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MEASURING INTERFACIAL TENSION BETWEEN

FLUIDS USING PENDANT DROP METHOD

UNDERGRADUATE THESIS
A thesis submitted in partial fulfilment of the requirement for the
degree of Sarjana Teknik

By

F.X. Arnold Giovanni H.


13112029

MECHANICAL ENGINEERING STUDIES


FACULTY OF MECHANICAL AND AEROSPACE
ENGINEERING
INSTITUT TEKNOLOGI BANDUNG
2017
Statement of Approval

Undergraduate Thesis

Measuring Interfacial Tension between Fluids Using Pendant


Drop Method

By

F.X. Arnold Giovanni H.


13112029

Mechanical Engineering Study Program


Faculty of Mechanical and Aerospace Engineering
Bandung Institute of Technology

Approved at the date of: April 13th 2017

Supervisor

Jooned Hendrarsakti, Ph. D


NIP 132320055
Tugas Sarjana
Mengukur Tegangan Antarmuka
F. X. Arnold
Judul antara Fluida dengan Metode Pendant
Giovanni H.
Drop
Program Studi Teknik Mesin 13112029
Fakultas Teknik Mesin dan Dirgantara
Institut Teknologi Bandung
ABSTRAK

Mikrofluida adalah ilmu yang mempelajari perilaku fluida pada skala


mikro. Interaksi gaya pada skala mikro berbeda dengan skala makro dikarenakan
efek penskalaan. Tegangan permukaan dan tegangan antarmuka merupakan
gaya-gaya yang amat mempengaruhi fenomena- fenomena mikrofluida. Oleh
karenanya, amatlah penting untuk mengukur gaya-gaya tersebut.
Alat pengukur tegangan permukaan komersil sudah tersedia namun
harganya mahal. Pada studi ini, metode pendant drop digunakan untuk menguk ur
tegangan permukaan dan antarmuka dengan menggunakan alat-alat yang murah
dan mudah didapatkan. Metode pendant drop dipilih karena akurasi, fleksibilitas,
dan kemudahannya. Pada metode pendant drop, bentuk tetesan dianalisis untuk
menentukan nilai tegangan permukaan/tegangan antarmukanya.
Pada studi ini, jarum suntik hipodermik digunakan untuk menghasilka n
tetesan dan sebuah kamera DSLR digunakan untuk memfotonya. Bentuk tetesan
kemudian diekstrak. Setelah itu, suatu rutin berulang digunakan untuk
mencocokkan bentuk tetesan teoritis dari persamaan Young-Laplace dengan
bentuk tetesan yang diekstrak dari foto. Bentuk yang paling cocok ditentuka
dengan meminimalkan jarak euklidean antara bentuk teoritis dan eksperimental.
Tegangan permukaan air demineralisasi, minyak zaitun, dan dua merek
minyak kelapa sawit diukur pada studi ini. Tegangan antarmuka antara air
demineralisasi dan minyak kelapa sawit juga diukur. Didapatkan bahwa metode
dan peralatan yang digunakan memberikan hasil yang dapat diterima dan sesuai
dengan nilai literatur untuk tegangan permukaan, namun hasil pengukuran
tegangan antarmuka antara fluida dengan densitas yang mirip tidak baik.
Kalibrasi dilakukan menggunakan nilai tegangan permukaan literatur
untuk menentukan faktor koreksi. Tegangan permukaan Pertamax dan Pertamina
Dex diukur dan hasilnya adalah 18.9 0.8 dan 25.2 0.5mN/m.
Kata kunci: mikrofluida, tegangan permukaan, tegangan antarmuka, pendant
drop
Final Project
Measuring Interfacial between Fluids F. X. Arnold
Title
Using Pendant Drop Method Giovanni H.
Major Mechanical Engineering 13112029
Faculty of Mechanical and Aerospace Engineering
Institut Teknologi Bandung
ABSTRACT

Microfluidics is an emerging science that study the behavior of fluids in


micro scale. The physics and interaction of forces in the micro scale is differe nt
compared to macro scale because of the scaling effect. An important force that
dictates the microfluidic phenomena is the surface or interfacial tension. Hence,
it is important to measure this surface or interfacial tension.
Commercially available apparatuses to measure surface or interfac ia l
tension are available, however it is costly. In this study, pendant drop method is
used to measure surface and interfacial tension by utilizing cheap and readily
available apparatuses. Pendant drop method is chosen because of its accuracy,
flexibility, and most importantly: its simplicity. In the pendant drop method, the
drop profile is analyzed to determine its interfacial tension.
In this study, hypodermic needle and syringe is used to produce the drop
and a DSLR camera is used to photograph the drop. Then the drop profile is
extracted. After that, an iterative routine is used to fit the theoretical drop profile
given by Young-Laplace equation to the extracted drop profile from the captured
image. The best fit is determined by minimizing the euclidean distance between
the theoretical and experimental drop profile.
The surface tension of demineralized water, olive oil, and two brands of
palm olein are measured in this study. The interfacial tension between palm olein
and demineralized water is also measured. It is found that the method and
apparatuses used in this study give acceptable result and agree with the accepted
value for surface tension measurement. However, the measurement result for
interfacial tension between fluids with similar density is poor.
A calibration is done using the accepted surface tension values to
determine the correction factor. The surface tension of Pertamax and Pertamina
Dex is measured and the value is 18.9 0.8 and 25.2 0.5 mN/m, respectively.
Keywords: microfluidics, surface tension, interfacial tension, pendant drop
Acknowledgement

I would like to express my gratitude to my family for their constant support during the period
of my study and for the completion of this final project. They always believe in me and
encourage me to complete my study and pursue my dreams. I also would like to thank many
people that helped me during my time working on this final project. Many thanks to:

1. Jooned Hendrarsakti, Ph. D, whom is my advisor, for his guidance, encouragement, and
time. His support is vital for the completion of my final project. I am forever indebted to
him.
2. ITB lecturers especially those who reside in Mechanical Engineering Department
3. Tania Ananta Hidayat for her constant support and naggings
4. My friends at ITB Student Orchestra especially Arya, Ato, Bram, Niku, and Fadil
5. Danish, Ben, and Adit for their friendship
6. My fellow friends in the Mechanical Engineering Study Program especially batch 2012
There are many more people that helped me in this study and it is impossible to mention
everyone. May they are blessed and have a great life.

I recognizes that this study has flaws and therefore critics and advices are welcome for the
improvement of this study.

Bandung, May 2nd 2017

F.X. Arnold Giovanni H.

i
Contents

Acknowledgement ...................................................................................................................... i
Contents ..................................................................................................................................... ii
List of Figures ........................................................................................................................... iv
List of Tables ............................................................................................................................ vi
Chapter 1 Introduction ............................................................................................................... 1
1.1. Background ..................................................................................................................... 1
1.2. Objectives of Study ......................................................................................................... 2
1.3. Scope of Study ................................................................................................................ 3
1.4. Methodology ................................................................................................................... 3
Chapter 2 Fundamental Theories ............................................................................................... 4
2.1. Surface and Interfacial Tension....................................................................................... 4
2.1.1. Surface Tension ........................................................................................................ 4
2.1.2. Interfacial Tension .................................................................................................... 5
2.2. Measurement of Interfacial Tension ............................................................................... 6
2.2.1. Direct Measurement Using a Balance ...................................................................... 7
2.2.2. Measurement of Capillary Pressure .......................................................................... 9
2.2.3. Analysis of the Balance between Capillary and Gravity Forces ............................ 11
2.2.4. Analysis of Gravity-Distorted Drops ...................................................................... 13
2.2.5. Comparison of Measurement Methods................................................................... 15
2.3. The Pendant Drop Method ............................................................................................ 16
2.3.1. History and Development of the Pendant Drop Method ........................................ 16
2.3.2. Theory of the Pendant Drop Method ...................................................................... 17
2.4. Needle Gauge ................................................................................................................ 20
Chapter 3 Research Method ..................................................................................................... 22
3.1. Image Acquisition ......................................................................................................... 22
3.1.1. Camera and Optics.................................................................................................. 22
3.1.2. Syringe and Needle ................................................................................................. 23
3.1.3. Light Source and Diffuser ...................................................................................... 25
3.1.4. Fluids ...................................................................................................................... 25
3.1.5. Others...................................................................................................................... 26
3.2. Cropping and Contrast Adjustment............................................................................... 27
3.3. Edge Detection .............................................................................................................. 28

ii
3.4. Interfacial Tension Calculation ..................................................................................... 29
3.5. Experiments Conducted ................................................................................................ 33
Chapter 4 Results and Analysis................................................................................................ 35
4.1. Fluid Density Measurement .......................................................................................... 35
4.2. Interfacial and Surface Tension Measurement .............................................................. 37
4.3. Uncertainty Analysis ..................................................................................................... 39
4.4. Correction Factor........................................................................................................... 41
4.5. Bond Number Effect on Measurements ........................................................................ 43
4.6. Needle Size Effect on Measurement ............................................................................. 45
4.7. Worthington Number Effect on Measurements ............................................................ 46
4.8. Pertamax and Pertamina Dex Surface Tension Measurement ...................................... 48
4.9. Density Effect on Surface Tension................................................................................ 49
4.10. Image Processing......................................................................................................... 50
Chapter 5 Conclusion and Recommendation ........................................................................... 52
5.1. Conclusions ................................................................................................................... 52
5.2. Recommendations ......................................................................................................... 52
References ................................................................................................................................ 53
Appendix A Fletchers Criteria for Setting [30] .................................................................. 58
Appendix B The Jacobian Matrix [30] .................................................................................... 60
Appendix C Calculating The Arc Lengths [30] ....................................................................... 62
Appendix D Fluid Density Determination ............................................................................... 63

iii
List of Figures

Figure 2.1 Water strider walking on water [11]...................................................................... 4


Figure 2.2 Illustration of surface tension [7] .......................................................................... 4
Figure 2.3 Real life soap film experiment to illustrate surface tension [12]........................... 5
Figure 2.4 Inner and surface force in a water droplet [13] ..................................................... 5
Figure 2.5 Illustration of interfacial tension [6] ...................................................................... 6
Figure 2.6 Classification of common interfacial tension measurement methods [18] ........... 7
Figure 2.7 Schematic of the Wilhelmy plate method [18] ...................................................... 7
Figure 2.8 Schematic of the ring method [9] .......................................................................... 8
Figure 2.9 Maximum bubble pressure method. ...................................................................... 9
Figure 2.10 Schematic of the capillary rise method [9] ........................................................ 12
Figure 2.11 Schematic illustration of drop volume or weight method [9]............................ 12
Figure 2.12 Definition of dimensions and coordinates describing the sessile drop [9] ........ 14
Figure 2.13 Simple schematic of pendant drop .................................................................... 15
Figure 2.14 The pendant drop shape [31] ............................................................................. 18
Figure 2.15 Pendant drop shape with the arc length from the drop apex, s, shown [30]...... 19
Figure 3.1 Research procedure.............................................................................................. 22
Figure 3.2 Experiment setup [30] ......................................................................................... 22
Figure 3.3 Sony 100 camera [32]........................................................................................ 23
Figure 3.4 Quantaray macro lens [33] .................................................................................. 23
Figure 3.5 Hypodermic needles and syringes used in the experiment.................................. 24
Figure 3.6 Comparison between uncut and cut tip of hypodermic needle [34] .................... 24
Figure 3.7 Oils used in the experiment ................................................................................. 25
Figure 3.8 Glass container and its layout for measurement between two liquids ............... 26
Figure 3.9 An example of a good droplet image .................................................................. 27
Figure 3.10 Cropping and contrast adjustment of the captured image ................................. 27
Figure 3.11 Edge detection procedure and explanation ........................................................ 28
Figure 3.12 A schematic of a pendant drop below a needle [30] ......................................... 29
Figure 3.13 Schematic of a pendant drop profile fitting process [30] .................................. 30
Figure 3.14 An example of interfacial tension measurement using open drop .................... 33
Figure 3.15 The balance and graduated cylinder used to measure mass and volume .......... 34
Figure 4.1 Comparison between measured and reference value........................................... 36
Figure 4.2 Comparison between measurement and literature value. .................................... 38
Figure 4.3 Calibration with literature value to determine correction factor ......................... 41
Figure 4.4 Effect of Bond number to demineralized water surface tension measurement ... 43
Figure 4.5 Effect of Bond number to olive oil surface tension measurement ...................... 43
Figure 4.6 Effect of Bond number to Tropical palm olein surface tension measurement .... 44
Figure 4.7 Effect of Bond number to Bimoli palm olein surface tension measurement ...... 44
Figure 4.8 A schematic of two drops with the same volume, but different Bond number ... 45
Figure 4.9 Relationship between needle size and Bond number .......................................... 45
Figure 4.10 Effect of Worthington number to demineralized water surface tension
measurement ..................................................................................................................... 46
Figure 4.11 Effect of Worthington number to olive oil surface tension measurement......... 46

iv
Figure 4.12 Effect of Worthington number to tropical palm olein surface tension
measurement ..................................................................................................................... 47
Figure 4.13 Effect of Worthington number to Bimoli spesial palm olein surface tension
measurement ..................................................................................................................... 47
Figure 4.14 Relationship between density and surface tension ............................................ 49
Figure 4.15 Image processing procedure .............................................................................. 50
Figure 4.16 The captured picture before and after bucket filling ......................................... 51
Figure D.1 Bimoli Spesial palm olein density ...................................................................... 63
Figure D.2 Tropical palm olein density ................................................................................ 64
Figure D.3 Pietro Coricelli olive oil density ......................................................................... 65
Figure D.4 Demineralized water density .............................................................................. 65

v
List of Tables

Table 2.1 Coefficient to use with Eq. (2.7) [20] ................................................................... 11


Table 2.2 Comparison of classic methods used in interfacial tension measurements [9]..... 16
Table 2.3 Comparison of needle gauge size ......................................................................... 21
Table 3.1 Camera specification............................................................................................. 23
Table 3.2 Surface and interfacial tension value from literature ............................................ 34
Table 4.1 Summary of fluid density measurement ............................................................... 36
Table 4.2 Density value used for interfacial tension calculation .......................................... 37
Table 4.3 Interfacial tension measurement results................................................................ 38
Table 4.4 Comparison between measured, calibrated, and literature ................................ 42
Table 4.5 Pertamax and Pertamina Dex density ................................................................... 48
Table 4.6 Pertamax and Pertamina Dex surface tension measurement results ..................... 48
Table 4.7 Comparison between density and surface tension ................................................ 49
Table 4.8 The constant value for liquids used in this experiment to be used with Eq. 4.16. 50
Table D.1 Bimoli Spesial palm olein density ....................................................................... 63
Table D.2 Tropical palm olein density ................................................................................. 64
Table D.3 Pietro Coricelli olive oil density .......................................................................... 64
Table D.4 Demineralized water density................................................................................ 66

vi
Chapter 1
Introduction

1.1. Background
Microfluidics is a branch in fluidic sciences that studies fluid behavior on the micro scale.
Research on microfluidics devices started in the late 1970s. Notable researches from that
era which have industrial impact are the development of ink jet printer nozzles at IBM [1]
and a micro electro-mechanical system (MEMS) used in airbag activation [2]. Recent
studies include microfluidic fuel cells and batteries [3], microfluidic systems used to
reduce time and cost in drug development [4], as well as microfluidic systems that can
detect HIV virus rapidly [5]. Given the vast discipline in which microfluidics is applicable
and its apparent benefits, it is important to continue research on microfluidics. However,
basic understanding of the forces affecting microfluidic phenomena must be understood
before complex microfluidic systems can be made.

To understand microfluidics phenomena, knowledge of the forces that dominate in the


micro scale is essential. The reason for this is because the interaction of forces in the micro
scale is different than in the macro scale. The difference can be explained by a concept
called the scaling law. A scaling law signifies: the law of the variation of physical
quantities with the size of the system or the object in question [2]. To put it simply, it is
a measure of change in a physical quantity caused by a change in length or dimension, for
example, area of an object is multiplication of two length scale and therefore the scaling
law of area is 2 . Another example is volume of an object, volume is the multiplication of
three length scale and consequently its scaling law is 3 . Higher order of scaling law
means the physical quantities will have bigger change when the length scale changed i.e.
1
when an object is shrink by half, its surface area will decrease by while its volume will
4
1
decrease by 8 . Consequently forces that have smaller scaling law will dominate those with

larger scaling law when the length scale is in the micro scale (shrink) such as surface or
interfacial tension.

Surface tension is defined as the free energy change, , when the surface area of a medium
is increased by unit area [6]. The difference between surface and interfacial tension is the
place where they happen. Surface tension happens on the surface of a liquid, in other words
it can be defined by one type of liquid. On the other hand, interfacial tension happens on

1
the interface of two or more different fluids. Hence, interfacial tension needs two or more
medium to define it, for example, between two immiscible liquids. Surface or interfac ia l
tension governs many microfluidic phenomena such as the formation of droplet [2],
capillary action [7], and maximum length of thread from droplet formation [8]. For this
reason, it is very crucial to measure the surface or interfacial tension.

Methods to interfacial tension are numerous. Drop shape analysis is a method that is
preferred now because of its simplicity. The drop shape analysis can be divided into two
types depending on the drop shape used the sessile drop method and the pendant drop
method. In the sessile drop method, the drop is resting on a surface, while in the pendant
drop method it is hanging freely from a needle. For both methods, accurate measureme nt
often becomes a problem because of the difficulty in determining the drop shape. This
holds true, especially in a liquid- liquid system interface. Furthermore, it is usually diffic ult
to precisely define the equator of the drop in the sessile drop method, which is essential
for this method [9]. That is why the pendant drop method is used in the current study. In
Indonesia, the measurement devices available are cost prohibitive and hard to find.
However, with the advancement of computing power, moderate numerical analysis and
image processing becomes readily available. In this study, readily available apparatuses
are used with the pendant drop method in an effort to determine if such method and tools
can be used to measure interfacial tension reliably.

1.2. Objectives of Study


The objectives of the current study are:
1. To determine the best method of measuring interfacial or surface tension using
readily available apparatuses
2. To calibrate the measurements done in this study with the accepted value and
determine the correction factor
3. To determine the interfacial tension of some commonly used liquids: Pertamax and
Pertamina Dex

2
1.3. Scope of Study
The scope of this study are:
1. This study uses the pendant drop method to measure interfacial tension
2. The method used is the curve fitting method by numerically solving the Young-
Laplace equation
3. The validity of the method used is determined by comparing the measured
interfacial tension with the accepted value from literature.

1.4. Methodology
The steps used in this undergraduate thesis is as follows:
1. Literature review
In the literature review, the basics of the pendant drop method is presented. This
will help in providing knowledge needed to understand the measurement of
interfacial or surface tension.
2. Experiment preparation
In this step, the tools and materials needed for the experiment are prepared.
3. Experiment
Experiments are conducted several times using various liquid. The measured
interfacial tension of each liquid is noted.
4. Analysis and Conclusion
The measured interfacial tension data are compared to literature data to determine
if the method used to measure the interfacial tension is valid or not.

3
Chapter 2
Fundamental Theories

2.1. Surface and Interfacial Tension


Surface and interfacial tension is somewhat similar. In both of them, cohesive forces are
involved. What differentiates them is which the dominant force is. Surface tension occurs
on the surface of a liquid and therefore there is no interaction with other substance.
Consequently, the cohesive force becomes dominant. On the other hand, the main force in
interfacial tension is the adhesive force because it occurs on the interface between the
liquid and either a solid, liquid, or gas phase of another substance. The interaction occurs
at the surface of the substances involved that is their interfaces [10].

2.1.1. Surface Tension


Surface tension is important in daily life and many engineering applicatio ns.
Surface tension plays a major role in many applications such as washing and
cleaning procedures, in lubricants such as those used in automobiles and cosmetics,
and in the formation of rain drops. It is even the phenomenon that allows the water
strider to walk on water [7].

Figure 2.1 Water strider walking on water [11]

Surface energy or surface tension is the free energy change when the surface area
of a medium is increased by unit area [6]. It can also be considered as the work
needed to create a unit of surface area [7]. Figure 2.2 illustrates the surface tension.

Figure 2.2 Illustration of surface tension [7]

4
In Figure 2.2, the work is equal to for a force equal to and moving a distance
. The increment in surface area is = .

Figure 2.3 Real life soap film experiment to illustrate surface tension [12]

Surface tension arises because of the imbalance of forces between the inner and
surface molecule of the liquid. Figure 2.4 illustrates the imbalance between the
inner and surface force in a water droplet.

Figure 2.4 Inner and surface force in a water droplet [13]

In the bulk of the liquid, each molecule is pulled equally in every direction by
neighboring liquid molecules, resulting in a net force of zero. The molecules at the
surface do not have the same molecules on all sides of them and therefore are pulled
inwards. This creates some internal pressure and forces liquid surfaces to contract
to the minimal area and therefore the surface tension arises.

2.1.2. Interfacial Tension


Interfacial tension is probably the most fundamental equilibrium properties of an
interface in liquid- liquid system. Its value is an important factor governing the
behavior of many systems, for example: the interfacial tension between an organic

5
liquid and water affects processes such as the formation of stable emulsions, the
resistance to flow through orifices, and the dispersion of droplets [14]. It is also
known that interfacial tension plays a major role in liquid- liquid extraction and
improved oil recovery [15]. A study by Taber [16] argues that the interfacial tension
between oil and water must be lowered at least to 0.03 mN/m for effective oil
recovery. Anatica et al. also shows that the knowledge of interfacial tension is vital
in the drug making processes [17].

While surface tension is defined by just one substance, interfacial tension, as the
name suggest, only happen when there are two or more mediums. When two
immiscible liquids are in contact, the free energy change in expanding their
interfacial area by unit area is known as interfacial tension or interfacial energy
[6]. This is illustrated in Figure 2.5.

Figure 2.5 Illustration of interfacial tension [6]

In Figure 2.5, 1 and 2 represents different substance. 11 and 22 is the cohesive


force of substance 1 and 2, respectively. 12 is the adhesive force between
substance 1 and 2 and therefore interfacial tension can be defined as:

1 1
12 = 11 + 22 12 = 1 + 2 12 (2.1)
2 2
Eq. (2.1) is often referred as the Dupr equation.

2.2. Measurement of Interfacial Tension


There are various methods to measure interfacial tension from a simple one to a highly
complex method employing atomic force microscopy. Several commonly used methods
are presented and reasons why the pendant drop method is selected are discussed. Methods
to measure interfacial tension can be classified to several categories. They are shown in
Figure 2.6.

6
Figure 2.6 Classification of common interfacial tension measurement methods [18]

2.2.1. Direct Measurement Using a Balance


Methods in this category uses a simple idea of measuring the force needed to break
away the different shaped body from the liquid- liquid interface as its basis. The
governing equation is shown in Eq. (2.2)


= (2.2)
cos()
where p is the perimeter of the three-phase contact (liquid-solid- liquid) line; is
the contact angle measured for the liquid meniscus in contact with the object in
surface; and is interfacial tension. The most common method in this category is
the Wilhelmy plate method and the Du Noy ring method.

2.2.1.1. Wilhelmy Plate Method


In the Wilhelmy plate method, a vertical thin plate is used. Figure 2.7
shows the schematic of the Wilhelmy plate method.

Figure 2.7 Schematic of the Wilhelmy plate method [18]

7
The plate is put in a fixed position relative to the horizontal surface of the
liquid then the force F vertically acting on the plate by using a microbala nce.
The force applied to the plate is equal to the weight of the liquid menisc us
uplifted over the horizontal surface. By measuring this force, the interfac ia l
tension can be calculated by using the Eq. (2.2) where p is the perimeter of
the plate which is twice the sum of width L and the thickness t of the plate.
The density of the liquids need not be known; however good wetting of the
test liquids to the plate is necessary, cos = 1.

2.2.1.2. Du Noy Ring Method


In the Du Noy ring method, the interfacial tension relates to the force
required to pull a wire ring off the interface as shown in Figure 2.8.

Figure 2.8 Schematic of the ring method [9]

Equation (2.2) still applies to this method. Here, the perimeter (p) of the
three-phase contact line is equal to twice the circumference of the ring: =
4. Additional volume of the liquid is lifted during the detachment of the
ring from the interface and therefore a correction factor (f) is required.
Therefore Eq. (2.2) is corrected as shown in Eq. (2.3)


= (2.3)
cos()
The correction factor varies from about 0.75 to 1.05 and depends on the
dimension of the ring (R,r), its surface wettability (), and difference in
fluid density (). The tabulated values in relation to / (for = 0) can
be found in a study by Harkins and Jordan [19].

8
2.2.2. Measurement of Capillary Pressure
Interfacial tension is defined as the work required to create a unit area of interface
at constant temperature, pressure, and chemical potential. Interfacial tension is
always positive for interfaces between immiscible phases and therefore it always
tends to decrease the area of interface. This tendency gives rise to a pressure
difference between fluids on either side of a curved surface, with the higher pressure
on the concave side of the interface. This pressure difference results in phenomena
such as capillary rise, bubble and drop formation, etc. A formula describing the
pressure difference () across the curved interface is known as the Young-Laplace
Equation as shown in Eq. (2.4).

1 1
= + (2.4)
1 2
where 1 and 2 are the radii of the curvature. The pressure difference across a
curved interface can be measured in a number of ways (e.g., using a pressure sensor
or observing a capillary rise or depression) and then be used to calculate the
interfacial tension if the radii of the curvature are known [9].

2.2.2.1. Maximum Bubble Pressure Method


The maximum bubble pressure method is the most common and probably
one of the oldest methods for surface tension measurements [18]. This
method is based on measuring the maximum pressure to force a gas
bubble out of a capillary into a liquid as shown in Figure 2.9.

Figure 2.9 Maximum bubble pressure method. 1: A sequence illustrating the shape of bubble at
three different stages of bubble growth. 2: Relationship between pressure inside the bubble and
radius of the bubble [18]

9
The measured pressure is the sum of capillary pressure () caused by
interfacial tension and the hydrostatic pressure ( ) exerted by the
liquid column above the orifice of the capillary:

= (2.5)
This pressure can be expressed as the height () of the column of an
imaginary liquid of density ( = ):


= (2.6)

Sugden [20] derived an expression to relate with the Laplace capillar y
constant = 2/() and the bubble meniscus:

1
2
= + (2.7)
2
where = 2 /, = 22 /2 , is the height of the bubble , and is the
curvature radius at the apex (lowest point of the bubble) as shown in Figure
2.9-1. Then he tabulated the minimum values of / as dependent of a

given value of / within the range 0 < < 1.5. This table is shown in

Table 2.1. Using this table, the surface tension can be calculated by
following an iteration procedure. A direct and easier calculation, although
a little less accurate, can be done by using an equation by Cantor [21] as
shown in Eq. (2.8).

2 ()2
= 1 (2.8)
2 3 6 2

10
Table 2.1 Coefficient to use with Eq. (2.7) [20]

/ 0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09
0.0 1.000 0.9999 0.9997 0.9994 0.9990 0.9984 0.9977 0.9968 0.9958 0.9946
0.1 0.9934 9920 9905 9888 9870 9851 9831 9809 9786 9762
0.2 9737 9710 9682 9653 9623 9592 9560 9527 9492 9456
0.3 9419 9382 9344 9305 9265 9224 9182 9138 9093 9047
0.4 9000 8952 8903 8853 8802 8750 8698 8645 8592 8538
0.5 8484 8429 8374 8319 8263 8207 8151 8094 8037 7979
0.6 7920 7860 7800 7739 7678 7616 7554 7493 7432 7372
0.7 7312 7252 7192 7132 7072 7012 6953 6894 6835 6776
0.8 6718 6660 6603 6547 6492 6438 6385 6333 6281 6230
0.9 6179 6129 6079 6030 5981 5933 5885 5838 5792 5747
1.0 5703 5659 5616 5573 5531 5489 5448 5408 5368 5329
1.1 5290 5251 5213 5176 5139 5103 5067 5032 4997 4962
1.2 4928 4895 4862 4829 4797 4765 4733 4702 4671 4641
1.3 4611 4582 4553 4524 4496 4468 4440 4413 4386 4359
1.4 4333 4307 4281 4256 4231 4206 4181 4157 4133 4109
1.5 4085

2.2.3. Analysis of the Balance between Capillary and Gravity Forces


Methods in this category are among the oldest surface tension measureme nt
methods in use. Here the capillary rise method and the drop volume or weight
method will be presented.

2.2.3.1. Capillary Rise Method


The basis for the capillary rise method is to measure the height of the
meniscus in a round glass tube having the known inner radius , as shown
in Figure 2.10. For small-diameter tubes (i.e., ) the shape of the
meniscus is spherical, and the surface tension can be calculated by using
Eq. (2.9).


= (2.9)
2 cos()

11
Figure 2.10 Schematic of the capillary rise method [9]

Since the glass tubes are easy to clean with acids, bases, and organic
solvents, and because many of the liquids perfectly wet the glass surface,
the cos() term in the Eq. (2.9) will often equal unity.

The capillary rise method can be one of the most accurate technique used
to measure surface tension. Technical problems with the technique are
related to the fabrication of a uniform bare capillary tube and precise
determination of its inside diameter. In addition, the capillary rise method
is not very convenient for measuring the interfacial tension between two
liquids.

2.2.3.2. Drop Volume or Weight Method


In this method, the weight or volume of drop falling from a capillary with
a radius is measured as shown in Figure 2.11.

Figure 2.11 Schematic illustration of drop volume or weight method [9]

12
The weight (W) of the drop falling off the capillary correlates with
interfacial tension through the equation showed in Eq. (2.10).


= = 2 3 (2.10)

where V is the drop volume, r is the radius of the capillary, and is the
correction factor required because only a portion of the drop volume is
released from the capillary during detachment.

The measurements of interfacial tension with the drop weight or volume


method are simple but sensitive to vibration. Vibration of the apparatus can
cause premature separation of the drop from the end of the capillary before
the drop reaches the critical size. The vibration can be minimized by
placing the apparatus on vibration- isolation table and making sure the
surrounding air is relatively static. To make the air relatively static, the drop
can be positioned in a closed chamber.

2.2.4. Analysis of Gravity-Distorted Drops

Interfacial tension causes interfaces to behave as elastic membranes that always


tend to compress the liquid. In the absence of other forces (e.g., in zero gravity), the
liquid surface has a natural tendency to form spherical shapes to minimize the
interfacial area per unit volume of liquid and thus, to minimize the excess energy
of the interface. The shape of an interface in a gravitational field (i.e. Figure 2.12,)
depends on the competition between the capillary and gravitational forces and can
be described by the Bashforth-Adams equation [22] as shown in Eq. (2.11).

sin() 1 2
+ = + (2.11)
1
Equation (2.11) is often expressed in a dimensionless form as:

sin() 1 2
+ =2+ (2.12)
/ 1 /
where is the interfacial tension, = equals the difference in density of
fluids, 1 is the radius of the curvature, is the radius of rotation of point around
the axis, is the angle of 2 vector with the axis of symmetry, is the radius of
curvature at the apex of the curvature, and is the acceleration due to gravity.

13
Figure 2.12 Definition of dimensions and coordinates describing the sessile drop [9]

Methods in this category are attractive to researchers because they do not require
advanced instrumentation. The interfacial tension can be calculated from the
dimensions taken from pictures of sessile drop or pendant drop and by using
numerical solutions to solve the Bashfort-Adams equation.

2.2.4.1. Sessile Drop Method


This method is based on the analysis of the drop sitting on a solid substrate
as shown in Figure 2.12. In a simple experiment, one first needs to locate
the equator of the drop, and then measure the height from the top of the
drop to its equator ( ). For a very large sessile drop, an analytica l
expression for the interfacial tension is as follows:

2
= (2.13)
2
It is usually difficult to precisely locate the equator of the drop. It is also
often difficult to locate the top of the drop.

2.2.4.2. Pendant Drop Method


A simple schematic of a pendant drop is shown in Figure 2.13. In a simple
approach, two parameters are needed to be determined to calculate the
interfacial tension using the pendant drop method. They are the equatorial
diameter and the diameter at the distance from the top of the drop.
The interfacial tension is then calculated with Eq. (2.14) [23]:

14
2
= (2.14)

Figure 2.13 Simple schematic of pendant drop

The shape dependent parameter () depends on a value of the shape factor



= . Tables including the set of 1/ vs. values are available in several

references such as by [23] and [24].

2.2.5. Comparison of Measurement Methods


The methods that have been discussed are mostly have been commercialized. Table
2.2 summarizes the accuracy, commercial availability, and suitability of these
techniques for various types of fluid- fluid systems. Most of the measureme nt
methods listed on Table 2.2 have been successfully applied to liquid- liquid systems.

As can be seen on Table 2.2, the pendant drop method is arguably the best method
to measure interfacial tension. The pendant drop method can be used in many
situations except those involving viscous liquid. It also has high accuracy,
especially if used on liquid- liquid systems; unlike the methods that use direct force
measurement using balance as its principle. However, the biggest plus for the
pendant drop method is its simplicity and lack of complex measurement apparatus.
A needle, a camera, and a light source are all that is needed for the pendant drop
method. That is why the pendant drop method is used in this study.

15
Table 2.2 Comparison of classic methods used in interfacial tension measurements [9]

Suitability for Suitability for


Accuracy Suitability for Suitability for Commercial
M ethod surfactant two-liquid
(mN/m) viscous liquids melted metals availability
solutions systems
Wilhelmy Not
~ 0.1 Limited Good Very good Yes
plate recommended
Du Noy Not Not
~ 0.1 Limited Reduced accuracy Yes
ring recommended recommended
M aximum
Not
bubble 0.1 0.3 Very good Very good Yes Yes
recommended
pressure
Very good,
Capillary Not Not
<< 0.1 Very good experimentally Not
rise recommended recommended
difficult
Drop Not
0.1 0.2 Limited Good Yes Yes
volume recommended
Pendant Not
~ 0.1 Very good Very good Yes Yes
drop recommended
Sessile drop ~ 0.1 Good Very good Very good Yes Not

2.3. The Pendant Drop Method


In this section, the basics of the pendant drop method will be discussed further.

2.3.1. History and Development of the Pendant Drop Method


Worthington was the first person that proposes the use of a pendant liquid drop
deformed by gravity to determine the interfacial tension [25]. He evaluated the
pressure drop across a portion of the curved interface of a drop hanging from a
ground glass tube. In 1883, Bashfort and Adams [22] solved the Young-Lap lace
equation numerically and formed a comprehensive table of the approximate
solutions. They showed that the shape of an axisymmetric pendant drop depended
on a single dimensionless quantity, which they called , defined as = 2 /,
where represents density difference, is the gravitational acceleration, is
the drop dimension, and is the interfacial tension. Later in 1948, the
dimensionless number is termed the Bond number by Merrington and Richardson
[26]. It represents the ratio of gravitational force to the capillary force.

By being able to determine the Bond number, then calculating the interfacial tension
is a trivial matter. The interfacial tension can be calculated from Eq. (2.15).

2
= (2.15)

However the determination of the Bond number proves to be difficult. Andreas et
al [23], devised a simple approach for determining this quantity by taking the ratio

16
of two easily measured dimension: the maximum drop diameter and the drop
diameter measured at a distance from the apex of the drop. The ratio =
/ could then be compared to tables of experimentally fitted data to determine
the Bond number. Several people also has experimentally define the equation for
the Bond number. For example, Hansen and Rdsud [27] defined or Bond
number as:

2 3
= 0.12836 0.7577 + 1.7713 0.5426 (2.16)

With the advance of computing technology, fitting the experimental drop profile to
the theoretical drop profile gained by solving the Young-Laplace equation becomes
easier. Many research has been dedicated to the development of the algorithm to
numerically solve the Young-Laplace equation and fitting the drop shape to obtain
the Bond number such as research by Rotenberg et al. [28] and Neumann [29].

Recently, Berry et al. [30] defined a new dimensionless number that can be used to
characterize the measurement precision called the Worthington number defined as:


= (2.17)

where is the density difference, is the gravitational acceleration, is the
maximum drop volume, is the interfacial tension, and is the diameter of the
needle. They also provide an open source program for the pendant drop method
available at www.opencolloids.com in an effort to test and develop the technique
further.

2.3.2. Theory of the Pendant Drop Method


The simplest way to derive the equation for the shape of the drop is by considering
that the fluid to be in equilibrium under the action of gravity and of a unifo r m
surface tension. Then:

1 1
= + (2.18)
1 2
where is the pressure difference between the inside of the droplet and the
surrounding, is the interfacial tension, 1 and 2 are the principle radii of
curvature at point on the surface as shown on Figure 2.14. Equation 2.18 is well-
known as the Young-Laplace equation.

17
Figure 2.14 The pendant drop shape [31]

From simple hydrostatic, it is known that:

= + (2.19)
where is the density difference between liquids, is the gravitatio na l
acceleration, is the vertical coordinate, and is a constant. Therefore:

1 1
+ = = + (2.20)
1 2
Equation (2.20) describes the balance of pressure difference (), between the
inside of the droplet and the surrounding with the interfacial tension at the surface.
The constant () depends in the location of the origin from which the vertical
distance is measured ( is parallel to gravity). At the droplet apex, , = 0, 1 =
2
2 = . Hence, = and since 2 = sin() , then:

1 sin() 2
+ = + (2.21)
1
is the angle between the drop axis and normal of the surface for a given point .

1
Using =
, =
, 1 = , and grouping physical properties and constants,

the dimensionless equation is shown in Eq. (2.22) and (2.23).

1 sin() 2
+ = + 2 (2.22)
1

18
1 sin()
+ = + 2 (2.23)
1
1 and sin() can be replaced in the following manner to achieve differentia l
equation that describes the curve in the form = ( ).

2
1 2
= 3
1 (2.24)
2 2
1 +


sin() =
1
2 2
(2.25)

1 +

Therefore:

3
2 2 1 2 2 (2.26)
+ 1 + ( )
= 2 + 1 +
2
Defining as the arc length measured from the drop apex as shown in Figure 2.15,

Figure 2.15 Pendant drop shape with the arc length from the drop apex, s, shown [30]

19
1
Then from the definition of sin() it can be seen that 1
= sin () =
since

the differential curve length is written as: = 1 . Similarly,
cos() and


= sin (). Using the auxiliary equations for the coordinates, the set of first order

differential equations that are to be solved simultaneously to give the drop shape
are shown in Eq. (2.27), (2.28), and (2.29)


sin()
= 2 (2.27)


= cos() (2.28)


= sin() (2.29)

The boundary conditions are:

= 0 = 0, = 0, = 0

Numerical solver such as fourth order Runge-Kutta solver can be used to


numerically solve the set of differential equations that would give the theoretically-
predicted interface (droplet) shape.

The fitted Young-Laplace solution can also be used to give additional data such as
drop volume and drop surface area , which are defined as:

= 2 sin() (2.30)

= 2 (2.31)

2.4. Needle Gauge


Hypodermic needles (injection needles) are available in a variety of sizes which classed
by gauge number. Smaller number has larger outside or inside diameter of the needle.
Table 2.3 is the table of needle gauges and the respected sizes [8]. For this research the
needles used are 21 G, 22 G, 23 G and 27 G. These variations are based on the availability
on Indonesia market.

20
Table 2.3 Comparison of needle gauge size

Nominal inner
Needle Nominal outer diameter Nominal wall thickness
diameter
Gauge mm tol. mm mm tol. mm mm tol.mm
20 0.9081 0.0064 0.603 0.019 0.1524 0.0064
21 0.8192 0.0064 0.514 0.019 0.1524 0.0064
22 0.7176 0.0064 0.413 0.019 0.1524 0.0064
22s 0.7176 0.0064 0.152 0.019 0.2826 0.0064
23 0.6414 0.0064 0.337 0.019 0.1524 0.0064
24 0.5652 0.0064 0.311 0.019 0.1270 0.0064
25 0.5144 0.0064 0.260 0.019 0.1270 0.0064
26 0.4636 0.0064 0.260 0.019 0.1016 0.0064
27 0.4128 0.0064 0.210 0.019 0.1016 0.0064
28 0.3620 0.0064 0.184 0.019 0.0889 0.0064
29 0.3366 0.0064 0.184 0.019 0.0762 0.0064

21
Chapter 3
Research Method

In this chapter, the method used in this research will be explained. The research will follow the
procedure illustrated in Figure 3.1:

Cropping and Interfacial


Image
Contrast Edge Detection Tension
Acquisition
Adjustment Calculation

Figure 3.1 Research procedure

In the following sections, each step shown in Figure 3.1 will be explained in more detail.

3.1. Image Acquisition


The setup for the experiment is shown in Figure 3.2.

Figure 3.2 Experiment setup [30]

Next sections will give in-depth discussion of each apparatuses and also the fluids that is
going to be measured.

3.1.1. Camera and Optics


The camera used in this experiment is Sony 100. The specifications of the camera
are given in Table 3.1. The picture of the camera is shown in Figure 3.3.

22
Table 3.1 Camera specification

Full model name Sony Alpha DSLR-A100


Sensor type CCD
Effective megapixels 10.2

Figure 3.3 Sony 100 camera [32]

The lens used to capture the images is Quantaray 50mm F2.8 MACRO lens. It is
shown in Figure 3.4.

Figure 3.4 Quantaray macro lens [33]

The lens is suitable for this experiment because it can capture image with signific a nt
magnification needed for the image processing and analysis.

3.1.2. Syringe and Needle


Hypodermic needles and syringes are used in this experiment because it is readily
available in several sizes that is usually used in pendant drop method. This is
important because different needle size will produce different drop shape and the
most convenient drop shape can be chosen for the analysis and calculation. In this
experiment hypodermic needles of 21, 22, 23, and 27 gauge corresponding to 0.8,

23
0.7, 0.65, and 0.4 mm outer diameter respectively are used. The syringes and
needles used in this study are by Terumo. These are shown Figure 3.5.

Figure 3.5 Hypodermic needles and syringes used in the experiment

The volume indicator shows the size of the syringe comes with the needle. However,
the 27G needle size cannot be bought with syringe without a doctors prescription.
Therefore the syringe used with the 27G size are those that come with the other
needle size.

The hypodermic needles have angled and sharp end, but for measurement using
pendant drop method a straight and blunt needle is needed. Therefore, the tip of the
hypodermic needles are cut through wire-cutting process. Figure 3.6 shows the
comparison of the tip of the hypodermic needle before and after the wire cutting
process. The wire cutting process is done at Bandung Polytechnic of Manufacture
using a CNC Wire-cut machine.

Figure 3.6 Comparison between uncut and cut tip of hypodermic needle [34]

24
3.1.3. Light Source and Diffuser
The light source used is a bright white LED light. The diffuser used is a piece of
white paper. A study by Hoorfar and Neumann [35] shows that using a band-pass
filter (i.e., a filter that transmits wavelengths between the two cutoff wavelengths
of the filter) will decrease chromatic effect that might occur when a white light is
used. They found that a mikkle blue filter (wavelength range: 400 500nm) is
themost effective filter to be used. In this experiment, such filter is not needed
because a simple white paper is adequate in producing a decent image for analys is.

3.1.4. Fluids
The fluids that can be measured using this pendant drop method is numerous.
Arashiro and Demarquettes study [36] shows interfacial tension measureme nt
between molten polymers using this method. However the pendant drop method
cannot measure the interfacial tension between two fluids that have similar density.
The accuracy of measurement also suffers if the drop has a low bond number.

The fluids used in this experiment are two brands of palm olein: Bimoli Spesial and
Tropical, olive oil from Pietro Coricelli, demineralized water, Pertamax gasoline,
and Pertamina Dex diesel fuel. Palm olein, olive oil, and demineralized water are
used because they have sufficient surface and interfacial tension data from literature.
Therefore they can be used for calibration means. Pertamax and Pertamina Dex are
chosen because both of them are the commonly used fuel in Indonesia. Knowing
their surface tension might be beneficial for further research.

Figure 3.7 Oils used in the experiment

25
3.1.5. Others
For measuring interfacial tension between liquids, a cube container made of glass
such as shown in Figure 3.8 can be used. The schematic depicting the layout of the
syringe and the glass container is also shown in Figure 3.8. It is important to note
that the lighter liquid must be in the glass container while the heavier liquid is in
the syringe.

Figure 3.8 Glass container and its layout for measurement between two liquids

The procedure to capture a drop image is as follows:

1. Prepare the fluids needed for the experiment. Fill the syringe with the heavier fluid
and the glass container with the lighter fluid (glass container is not needed in surface
tension measurement). Try to remove the air trapped in the syringe during filling
process.

2. Place all tools according to the layout shown in Figure 3.2.

3. Turn on the light source used to illuminate the drop and turn off the room light.

4. Deliver a drop at the tip of the needle manually. Try to get the biggest drop that is
possible.

5. Set the camera position and focus so a good image of drop profile can be acquired. An
example of a good image is shown in Figure 3.9.

6. Repeat to capture as many image as needed.

26
Figure 3.9 An example of a good droplet image

3.2. Cropping and Contrast Adjustment


To simplify the edge detection process, a smaller image that focuses only on the droplet
and needle is preferred. Other than that, a high contrast grayscale or black and white image
is essential for a good edge detection result. These processes are illustrated in Figure 3.10.

Contrast
Cropping Adjustment

Captured Image Cropped Image Edited Image

Figure 3.10 Cropping and contrast adjustment of the captured image

Cropping can be done using the image viewer from Windows or other similar program.
The contrast adjustment was done using GIMP (GNU Image Manipulation Program) [37],
a free and open-source image editor. Other similar program should also be able to perform
the task. However, if the captured image already has good contrast between the
background and the droplet, so the edge of the drop is easily visible, then contrast
adjustment is not necessary. The captured image can immediately be used after it has been
cropped.

27
3.3. Edge Detection
The next step before calculating the interfacial tension is to extract the shape of the droplet
from the acquired image. This is accomplished by using edge detection feature in an image
processing program. In this study, MATLABs edge detection routine from its image
processing toolbox is utilized. Several edge detection methods are available in the
MATLABs image processing toolbox. The Canny method [38] is used in this experime nt
due to its robust nature over a range of contrast conditions. In the Canny method, edges
are found by looking for local maxima of the gradient of the image. This method uses two
thresholds to detect strong and weak edges, including weak edges in the output if they are
connected to strong edges. By using two thresholds, the Canny method is less likely than
the other methods to be fooled by noise, and more likely to detect true weak edges [39].

The steps of this process is shown on Figure 3.11.

Original Image Edge Detected Cleaned Image Outline over


Image Original Image

Canny Edge Detection Clean the Image Extract Profile and Overlaying
The edge are detected. In this The noise are removed and The location of the perimeter are
case, edge are described as the the area inside the detected extracted as x and y coordinate and
local maxima of the gradient of edge is turned into white then overlaid above the original
image to visually check the quality of
the image. color.
the edge detection.

Figure 3.11 Edge detection procedure and explanation

The noise from the captured image is removed by performing an operation known as area
opening. In this operation, all connected components that is less than specified pixel is

28
removed. Hence, noises which are usually smaller than the object of interest can be
removed. In MATLAB, this is achieved using the command bwareaopen.

As stated in Figure 3.11, the drop profile is extracted as x and y coordinate. Therefore,
finding the dimensions needed for interfacial tension calculation is possible. Comparing
the profile with the theoretical profile from the Young-Laplace equation is also possible,
which is the next step in this experiment.

3.4. Interfacial Tension Calculation


It has been explained in Chapter 2 that the droplet shape can be theoretically explained
using the Young-Laplace equation:

1 1
+ = = + (3.1)
1 2
which has been shown can be obtained as a coupled sets of dimensionless differentia l
equations in terms of the arc length measured from the drop apex:


sin()
= 2 (3.2)


= cos() (3.3)


= sin() (3.4)

where * indicates dimensionless quantities scaled by , the radius of curvature at the drop
apex. All variables are shown in Figure 3.12.

Figure 3.12 A schematic of a pendant drop below a needle [30]

29
In Eq. (3.2), is the Bond number, defined as the ratio between gravitational and
capillary force as shown in Eq. (3.5).

2
= (3.5)

Equation (3.2), (3.3), and (3.4) must be numerically solved. The associated boundary
conditions are:

= 0, = 0, = 0 = 0

The shape of the pendant drop is therefore dependent on a single dimensionless quantity,
the Bond number, Bo. If the Bond number associated with a pendant drop can be
determined together with the drop radius at the apex, the interfacial tension is then
readily obtained from Eq. (3.5).

To determine the Bond number, The Young-Laplace equation is repeatedly solved to find
the physical parameters that most precisely describe the extracted drop profile using
optimization techniques. The optimization techniques used in this study is based on the
work of Berry et al. [30]. The process of this optimization technique is shown
schematically on Figure 3.13.

Figure 3.13 Schematic of a pendant drop profile fitting process [30]

Once a suitably accurate experimental droplet profile has been obtained as , coordinates,
the theoretical pendant drop profile is fitted to the extracted experimental data by
minimizing the sum of squared residuals.

= 2 = min

{ ( )2 + ( )2 } (3.6)

=1 =

30
where the th residual, , is defined as the minimum Euclidian distance between data
points ( , ) and any point on the theoretical drop profile ((), ()). The squared
residual can be expressed in terms of a horizontal and a vertical component.
Therefore, the residual vector elements = where

2 = ( )2 + ( )2 (3.7)
Note that the arc length has been introduced which corresponds to the closest
theoretical point to the th data point. By trigonometry:

( ) = |( ) cos() ( ) sin ()| ( )


(3.8)
= {( ) cos() ( ) sin()} ( )
( ) = ( ) sin() + ( ) cos() ( ) (3.9)
Here, and are the coordinates of the droplet apex, and is the rotational angle of
the experimental image relative to the gravity. This is shown in Figure 3.12.

The required fitting routine can be recast as a minimization of the non-linear function (),
where = { , , , , } are the parameters that determine the theoretical drop
profile. The LevenbergMarquardtFletcher [40] automated optimization (LMFAO)
algorithm is chosen because it is particularly well suited to this fitting routine as it
combines the speed of GaussNewton with the stability of steepest descent. LMFAO
updates the parameter set according to:

(+1) = () + (3.10)
where is determined by solving

J J + diag(J J) = J (3.11)
where is the vector of residuals and J is the Jacobian matrix. Details of how the Jacobian
matrix is calculated can be found in Appendix B , and details of the optimization routine
for determining the arc-length at which the associated Euclidian distance is minimized at
each point is given in Appendix C. In Eq. (3.11), the value of is chosen at each step to
ensure convergence. In this work the value of is set according to Fletchers criteria [40],
see Appendix A for details.

The parameters () can be updated according to Eq. (3.10) until one of the following
convergence criteria are met:


i. convergence in the objective function, +1
< 1, or

31
( ) ( )
ii. convergence in the parameters, max +1 < 2, or

iii. convergence in the gradient, max < 3,


with the addition of a maximum number of allowed iterations. Here and = 5 are the
number of data points and the number of fitted variables respectively, and 1,2,3 are
tolerances typically of order 104 107 .

In summary, the optimization proceeds as follows:

0. The parameters are initialized by fitting a circle to experimental data points that define
the bottom 10% of the drop, giving initial guesses for both the center ( , ) and
radius . The rotation is initially set to zero. The Bond number is initialized from
an expression based on the work of Hansen & Rdsud [27]. Further, the parameter
is initialized as 0.

1. The solution to the YoungLaplace equation is generated based on the current values
( ) ( ) ( )
of () = , , , () , () .

2. For each experimental data point , the arc-length that minimizes the Euclidea n
distance is calculated (Appendix C).

3. The Jacobian matrix entry is calculated for each experimental data point and
parameter (Appendix B).

4. Equation (3.11) is solved to find

5. Equation (3.10) is solved to find the updated parameter set (+1) =


( ) ( ) ( )
+1 , +1 , +1 , (+1) , (+1) and a new estimate for is generated.

(Appendix A).

6. Steps 1-5 are repeated until convergence is reached.

Once the final value of and the Bond number has been obtained, the interfacial tension
can be calculated using the following Eq. (2.15).

32
This circle fitting method is implemented in an open-source program provided by Berry
et al. [30] called Open drop. In Figure 3.14, an example of interfacial tension
measurement using this program is shown.

Figure 3.14 An example of interfacial tension measurement using open drop

A spreadsheet file containing the variables value is also created. The measured interfac ia l
tension using this program on this example is 27.8 mN/m.

3.5. Experiments Conducted


The experiments are all conducted inside the Thermal Laboratory of Mechanical and
Aerospace Engineering Faculty, Bandung Institute of Technology. The ambient
temperature is 25C. Before commencing the procedure shown in Figure 3.1, the density
of the fluids used are calculated by measuring mass of the fluids at several volume. To
measure the mass an OHAUS balance model SP202 is used. It has 200g capacity with
readability of 0.01g, repeatability of 0.01g, and linearity of 0.01g [41]. Before the
balance is used, it is calibrated using the supplied test weight. For the volume, a graduated
cylinder is used. It is accurate to 0.01ml, however, the reading error associated with this
graduated cylinder is estimated to be around 0.3 because of the difficulty in
determining the meniscus of the liquid during measurement and there is residual fluid
present when fluid is added to the graduated cylinder. These instruments are shown in
Figure 3.15.

33
Figure 3.15 The balance [42] and graduated cylinder [43] used to measure mass and volume

Several surface and interfacial tension measurements were conducted in this study:

1. Surface tension of Bimoli Spesial brand palm olein


2. Surface tension of demineralized water
3. Surface tension of Tropical brand palm olein
4. Surface tension of Pietro Coricelli olive oil
5. Interfacial tension between Bimoli Spesial and Demineralized Water
6. Surface tension of Pertamax
7. Surface tension of Pertamina Dex
The measurements involving palm olein, olive oil, and water are meant to be the standard
to determine the accuracy of measurement. This is because the surface and interfac ia l
tension value for those fluids are well documented. For the purpose of this study, the
literature value that will be used are:

Table 3.2 Surface and interfacial tension value from literature

Temperature
Fluid 1 Fluid 2 Interfacial Tension (mN/m) Reference
(C)
Palm Olein Air 20 33.2 [44]
Palm Olein Air 60 30.9 0.1 [45]
Palm Olein Water 60 25.0 0.3 [45]
Demineralized Water Air 25 71.99 0.36 [46]
Olive Oil Air 20 33 [47]
The uncertainties of the value are also listed except when the reference does not state their
measurement uncertainty. It should be noted that most of the literature value in Table 3.2
are not measured in the same temperature as this study (25C). These values are chosen
because they are the most relevant available data for this study. However, several studies
have showed that with increasing temperature, the interfacial and surface tension will
decrease [31] [46] [48] [49]. Hence lower surface tension can be expected for palm olein
and olive oil. While interfacial tension between water and palm olein is more likely to be
higher than the literature value. Surface tension of Pertamax and Pertamina Dex are
measured because the data is not yet available from the specification. It is hoped that this
measurement become beneficial and can be used for further studies.

34
Chapter 4
Results and Analysis

This chapter will discuss the results of the measurements. First, a discussion of fluid density
measurement will be presented. After that, the interfacial tension measurement results will be
compared to the literature value to find disparities and what might cause it. An uncertainty
analysis is presented to determine which variable uncertainty is the most important in
determining the interfacial tension. An attempt to calibrate the measurement results with the
literature value will be made and finally the surface tension of Pertamax and Pertamina Dex
will be measured.

4.1. Fluid Density Measurement


The mass of the fluid at several volume is measured using a balance and then the results
are plotted. Linear regression is conducted on the plotted results to obtain the density of
the fluid. The slope of the line or the density of the fluid is calculated using Eq. 4.1.


= (4.1)
2
The uncertainty associated with volume measurement is much larger than mass
measurement (0.3compared to 0.01). Hence, the uncertainty associated with mass
measurement can be neglected. The equivalent error in mass caused by the error in volume
measurement equals to the slope or density times the volume measurement error as shown
in Eq. 4.2.

= (4.2)
The slope or density error is therefore defined by Eq. 4.3.


= (4.3)
2
Further explanation on linear regression and uncertainties associated with it can be found
in Reference [50].

The measurement results for each liquids and its plots can be seen in Appendix D. The
summary is shown on Table 4.1.

35
Table 4.1 Summary of fluid density measurement

Measured Literature Discrepancy Literature


Fluid Density Value Temperature Reference
3
(kg/m3 ) (kg/m3 ) kg/m % Reference (C)
Bimoli Spesial 870 10 870 4 0 0.0% 15 [51]
Tropical 880 20 870 4 10 1.1% 15 [51]
Demineralized 997.0470
980 10 -17 -1.7% 25 [52]
Water 0.00083
Pietro Coricelli 890 20 912 3 -22 -2.4% 25 [53]
A figure comparing both value and their respective uncertainty is made to visualize the
difference between the measured and reference density values. It is shown on Figure 4.1.

Measured Density Reference Density

1050

1000
Density (kg/m3 )

950

900

850

800

750
Bimoli Spesial Tropical Demineralized Pietro Coricelli
Water
Fluids

Figure 4.1 Comparison between measured and reference value

It can be seen from Figure 4.1 that the value for both palm oleins agree with the literature
value. It is true that the literature value is meant for 15C condition, however, usually the
decrease in density for 10C is around 2 kg/m3 . Hence, it is reasonable to conclude that
the measurement value for both palm oleins can be used for further calculation.

For the demineralized water, the measured value is still close to the literature value. It is
unclear what might cause the discrepancy, but the error in determination of volume might
cause it. There is also a possibility of impurities because the same graduated cylinder is
used for water and oil and residual oil might be present because of improper cleaning.
Considering these reasons and also the fact that the value stated in the reference is very
accurate, it is better to use the literature value for further calculation.

36
The discrepancy for olive oil density measurement is quite large, however, the uncertainty
still overlap. The discrepancy is quite possibly caused by the volume measurement error.
It is also possible that the olive oil used in the experiment is different than the one used in
the literature. Measurement of different brands of olive oil is needed to compare the results.
Regardless, it is safe to assume that the measured value can be used for further calculatio n.

It is clear that the measured density values suffer because of the reading error associated
with volume measurement. To mitigate this, a bulb pipette should be used because it is
easier to determine the liquids meniscus in a bulb pipette compared to a graduated
cylinder.

For the interfacial tension calculation, the density value is needed. The density values that
is used for further calculation is presented in Table 4.2.

Table 4.2 Density value used for interfacial tension calculation

Fluid Density Used (kg/m3) Source


Bimoli Spesial 870 10 Measurement
Tropical 870 10 Measurement
Demineralized Water 997 0 [52]
Pietro Coricelli 890 20 Measurement

4.2. Interfacial and Surface Tension Measurement


The interfacial tension calculation results from measurement for palm olein, olive oil, and
demineralized water are presented here. The interfacial tension is calculated using Eq. 4.4.

2
= (4.4)

The value for density difference is calculated from the density value that is known
from Table 4.2. The acceleration of gravity, , is considered constant at 9.81/ 2 . The
value for the radius of curvature at the apex of the drop, , and the Bond number, , is
determined from the iteration procedure described in section 3.4. The summarized results
are presented in Table 4.3. The results are averaged from several measurements for each
needle size. The uncertainties listed is the sample standard deviation. The accepted
literature values and the discrepancy of the measurement results to it are also shown.

37
Table 4.3 Interfacial tension measurement results

Needle Measured Literature Discrepancy Bond Worthington


Fluid 1 Fluid 2
S ize (mN/m) (mN/m) (%) Number Number
27G 7.9 0.4 -68 0.17 0.69
Demineralized Bimoli
22G 52 3 25.0 0.3 107 0.11 0.51
Water Spesial
21G 18 2 -27 0.18 0.61
27G 66 3 -8 0.17 0.72
Demineralized 23G 70 1 71.99 -3 0.22 0.75
Air
Water 22G 65 2 0.36 -9 0.23 0.72
21G 67 1 -7 0.24 0.72
23G 31.4 0.9 -4 0.27 0.80
Olive oil Air 33
21G 29.2 0.3 -11 0.31 0.79
23G 31.7 0.9 -4 0.27 0.81
Tropical Air 33.2
21G 28.7 0.4 -14 0.30 0.79
23G 31.1 0.5 -7 0.27 0.82
Bimoli Spesial Air 33.2
21G 27.3 0.9 -18 0.30 0.74
Figure 4.2 visualizes the data in Table 4.3 and compares the interfacial tension value from
measurement and the accepted literature.

80
70
60
50
(mN/m)

Literature
40
21G
30
22G
20
23G
10
0 27G
DM Water - DM Water - Air Olive - Air Tropical - Air Bimoli - Air
Bimoli
Fluid Pair

Figure 4.2 Comparison between measurement and literature value. The error bars shown represents three standard
deviation

As can be seen from Table 4.3 and Figure 4.2, the surface tension measurement results
(between liquid and ambient air: DM water air, Olive oil air, Tropical air, and Bimoli
air) are quite similar to the literature value. These measurement value overlap within 3
standard deviations regardless of the needle size used. One other thing to note is the
measurement results give consistently lower value compared to the literature value. This
suggests that there might be a systematical error that is present and overlooked in the
experiment. Regardless, the results for surface tension measurement is quite satisfactor y
and suggest that the apparatuses and method used in this study might be used to measure
the surface tension of liquids.

38
While the measurement of surface tension gives decent results, the interfacial tension
measurement between demineralized water and Bimoli is unsatisfactory. The
measurement results of interfacial tension between demineralized water and Bimoli
special have very high discrepancy especially those that use the 22G needle. It is unclear
what might cause this poor results. It is suspected that the small density difference between
demineralized water and palm olein results in small Bond number (less than 0.2), hence
lowering the sensitivity of the measurement. The glass container used in the experime nt
might also contribute to optical aberration, making the picture captured by the camera
inaccurate.

Overall, the current method and apparatuses give satisfactory result for surface tension
measurement but it gives poor result when used to measure interfacial tension between
fluids with similar density. The accuracy of surface tension measurement might be able to
be improved by introducing correction factor. The correction factor can be determined by
calibrating the current measurement results with the accepted literature value. For
interfacial tension measurement, further investigation is needed. Measuring interfac ia l
tension of different fluids with high density difference needs to be conducted. If the
interfacial tension measurement of liquids with high density difference gives satisfactor y
results, then the similar density of demineralized water and palm olein can be determined
as the main factor that contributes to the poor results of interfacial tension measurement.

4.3. Uncertainty Analysis


The interfacial tension is calculated using Eq. 4.4. The error in calculating the interfac ia l
tension is caused by error propagation from each measured variables. It can be determined
by using Eq. 4.5.

2 2 2
2

= + + (4.5)

where , , , and is the error associated with interfacial tension, density
difference, radius of curvature at the apex of the drop, and Bond number, respectively.
The acceleration of gravity, , does not contribute to interfacial tension error because it is
assumed constant at 9.81 / 2 . From Eq. 4.4, then the partial derivatives can be
determined. They are shown on Eq. 4.6, 4.7, and 4.8.

39
2
= (4.6)

2
= (4.7)

2
= (4.8)
2
The error associated with density difference, , can be found on Table 4.2. It is in the
10 /3 range.

To determine the error associated with the radius of curvature at the apex of the drop, ,
the method in which is measured has to be considered. is measured by fitting a
circle to the drop profile. The drop profile is extracted from the edge detected image. Thus
the accuracy is limited by the image resolution and the magnification of the lens. By
knowing the outer diameter of the needle and measuring the number of pixel it represents
in the image, then the dimension which a pixel represents in the image can be calculated.
In this study that ratio is in the range of 0.006 mm/pixel and therefore can be safely
assumed as half of that ratio. This gives in the 0.003 mm range.

The Bond number is defined as the ratio of gravity forces to the capillary forces as shown
in Eq. 4.9.

2
= (4.9)

Assuming the and to be constant for a given system in steady state then the error
associated with the Bond number can be determined by Eq. 4.10.

2 2 2 2
= + (4.10)

Substituting Eq. 4.6, 4.7, 4.8, and 4.10 to Eq. 4.5 gives the error associated with interfac ia l
tension calculation as shown in Eq. 4.11.

2 2 2 2
= 2 + (4.11)

It can be seen from Eq. 4.11 that the error associated with interfacial tension calculatio n
is affected by the error from density and radius of curvature at the apex of the drop
measurement. The error from has more significance compared to the error from as
given by Eq. 4.11. However, the error from density measurement in this study is much

40
larger than the error from measurement (by a factor of 10) and therefore the error in
the interfacial tension calculation caused by the error in can be neglected.

From this error analysis, it is clear that the accurate determination of is crucial for the
pendant drop method hence high resolution camera and big magnification of the drop
shape is important. The needle diameter used to determine the ratio of how much distance
a pixel represents also needs to be measured accurately. This helps to increase the accuracy
of measurement. In any case, the density measurement is also important. It is preferred
that the density and measurement has similar error level for better determination of
interfacial tension.

4.4. Correction Factor


Based on Figure 4.2 and Table 4.3, the measurements made using the 23G needle size
have the least discrepancy and therefore the data is used to calibrate the measureme nt.

Figure 4.3 shows the result for in an attempt to calibrate the measurement with

the accepted literature value.

1
0.99
/

0.98
y = 0.0006x + 0.93
0.97
0.96
0.95
0.94
0.93
0.92
0.91
0 10 20 30 40 50 60 70 80

Figure 4.3 Calibration with literature value to determine correction factor

It is very unfortunate that the data points available are limited. Measurement of a liquid
with surface tension in the 40-50 mN/m and less than 30 mN/m are needed to increase
calibrations accuracy. Regardless, using the current calibration, the measured value can
be calibrated by using Eq. 4.12.

41

= (4.12)
(0.0006 0.0003) + (0.93 0.01)
The uncertainties in Eq. 4.12 are the standard error of the slope and intercept. Table 4.4
shows the comparison between the measured, calibrated, and literature surface tension.

Table 4.4 Comparison between measured, calibrated, and literature

Fluid Needle Measured Calibrated Literature Discrepancy


Fluid 1
2 Size (mN/m) (mN/m) (mN/m) (%)
Demineralized
Air 23G 66 3 72 1 71.99 0.36 0.3
Water
Olive oil Air 23G 31.4 0.9 33 1 33 0.9
Tropical Air 23G 31.7 0.9 33 1 33.2 0.6
Bimoli Spesial Air 23G 31.1 0.5 32.9 0.6 33.2 -1.0
The discrepancy shown on Table 4.4 is between the calibrated and literature surface
tension. The uncertainty listed on Table 4.4 associated with calibrated surface tension is
calculated using the same principle of propagation of error. From Eq. 4.12, the error
associated with calibrated surface tension can be deduced as shown on Eq. 4.13.

2 2 (4.13)
0.00032 + 0.012
= +
0.0006 + 0.93
The correction factor for the measured interfacial tension can be obtained from Eq. 4.12
and it is shown on Eq. 4.14.

1
= (4.14)
(0.0006 ) + (0.93)
The calibrated interfacial tension can be calculated with Eq. 4.12 and its uncertainty can
be obtained from Eq. 4.13.

Using Eq. 4.12, the method and apparatuses used in this study can be used to measure the
surface tension of liquids with satisfactory results. The measured value that has been
calibrated can be expected to be in the range of 2% value from the true value.

42
4.5. Bond Number Effect on Measurements
To investigate the effect of Bond number on the measurement, a plot of against is
made. This is shown on Figure 4.4, Figure 4.5, Figure 4.6, and Figure 4.7 for each surface
tension fluid pair.

21G 22G 23G 27G Literature

74.00

72.00

70.00

68.00
(mN/m)

66.00

64.00

62.00

60.00

58.00
0.10 0.15 0.20 0.25 0.30
Bo

Figure 4.4 Effect of Bond number to demineralized water surface tension measurement

21G 23G Literature

33.5
33
32.5
32
31.5
(mN/m)

31
30.5
30
29.5
29
28.5
0.2 0.22 0.24 0.26 0.28 0.3 0.32 0.34 0.36 0.38 0.4
Bo

Figure 4.5 Effect of Bond number to olive oil surface tension measurement

43
21G 23G Literature

34

33

32
(mN/m)
31

30

29

28

27
0.2 0.25 0.3 0.35 0.4
Bo

Figure 4.6 Effect of Bond number to Tropical palm olein surface tension measurement

21G 23G Literature

34
33
32
31
(mN/m)

30
29
28
27
26
25
0.2 0.25 0.3 0.35 0.4
Bo

Figure 4.7 Effect of Bond number to Bimoli palm olein surface tension measurement

It can be seen that with higher Bond number the measured interfacial tension becomes less
spread. This indicates that with higher Bond number the precision of the measurement is
better. While the bond number can be used to judge the precision of the measurement, it
cannot be used to determine the accuracy of the measurement.

Several studies have showed that the measurement will be less precise at low Bond number
[35]. A small Bond number implies that the interfacial forces dominate the gravitatio na l
force, with the resulting drop profile only slightly deformed away from spherical shape as
shown in Figure 4.8.

44
Figure 4.8 A schematic of two drops with the same volume, but different Bond number [30]

In this regime, the sensitivity of the method is inherently low, since a small change in the
drop profile results in a large change in the apparent interfacial tension. Sometimes this
limitation may be circumvented by making a larger drop, although if the droplet and
continuous phases have similar densities, this may not be possible.

As shown in Table 4.3, several data has low Bond number. Bery et al. [30] showed that
for precise measurement, Bond number must be at least 0.2. Therefore many measureme nt
data obtained in this study are considered not precise. To increase the Bond number a
bigger drop is suggested. This can be achieved by using different needle size, hence
making the drop bigger and consequently the Bond number higher.

4.6. Needle Size Effect on Measurement


To investigate the effect of needle size to the measurement, first a plot of needle size
against Bond number is made. It is shown on Figure 4.9.

DMWater-Bimoli DMWater-Air Olive-Air Tropical-Air Bimoli-Air

0.35
0.3
0.25
0.2
Bo

0.15
0.1
0.05
0
0 0.2 0.4 0.6 0.8 1
Needle Outer Diameter (mm)

Figure 4.9 Relationship between needle size and Bond number

45
It can be seen clearly that with increasing needle size then the Bond number becomes
larger and therefore increasing the sensitivity. Hence, measurements made using bigger
needle should be more precise. A study by Saad et al. [54] inspect the effect of needle size
used to the accuracy of the pendant drop method. In that study the Bond number is a
function of needle outer diameter, not the radius of curvature at the apex of the drop. The
study suggest that for liquid with surface tension of 38 mN/m, a needle with diameter
between 4.0 mm and 8.5 mm should be used to ensure maximum error of 0.1 mN/m.
Based on that study, the needle used in this study is too small and therefore it is
recommended to do measurement again with bigger needle.

4.7. Worthington Number Effect on Measurements


A plot of Worthington number against measured interfacial tension is presented on Figure
4.10 to Figure 4.13.

21G 22G 23G 27G Literature

74.00
72.00
70.00
68.00
(mN/m)

66.00
64.00
62.00
60.00
58.00
0.50 0.60 0.70 0.80 0.90
Bo

Figure 4.10 Effect of Worthington number to demineralized water surface tension measurement

21G 23G Literature

34
33
32
(mN/m)

31
30
29
28
0.7 0.75 0.8 0.85 0.9
Wo

Figure 4.11 Effect of Worthington number to olive oil surface tension measurement

46
21G 23G Literature

34
33
32

(mN/m)
31
30
29
28
27
0.7 0.75 0.8 0.85 0.9
Wo

Figure 4.12 Effect of Worthington number to tropical palm olein surface tension measurement

21G 23G Literature

34
33
32
31
(mN/m)

30
29
28
27
26
25
0.7 0.75 0.8 0.85 0.9
Wo

Figure 4.13 Effect of Worthington number to Bimoli spesial palm olein surface tension measurement

Unlike the effect of Bond number, which is clearly visible, the effect of Worthingto n
number is not apparent. The measurement results do not become less spread with
increasing Worthington number. It can be described as random, at best. This contradicts
the study of Berry et al. [30] that said Worthington number can be used as an indicator of
measurement precision. However, it must be noted that the Worthington numbers obtained
in this study are similar to each other. It might be possible that the effect of Worthingto n
number on measurement is only apparent with large difference of Worthington number.

Another thing to note is that in this study the Worthington number is in the range of 0.5
0.9. The average is 0.8. This means the droplet size is considered big for the given needle
size because the Worthington number represents the ratio of the actual droplet volume to

47
the theoretical maximum droplet volume and therefore the maximum value is 1. Hence, if
bigger droplet size is needed, the needle size used must be increased.

4.8. Pertamax and Pertamina Dex Surface Tension Measurement


Using the correction factor shown in Eq. 4.14, the surface tension of Pertamax and
Pertamina Dex is determined. The density value used for the calculation is shown on Table
4.5. The results are shown on Table 4.6.

Table 4.5 Pertamax and Pertamina Dex density

Fluid Density (kg/m3) Reference


Pertamax 743 27 [55]
Pertamina Dex 840 20 [56]

Table 4.6 Pertamax and Pertamina Dex surface tension measurement results

Calibrated
Fluid 1
Fluid Needle Measured using Eq. 4.12
Bond Worthington
2 Used (mN/m) Number Number
(mN/m)
Pertamax Air 23G 17.7 0.7 18.9 0.8 0.29 0.77
Pertamina
Air 23G 23.7 0.4 25.2 0.5 0.29 0.80
Dex
The surface tension of fuels determine the droplet formation during injection and therefore
it has effects on atomization and combustion process of the fuel. In general, lower surface
tension means faster droplet formation leading to better atomization and combustion. A
study by Thangaraja et al. [57] shows that the surface tension of biodiesel is between 26
and 30 mN/m. They also said that fossil fuel diesel generally have lower surface tension
compared to biodiesel. Therefore the measurement result for Pertamina Dex is reasonable.

The effect of fuels surface tension on combustion have not been rigorously studied. The
surface tension of fuel also is not needed to be stated in standard. This give opportunities
for further study regarding the effect of surface tension of fuels on engine performance. If
it is proved to be significant then it might have to be included in the standard.

48
4.9. Density Effect on Surface Tension
To investigate the effect of density to surface tension, a graph of density against surface
tension is made. The data used is the measurements taken using 23G needle. The data is
shown on Table 4.7 while the plot is shown on Figure 4.14.

Table 4.7 Comparison between density and surface tension

Fluid Density (kg/m3) (mN/m)


DM Water 997 0 72 1
Tropical 870 10 33 1
Bimoli 870 10 33 1
Olive 890 20 32.9 0.6
Pertamax 743 27 18.9 0.7
Pertamina dex 840 20 25.2 0.5

90
80
70
= 1.6E-124.5344
60 R = 0.9265
(mN/m)

50
40
30
20
10
0
0 200 400 600 800 1000 1200
(kg/m3 )

Figure 4.14 Relationship between density and surface tension

It is clearly shown that with higher density, the surface tension tends to be higher too. An
attempt to do non-linear regression is made. The data is fitted to a power function because
the relationship between density and surface tension is clearly not linear. At = 0, the
surface tension should also be 0, hence a power function is considered to be the logica l
choice. From the regression, the surface tension of a liquid can be predicted by Eq. 4.15.

= 1.612 4.5 (4.15)


This result agree with a study by Macleod [58] that said the surface tension of a liquid can
be predicted by using Eq. 4.16.

49

= (4.16)
( )4
where is the surface tension, is the liquid density, is the vapor density, and is a
constant for each liquid. Based on Macleods equation that said the constant value is
specific to each liquid, then the generalized equation for all liquid such as Eq. 4.15 might
be incorrect. It is better to find the value of the constant for each liquid and calculate the
surface tension using Eq. 4.16. Macleod equation can be used to predict the surface
tension at different temperatures as long as the densities used in the equation is measured
at the same temperature. At low temperature, the vapor density is very small compared to
the liquid density and therefore can be neglected. Using the available data from this
experiment, the constant value for each liquid can be calculated and is presented on Table
4.8.

Table 4.8 The constant value for liquids used in this experiment to be used with Eq. 4.16

/
Fluid Density (g/cm3) (mN/m) C (/)
DM Water 0.997 72.2 73.1
Tropical 0.87 33.5 58.5
Bimoli 0.87 33.2 57.9
Olive 0.89 32.9 52.4
Pertamax 0.743 18.9 61.9
Pertamina dex 0.84 25.2 50.6
With constant on Table 4.8 and Eq. 4.16, the surface tension of the liquids at differe nt
temperature can be predicted by knowing the liquid and vapor density at the desired
temperature.

4.10. Image Processing


The image processing used to extract the drop profile in this study consists of four steps
illustrated in Figure 4.15.

Contrast Edge Noise


Cropping
Adjustment Detection Removal

Figure 4.15 Image processing procedure

The cropping is meant to reduce the image size by only focusing on the droplet and needle,
discarding the background. With reduced image size, the processing time is also decreased.

50
The background have no important information and therefore the cropping does not affect
the measurement result.

The contrast adjustment helps the edge detection routine by increasing the contrast
between the droplet and needle with the background. By increasing the contrast, the edge
become clearer and the Cany edge detection routine can easily determine the local maxima
of the gradient of the image. Hence, easily detecting the edges. This step can be skipped
if the captured image already have sufficient contrast. Another method that can be used to
help the edge detection routine is to use the bucket fill tool in many image processing
software. The bucket fill method can also help when the image captured is a little out of
focus. As illustrated in Figure 4.16.

Figure 4.16 The captured picture before and after bucket filling

As can be seen in Figure 4.16, the captured image is a little blurry and this contributes to
poor edge detection. By strengthening the edges using bucket fill tool then the edge
detection results will be better. Basically, the droplet and needle must be sufficie ntly
different to the background for the image detection routine to give satisfactory results.
Poor separation between the needle and droplet with the background might results
erroneous surface or interfacial tension measurement because the drop profile that is
extracted does not represents the actual drop profile.

The noise removal procedure might be needed or not depending on the captured image.
This procedure is meant to remove falsely detected edge. The noises are usually small
compared to the true edge and therefore a filter can be used to discard these noises. By
specifying the minimum area to be considered as edges, the noises can be removed. If the
edge detected has too many noises, the extracted drop profile might not be accurate.

51
Chapter 5
Conclusion and Recommendation

5.1. Conclusions
This study has successfully measured surface tension by means of the pendant drop
method using readily available apparatuses. These things can be concluded:

1. The apparatuses and method described in this study can be used to measure surface
tension with good results. However, it is not recommended to measure interfac ia l
tension between fluids with similar density

2. The correction factor to be used when using this studys method to measure surface or
interfacial tension is

1
=
(0.0006 ) + (0.93)

The equation to be used to calibrate the measured surface or interfacial tension is

3. Surface tension of Pertamax and Pertamina Dex have been measured. The results are
18.9 0.8 and 25.2 0.5 mN/m, respectively.

5.2. Recommendations
Here are several things that is recommended for further study

1. Use more accurate instruments to measure mass and volume in order to calculate the
fluids density

2. Use bigger size needle to obtain bigger drop profile, increasing the bond number.
Hence increasing sensitivity

3. Conduct real time measurement of interfacial tension

4. Use a blunt ended needle supplied by factory to ensure that the needle is better than
the one processed by wire-cutting process

5. Calculate other interfacial or surface tension of liquids commonly used in Indonesia

52
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57
Appendix A
Fletchers Criteria for Setting [30]

The LevenbergMarquardtFletcher algorithm updates the parameter set according to

(+1) = () + (A.1)
where is determined by solving

+ diag( ) = (A.2)

In this Appendix we outline the criteria outlined by Fletcher [40] for setting . From Eq. (A.2),
when = 0 this routine reduces to GaussNewton, while as the parameters are updated
in a step parallel to steepest descent. This method essentially interpolates between these two
routines based on the value of .

In his method, Fletcher introduced the ratio of the actual reduction in the objective (S
is the previous objective function, is the new objective function) to the predicted reduction if
the system was converging quadratically as predicted by GaussNewton,

(A.3)
=
2
where = T and = . This ratio quantifies the rate of convergence for the algorithm. By
comparing this rate to two predetermined values and (with 0 < < < 1, Fletcher suggests
taking = 0.25 and = 0.75), it is possible to determine if the convergence is rapid, > ,
or poor, < . If the convergence is rapid ( > ), the value of is reduced by a factor of 2,
while if the convergence is poor ( < ), the value of is increased by a factor . For
intermediate convergence rates ( ), the value of is left unchanged.

For the case where the convergence is poor ( < ), is determined by minimizing a quadratic
interpolation of the objective function in the direction of . Minimizing this interpolatio n
leads to the optimal step size

1 (A.4)
=
2 ( )/( )
From this the multiple 1/ is determined which is used to update . This multiple is
replaced by 2 or 10 if it is less than 2 or greater than 10, respectively.

58
In addition, Fletcher introduction a cut-off value , below which is set to zero, thus
allowing the algorithm to adopt the complete GaussNewton algorithm. Fletcher provides a
theoretical justification for the choice of to be the reciprocal of the smallest eigenvalue of
1 . As this is computationally expensive, he underestimates this

1 1 (A.5)
=
1 max|1 |
and only calculates this when is increased from zero. The complete LevenbergMarquardt
Fletcher algorithm is illustrated in

Appendix Figure 1 - Flow chart for the LevenbergMarquardtFletcher algorithm. When > , convergence is rapid
resulting in a smaller value of , biasing the system towards the GaussNewton algorithm, whereas for poor convergence,
< , the value of is increased, thereby biasing the system towards steepest descent. Adapted from Fletcher [40]

59
Appendix B
The Jacobian Matrix [30]

We proceed by deriving expressions for the residual vector and the Jacobian matrix, before
discussing an iterative procedure for calculating the arc lengths in the next section. The
residual vector has elements = where

2 = ( )2 + ( )2 (B.1)
where we have introduced the arc length which corresponds to the closest theoretical point
to the th data point. By trigonometry:

( ) = |( ) cos() ( ) sin()| ( )
(B.2a)
= {( ) cos() ( ) sin()} ( )
( ) = ( ) sin () + ( ) cos() ( ) (B.2b)
The Jacobian matrix can be determined by applying the chain rule to Eq. (B.1);

1 (B.3)
= = ( 2 )
2

1
= ( ) + ( ) (B.4)
( )2 + ( )2

We now calculate the derivatives / and / by differentiating Eq. (B.2) with


respect to each of the parameters in = { , , , , }:


= cos() = sin() (B.5a)


= sin() = () (B.5b)


= ( ) sin() + ( ) cos()

(B.5c)

= ( ) cos() ( ) sin()


= ( ) = ( ) (B.5d)


= = (B.5e)

60
where the ambiguous signs in Eq. (B.5), are taken to match the choice of sign in Eq. (B.2a).
Each of these partial derivatives are known explicitly, except for the partial derivatives with
respect to the Bond number in Eq. (B.5e), which arise due to the implicit dependence the
functions and have on the Bond number from Eq. (B.6).

sin() (B.6)

= 2


= cos()


= sin()

( ) ( ; ), ( ) ( ; ) (B.7)
The partial derivatives with respect to the Bond number must therefore be determined by
solving a set of coupled differential equations, formed by differentiating Eq. (B.6) with respect
to the Bond number Bo, and then interchanging the order of differentiation. This leads to a set
of coupled partial differential equations. For constant Bo, these derivatives can be integrated
numerically as a set of coupled ordinary differential equations.


cos sin
+ + (B.8a)
2

+ sin (B.8b)



+ cos (B.8c)

where the associated boundary conditions are determined by differentiating the boundary
conditions:

= 0, = 0, = 0 = 0

leading to


= 0, = 0, = 0 = 0 (B.9)

61
Appendix C
Calculating The Arc Lengths [30]

We now outline the method used to calculate the arc length that minimize the associated
Euclidean distance between the th data point and the theoretical drop profile, enabling the
residual vector and the Jacobian matrix to be determined from Eq. (B.1) and (B.4).

The arc length is the arc length for which the Euclidean distance between the th data point
and the theoretical curve is minimized

2 ( )2 + ( )2 min

{ ( )2 + ( )2 } (C.1)

Introducing the function ( ) which is the derivative of the distance between the th dat
appoint and the theoretical drop profile, we can find by finding the root of ( ). To
perform this procedure we implement a Newton-Rhapson routine, which iteratively updates
( )
according to

()
(+1) = () () () (C.2)
()

This iteration is repeated until the arc length converges to within a specified tolerance, i.e.
( +1) ( ) ( )
( < . Through differentiation the required function can be

found


( ) = ( ( )2 + ( )2 ) = 2 ( ( ) cos ( ) + ( ) sin ( )) (C.3)

and


( ) = 2 { +

( ( ) sin ( ) ( ) cos ( )} (C.4)

Combining Eq. (C.3) and (C.4) leads to an expression for ( ), defined in Eq. (C.2),

( ) cos ( ) + ( ) sin ( )
( ) =
(C.5)
+ ( ){ ( ) sin ( ) ( ) cos ( )}

62
Appendix D
Fluid Density Determination

Table D.1 Bimoli Spesial palm olein density


i 0.3() 2 ( 2 ) ()
( )
1 2.0 4.0 1.62 3.24
2 4.0 16.0 3.35 13.40
3 4.0 16.0 3.36 13.44
4 5.0 25.0 4.24 21.20
5 5.0 25.0 4.32 21.60
6 6.0 36.0 5.16 30.96
7 6.0 36.0 5.17 31.02
8 7.0 49.0 6.11 42.77
9 7.0 49.0 6.14 42.98
10 8.0 64.0 7.00 56.00
11 8.0 64.0 7.09 56.72
12 9.0 81.0 7.92 71.28
13 9.0 81.0 7.91 71.19
14 10.0 100.0 8.81 88.10
15 10.0 100.0 8.82 88.20
SUM 100.0 746.0 87.02 652.10
0.87 g/ml 0.26 g
0.01 g/ml

10.00
9.00 y = 0.87x
8.00 R = 0.9982
7.00
6.00
m(g)

5.00
4.00
3.00
2.00
1.00
0.00
0.0 2.0 4.0 6.0 8.0 10.0 12.0
V(ml)

Figure D.5.1 Bimoli Spesial palm olein density

63
Table D.2 Tropical palm olein density


i 0.3() 2 ( 2 ) ()
( )
1 2.0 4.0 1.76 3.52
2 4.0 16.0 3.51 14.04
3 6.0 36.0 5.26 31.56
4 8.0 64.0 7.02 56.16
5 10.0 100.0 8.78 87.80
SUM 30.0 220.0 26.33 193.08
0.88 g/ml 0.26 g
0.02 g/ml

10.00
9.00 y = 0.88x
R = 1
8.00
7.00
6.00
m(g)

5.00
4.00
3.00
2.00
1.00
0.00
0.0 2.0 4.0 6.0 8.0 10.0 12.0
V(ml)

Figure D.5.2 Tropical palm olein density

Table D.3 Pietro Coricelli olive oil density


i 0.3() 2 ( 2 ) ()
( )
1 2.0 4.0 1.77 3.54
2 4.0 16.0 3.54 14.16
3 6.0 36.0 5.30 31.80
4 8.0 64.0 7.09 56.72
5 10.0 100.0 8.90 89.00
SUM 30.0 220.0 26.6 195.2
0.89 g/ml 0.27 g
0.02 g/ml

64
10.00

9.00 y = 0.89x
R = 1
8.00

7.00

6.00
m(g)

5.00

4.00

3.00

2.00

1.00

0.00
0.0 2.0 4.0 6.0 8.0 10.0 12.0
V(ml)

Figure D.5.3 Pietro Coricelli olive oil density

12.00

10.00 y = 0.98x
R = 0.9999

8.00
m(g)

6.00

4.00

2.00

0.00
0.0 2.0 4.0 6.0 8.0 10.0 12.0
V(ml)

Figure D.5.4 Demineralized water density

65
Table D.4 Demineralized water density


i 0.3() 2 ( 2 ) ()
( )
1 2.0 4.0 1.95 3.90
2 2.0 4.0 1.91 3.82
3 2.0 4.0 1.92 3.84
4 2.0 4.0 1.92 3.84
5 3.0 9.0 2.92 8.76
6 4.0 16.0 3.90 15.60
7 4.0 16.0 3.94 15.76
8 4.0 16.0 3.88 15.52
9 4.0 16.0 3.94 15.76
10 4.0 16.0 3.93 15.72
11 5.0 25.0 4.87 24.35
12 5.0 25.0 4.92 24.60
13 6.0 36.0 5.90 35.40
14 6.0 36.0 5.92 35.52
15 6.0 36.0 5.90 35.40
16 6.0 36.0 5.95 35.70
17 6.0 36.0 5.92 35.52
18 7.0 49.0 6.86 48.02
19 7.0 49.0 6.88 48.16
20 8.0 64.0 7.88 63.04
21 8.0 64.0 7.83 62.64
22 8.0 64.0 7.90 63.20
23 8.0 64.0 7.87 62.96
24 8.0 64.0 7.83 62.64
25 9.0 81.0 8.89 80.01
26 9.0 81.0 8.86 79.74
27 10.0 100.0 9.84 98.40
28 10.0 100.0 9.88 98.80
29 10.0 100.0 9.85 98.50
30 10.0 100.0 9.86 98.60
31 10.0 100.0 9.82 98.20
SUM 193.0 1415.0 189.6 1391.9
0.98 g/ml 0.30 g
0.01 g/ml

66

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