring of D.O.
levels in aquariums and fish ponds.
For our experiments, D.O. was measured using ExStik DO600 meter (with temperature
sensor) capable of reading values up to 25 mg/L. Figure 3.7 shows the effect of pressure on D.O.
and is found to have a direct linear correlation.
(a)
60
D.O. (mg/l)
(b)
50
40
30
20
10
0
0
2
3
4
Pressure (bar)
2
3
4
Pressure (bar)
9.0
8.8
8.6
8.4
8.2
8.0
7.8
7.6
33
Before Aeration
After Aeration
After Aeration
Before Aeration
34
No.
Pressure
(bar)
Micro-bubble Generator
Macro-bubble Generator
5.67
5.67
2.6
7.73
5.9
3.8
8.30
5.77
4.4
8.55
6.19
5.2
8.82
6.2
(3-5)
35
System
Time
D.O.
% Saturation
Saturation Limit
Pressure
(10-4 m3/min)
(minutes)
(mg/L)
5.7
46.36
At 20 C,
6.2
50.42
6.9
56.12
8.18
66.53
1.38 psi)
12
8.32
67.66
12.295
5.7
46.36
12.295
6.35
51.64
8.01
65.14
8.57
69.71
12
9.43
76.7
(mg/L)
(bar)
8.5
10.0
9.0
C (mg/l)
4.2
D.O.
2.8
8.0
7.0
6.0
5.0
0
Time (min)
Figure 3.9: D.O. Vs Time
36
10
12
2.8 bar
4.2 bar
Linear (2.8 bar)
Linear (4.2 bar)
2.0
ln(Cs-C)
1.8
1.6
R = 0.945
1.4
1.2
R = 0.9793
1.0
0.8
0
10
12
t (min)
Figure 3.10: Rate of Change of D.O. Concentration
(3-6)
(3-7)
(3-8)
37
For our experiments, a rectangular tank column was used in contrast to cylindrical
columns. The reason
being the pressure at which our system is operated is sufficiently low and
doesnt necessitate a smooth column. Also, with rectangular columns distortions in bubble image
is minimized when compared to cylindrical columns. Cross sectional area of the column, Acrosssection
= .0484 m2
No.
kLa
(10-4 m3/min)
(10-4m/s)
(1/s)
1.01
0.0468
8.5
2.93
0.0712
0.08
kla (1/s)
0.06
0.04
0.02
0.0002
0.0004
0.0006
0.0008
jG (m/s)
Figure 3.11: Effect of Superficial gas velocity on volumetric mass transfer co-efficient
38
(3-9)
(3-10)
Table 3.5: Specific Interfacial Area and Liquid phase mass transfer co-efficient
kl (10-5m/s)
.074
8.880
0.527
8.5
0.193
33
0.216
39
The values are plotted individually as a function of superficial gas velocity and compared
with [49] as follows:
Tap Water [49]
Sea Water [49]
100000
Tap Water-Experimental
a (m-1)
10000
1000
100
10
1
0
0.0002
0.0004
0.0006
0.0008
0.001
jG (m/s)
Figure 3.12: Effect of Superficial gas velocity on Specific Interfacial Area
0.0002
0.0004
0.0006
0.0008
0.001
1
Tap Water [49]
Sea Water [49]
Tap Water-Experimental
kl (m/s)
0.1
0.01
0.001
0.0001
0.00001
jG (m/s)
0.000001
Figure 3.13: Effect of Superficial gas velocity on liquid phase mass transfer co-efficient
40
From the Figures 3.12 and 3.13, it is evident that the exponential increase of volumetric
mass transfer rates in our experiments is attributed to the bubble size. This emphasizes that the
smaller the bubble, the higher is the volumetric mass transfer rates. The liquid phase mass
transfer co-efficient didnt show any significant improvement in our experiments and this trend
is similar to correlations made by [50]. Although, the quality of tap water might vary, the values
are large enough to sufficiently base the interpretation on bubble sizes and interfacial area. Its
also supported by the fact that sea water [49] is bound to have higher total dissolved solids
compared to tap water, at any instance.
41
Chapter 4
Particle Size Analysis
Some of the most common means of particle size measurement include: Optical
microscopy, Laser diffraction, Electro-impedance volumetric zone sensing (ES) and the like.
Laser diffraction is amongst the chief size measurement technologies on the contemporary scene
and is capable of recording finer sized particles in comparison to counterparts [51], though there
is an accusation that additional stresses are placed on the particles in such technologies during
the actual measurement process unlike optical microscopy.
42
43
The Particle size analyzer used in out experiments is the Microtrac Bluewave Particle
size Analyzer capable of measuring 0.01 to 2000 microns. The Microtrac Bluewave complies
with or exceeds ISO 13320-1 particle size analysis- light diffraction methods.
It is designed to work using the tri-laser technology but with the advancement of blue
laser diodes in place of two red lasers. Blue laser diodes are of higher sensitivity ow ing to the
shorter wavelengths and provide better particle size measurement in the micron and sub-micron
range.
In retrospect, putting the analyzer to effect right away had its difficulties. Bubbles in
general are neither lasting nor rigid as in case of particles. So minimal handling becomes a
necessity for accurate measurements and subsequent interpretation. Our MBG outlet, as seen
from fig- , has a cylindrical assembly through which the micro-bubbles dispersed in water flow
outward and are collected. Meanwhile, the inlet to the particle size analyzer had a very narrow
opening with almost no room for additional mounts or tubing.
Originally, the samples (mostly particles dispersed in a liquid) are collected in a sampling
vessel and poured into the unit called SDC which has an internal circulating mechanism to
deliver the sample at the laser juncture and recirculate for multiple readings of the same sample.
But the dead volume is quite large, especially when dealing with bubble measurement. Then
came in the part called USVR which is basically a station with a small rotating spindle to force
the sample directly for size measurement. This way the dead volume in between bubble
generation and size measurement is made minimal.
Also to minimalize sample handling a direct connection was made between the USVR
and MBG outlet using a rubber coupling with SS clamps as seen from fig. that closed the MBG
outlet from the outside and delivered the bubbles directly into the cup of USVR.
44
ii.
iii.
Each distribution shows a slight variation from one another and this is due to the
formulations involved. Volume based particle size distribution is used as a general rule, though
both distributions are presented for important cases. Number based particles size distribution
make more sense if particle counting is the chief detail to lookout for.
A simple analogy to explain the difference is as follows: Consider three bubbles: A=1
micron, B=1 mm and C=1 m.
45
In a container holding these three bubbles, a number size distribution will display each
particle to be one third of the total (1:1:1). A volume distribution will display C to occupy a
bigger space with B and A following in the volume hierarchy (3:2:1). Volume distribution is
more comprehensive individually but when combined with number distribution, more precise
analysis could be made, more so in the context of bubble swarm.
An example from present situation is as given below in Figure 4.5:
Figure 4.6: Volume based size distribution (top), Number based size distribution (bottom)
46
Looking at the top distribution in Figure 4.6, it is natural to assume the following:
i.
ii.
iii.
Now, if we take a look at the number based size distribution, the milli-bubble population
that were encountered in interpreting the former size distribution seem to be negligible,
apparently.
Depending primarily on number based size distribution isnt acceptable due to the fact
that the values for number based distribution base their correlation on volume based distribution.
However, supplementing the volume based distribution with number based distribution for result
interpretation provides an invariably better perspective.
Pressure
(bar)
Cycle
Time (s)
Mean
(um)
10
24.5
6.28
20
162.5
79.98
30
351.5
199.2
40
436.7
216.3
47
Bubble
Size
Smallest bubble
size (um)
The time recorded on top of each bubble size distributions is the time interval between
successive measurements (i.e) the time since the bubble was generated.
It can be seen in Figure 4.7, by the end of 10 seconds, the distribution is spread over a
little in the range 5-100 microns with multiple peaks around 20 microns and a sub-region around
1000 microns.
As time progresses or in other words, as the bubbles rise, there is shift in the curve as the
peak moves towards a larger bubble size range and the sub-region at 1000 microns are getting
bigger. This trend steadies with time and by the end of the fourth run at 40s, the micro-bubble
range has vanished and the milli-bubbles are getting populated. An important cause for this shift
in bubble size distribution over time is attributed to coalescence.
48
ii.
iii.
49
One of the key alternatives to reduce if not prevent the coalescence is by using
surfactants. Though electricity can be used to greater effectiveness to well disperse the solution,
the cost associated with it is not viable for industrial-scale accommodation.
4.3.1 Surfactants
Surface activating agents abbreviated as surfactants are compounds that comprise of
hydrophilic and hydrophobic elements built into the same structure. They are primarily used to
reduce to the surface (interface) tension of a liquid and may be of anionic, cationic or non-ionic
types.
Felix Sebba was the pioneer in microbubble stabilization using surfactants and proceeded
with production of small bubbles of the order of 20 microns inside a dilute surfactant solution
and tagged them microfoams [55]. He also suggested the type of surfactant isnt the critical
parameter. A schematic of the microfoam generator developed by Felix Sebba is as shown in
Figure 4.9.
50
Surfactants play an important role in stabilizing the microbubbles and preventing their
shrinkage and eventual collapse under the surface of water. Surfactants, especially biosurfactants find an increasing demand in the field of medicine and instrumentation where
stabilization of drugs and lipids of the order of microns are required. Surfactants are more
efficient and microbubbles stability is more pronounced at a higher pH value [56].
In the following years, following advancements of technology, a more convincing
explanation than microfoams was developed and the FAD colloidal gas aphrons (CGA)
which refers to microbubbles covered with a surfactant shell which in turn is composed of two
layers of alternating hydrophilic and hydrophobic tails, came into reference as represented in
Figure 4.10. Studies on the properties and significance of the CGA for applications like protein
recovery and similar were made by [57-58]. It was interpreted that stability of the CGA varied
proportionally with the concentration of surfactant but inversely with the salt concentration in the
liquid. However, on contrary to [56], effect of pH was not signified then.
51
particles will effectively suppress the bubble coalescence. Or in other words, the outward
diffusion of gas from the bubbles should not be strong enough to disperse the surfactant
molecules on its surface.
52
Most of the early researchers have focussed on stabilizing a single large bubble in a
quiescent liquid with Davidson et al. [61] being one among the popular, then. With micro-bubble
technology being a relatively new and commercially blooming field, effective suppression of
coalescence especially in a dynamic medium is a critical issue to be dealt.
Micro-bubbles have excellent self-pressurizing effect which can be combined with the
coalescence suppression application of surfactant to enhance the efficiency of the bubble
generator.
53
Surfactants are broadly classified into three categories based on the charge on their polar
head group as follow:
1. Non-ionic
2. Cationic
3. Anionic
As their names indicate, non-ionic surfactants carry no charge on their polar head;
Cationic surfactants have a positively charged head and anionic surfactants carry a negative
charge on their head as schematically shown in Figure 4.13.
In addition to the charge, the balance between the head group and tail group in terms of
percentage is an important parameter to be noted as it determines the property of the product
[62]. This is referred to as the hydrophile-lipophile balance (H-P-B) and ready-to-use equations
have been formulated to calculate the value in a mixture [63]. HPB equations are more prevalent
in the emulsion industry where oil or particle size stabilization is primary.
54
4.3.1.3 Polysorbate-20:
As mentioned in [18], bubbles carry a small negative charge at their interface and
addition of charged surfactants would require additional monitoring as they combine more than
one effect to influence the bubble dynamics.
Polysorbate-20, known by brand name, Tween-20 is the selected non-ionic surfactant for
our experiments. The foremost character is its non-ionic property which nullifies the effect of
any electrical charges on the interface.
Structure of Polysorbate20 encompasses the water soluble chains and aromatic links in
their tail as represented in Figure 4.14 as follows:
The HPB number for Tween-20 is 16.7 which makes them soluble in water. The higher
the value on a HPB scale of 1-18, the better is its solubility in water.
Tween-20 has been used in the context of stabilizing bubbles in air-water interface [64,
65]. It is reported that increasing the concentration of surfactant slightly affects the stabilization
55
positively which is speculated to be due to packaging at the bubble interface but large amounts
prove detrimental [65]. The use of tween-20 to stabilize micro-bubbles hasnt been well
documented in literatures and if at all, they follow batch type processes [66]. Key aspects like
non-ionic property ease of availability and limited literatures in the field of micro-bubble
generation technology especially dynamic bubble generation methods.
Tween-20 is a yellow viscous liquid giving a yellowish solution when added to water. It
has a molecular weight of 1228 g/mole. Molecular-biology grades of tween-20 were purchased
from med-store at the University of Toronto in bottles of 500 ml.
Two molecular concentrations of Tween-20 are tested in our experiments, both well
above its CMC. CMC value of Critical Micelle Concentration: 8.04105 M at 21 C
Molecular Concentration are linked by the dormula:
C = (m/V) * (1/M.W)
(4-1)
Case
Surfactant
Concentration of Surfactant
(M)
Tween-20
10-4
Tween-20
10-3
56
Pressure (bar)
Cycle
Time (s)
10
63.97
33.21
20
63.06
37.54
30
66.45
37.84
40
96.76
53.23
50
103
56.12
60
116
61.60
70
114.9
55.83
80
136.9
58.45
A third case for a much higher concentration of 10 -2 M was tested but the MBG started
foaming at the outlet making the flow unsteady to be run through the particle size analyzer for
size characterization measurements.
White foamy agglomerates that were produced at the 10 -2 M tween-20 concentration are
essentially due to the excess of surfactant molecules in the solution that started precipitating due
to the sudden pressure release. Similar occurrence were noted when the pressure was increased
even for lower concentrations. This helps us understand that there is a threshold to operate the
MBG to effectively make use of the surfactant.
Henceforth, the MBG was operated at pressures no greater than 3.2 bar (fluctuating
between 3 to 3.2 bar). Also to be seen is the concentration of Tween-20, which is to be kept
above the CMC but below 10mM.
These two cases are then compared with the initial characterization made at the same
pressure of 3 bar but without the surfactant. Its to be noted that addition of surfactant only
affects the bubble dynamics and not the flow itself. Hence no pressure or flow rate changes were
encountered in the experimentation as a direct effect of surfactant addition.
57
58
Figure 4.15: Bubble size distribution: Case 1
Pressure (bar)
Cycle
Time (s)
10
68.47
30.51
20
51.07
22.01
30
57.25
25.90
40
62.83
28.43
50
67.45
30.25
60
70.22
33.34
70
72.51
34.26
80
82.93
34.25
90
150.8
57.62
A slight dip in the size of the bubble after 10 seconds is observed. This is speculated due
to the delay in reaching steady state conditions to produce microbubbles. The volume based
bubble size distribution charts are as shown in Figure 4.16 below.
59
60
Figure 4.16: Bubble size distribution : Case 2
4.4 Observations:
Its observed that the surfactant addition positively affects the micro-bubble as the
bubbles are prevented from sharp increase in their sizes as opposed to the initial case. However,
the presence of outward diffusion happens to be prevalent though at a reduced scale.
Rise velocities can be predicted using stokes equation but axial rise distance cannot be
accurately estimated as theres no correlation of change in size of the bubble over ti me. A 40um
bubble is predicted to rise at 1 mm/s but during the rise the shape and size of the bubble are
getting altered. This makes comparing our rise velocity calculations to stokes rise velocity less
meaningful. However the time dependence is coupled to the rise velocity equation to estimate the
axial rise distance as follows:
L1=
Vdt + L
(4-5)
Where L1 and L0 are the final and initial distance respectively, V is the rise velocity and dt is the
time interval. Also shown in Figure 4.18 is a comparison of axial rise distance of bubble as a
function of time. The values are calculated by fitting the values into the following equations for
each case
Initial Case, without surfactant:
y = 0.1561x2 + 5.3005x
(4-2)
Case 1:
(4-3)
Case 2:
(4-4)
Figure 4.17 shows the effects of surfactants on the bubble size as a function of time.
61
62
From the plot Figure 4.18, an air micro-bubble in water without any surfactant added to
the solution will have moved an axial distance of 7.62 mm from the point of generation in 10
seconds. However this distance is made half by surfactant addition, for either case. The effect of
molecular concentration of tween-20 isnt commendable at the onset or early stages. However,
the stabilization of bubble or prevention of coalescence is gradually amplified as the two
surfactant curves show divergence as time increases gradually.
Another important aspect to be noted is in a dynamic bubble generation system as ours,
bubbles are constantly generated at the bottom and an older bubble is always affected by a newer
one as it passes on a thrust force to the former. This invariably affects the rise distance and this
justifies our results as they show a sharp increase during the onset and the curves flatten
gradually over time.
These equations are also used to estimate the individual rise velocities for each case as
shown in Figure 4.19-4.21
1000
100
Without Surfactant
10
1
0
10
20
30
40
50
60
70
Figure 4.19: Rise velocity of bubbles for the initial case without surfactant
63
100
1
0
50
100
150
100
1
0
50
100
150
64
200
Chapter 5
Summary and Future Work
Figure 5.1 shows an image of a OLED processing glass covered with deposits that are to
be cleaned. MBG used in our experimentation was deployed to wash this glass using ozone
micro-bubbles. The cleaning was carried out at KIMMs Korean site with specifically assembled
ozone generation module as represented in Figure 5.2.
The MBG was operated at the maximum system pressure so that the bubbles generated
are of the smallest size range at relatively larger bubble density as supported by [59].
The air/water ratio is always maintained below 10-15 % as increasing the gas flow rates
hinder the generation of smaller sized bubbles. The cleaning was done as a five step process
represented in Figure 5.3 and listed in the order as follows:
Step 1: Hot water soaking.
Step 2: Brushing to remove relatively larger dirt particles.
Step 3: Ozone purifying, where the actual MBG is utilized in the process of cleaning.
Step 4: Fine brushing to remove any dust or sticky substances and to expose the effect of
MBG ozonation.
Step 5: Second Ozone purifying before the part can be put to use.
66
67
Figure 5.2: Ozone microbubble generation assembly
Figure 5.3: Cleaning Procedure a: Hot bath, b: Initial Brushing, c: MBG Ozonation Cleaning,
d: Fine Brushing, e: 2 nd Ozonation
68
Optimization of the nozzle and outlet assembly to downtrend the bubble size
6. Optical recording of bubble dynamics to calibrate the existing particle size analyzers
Initial steps were taken to visualize the bubbles using a ccd camera set-up. However
controlling the flow rates and channelling the flow through a custom-built optical chamber was
not triumphant as our MBG is dynamic in nature. Continuous efforts are being put into this plan
to capture bubble images. The preliminary actions towards optical recording are shown in
Figures 5.4-5.5. Figure 5.4 shows a rubber coupling that was added to the outlet portion of the
MBG to increase the final flow rate by sustaining a positive pressure with gradual reduction to
ambient conditions. Figure 5.5 displays an optical chamber built with polycarbonate with
adjustable chamber thickness.
69
70
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78
Appendix A
Salinity Calculation Equation:
79
80
Number based Bubble size distribution: No Surfactant
81
Number based Bubble size distribution: Case 1
82
Number based Bubble size distribution: Case 2