1

<TYPE YOUR TITLE HERE>

A THESIS

Submitted by

<NAME INITIAL>

in partial fulfillment of the requirements for the degree of

DOCTOR OF PHILOSOPHY

FACULTY OF <CIVIL ENGINEERING>

ANNA UNIVERSITY
CHENNAI 600 025

<APRIL 2015>

ANNA UNIVERSITY
CHENNAI 600 025

CERTIFICATE

The research work embodied in the present Thesis entitled <TYPE

YOUR TITLE HERE> has been carried out in the <Name of Department>,
<Name of the college>, <place>. The work reported herein is original and does
not form part of any other thesis or dissertation on the basis of which a degree or
award was conferred on an earlier occasion or to any other scholar.
I understand the Universitys policy on plagiarism and declare that the
thesis and publications are my own work, except where specifically
acknowledged and has not been copied from other sources or been previously
submitted for award or assessment.

<NAME INITIAL>

Dr. <NAME>

RESEARCH SCHOLAR

SUPERVISOR
<Academic Desigantion>
<Department Name>
<Name of College>
<Place>

ABSTRACT

3
Recent technological developments in optics and photonics have been
drastically influenced by the field of nonlinear optics. Nonlinear optical
phenomena plays a pivotal role in many special optical device functions such as
direct optical amplification.

ACKNOWLEDGEMENT

4
I wish to record my deep sense of gratitude and profound thanks to my
research supervisor Dr. <Name>, <Designation>, <Department name>,
<college name>, <Place>, for his keen interest, inspiring guidance, constant
encouragement with my work during all stages, to bring this thesis into fruition.
I am extremely indebted to Dr. <Name>, <Designation>, <Department
name>, <college name>, <Place>, for their valuable suggestions and support
during the course of my research work.
I also thank the faculty and non-teaching staff members of the
<Department name>, <college name>, <Place>, for their valuable support
throughout the course of my research work.

<NAME INITIAL>

TABLE OF CONTENTS

5
CHAPTER NO.

TITLE

PAGE NO.

ABSTRACT

iii

LIST OF TABLES

III

LIST OF FIGURES

III

LIST OF ABBREVIATIONS

III

INTRODUCTION TO NONLINEAR OPTICS AND CRYSTAL

GROWTH

1.1 INTRODUCTION

1.1.1 Theories of Liquid State

1.2 TYPES OF MOLECULAR INTERACTIONS
1.3 LITERATURE
2

3
3

EXPERIMENTAL TECHNIQUES AND THEORY OF SOME

ACOUSTICAL PARAMETERS

2.1
2.2
2.3
2.4

3
3
3
3

SCOPE AND OBJECTIVE

PURIFICATION OF CHEMICALS
TEMPERATURE CONTROL
ULTRASONIC VELOCITY MEASUREMENT
2.4.1 Ultrasonic Interferometer Measurement

2.5 ULTRASONIC INTERFEROMETER (MODEL F-05)

EXPERIMENTAL ARRANGMENT OF WORD

2.5.1 Working Principle Ultrasonic interferometer (Model

F-05)
2.5.1.1 Description
2.5.1.1.1

3
Measuring

2.5.1.1.1.1
2.5.2
2.5.3
2.5.4
2.5.5

Experimental Procedure

3
3

Measurement
Study with the Variation of Temperature
Salient Features
Trial Ultrasonic Velocity for Known Liquids

REFERENCES

6
LIST OF PUBLICATIONS

LIST OF TABLES

TABLE NO

1.1

TITLE

Variation of pH of the growth solution at

different measurement
3.1
Layout of quadrature VCO with LO buffer
Variation
5.1 of pH of the growth solution at different temperatures
2.5
Layout of quadrature
2.8

1dB compression point

3.1

Variation of pH of the growth solution at

different measurement at various temperature at

PAGE NO

25
23
28
29
35

25

different
5.1

Variation of pH of the growth solution at

different measurement at various temperature at

LIST OF FIGURES

26

8
FIGURENO

TITLE

PAGE
NO.

2.1

Experimental arrangement for the measurement

16

2.2

of Ultrasonic velocity in liquids

Ultrasonic Interferometer (Model F-05) the

16

2.3
2.4

measurement of Ultrasonic velocity in liquids

Cross Section of measuring cell
Position of reflection s Crystal current

2.6

Experimental arrangement for the measurement

2.7

of ultrasonic velocity in liquids

Ultrasonic interferometer (Model F-05)

17
17

28
the

measurement of ultrasonic velocity in the liquid

LIST OF ABBREVIATIONS

9
ALU

Arithmetic Logic Unit

ANSI

American National Standards Institute

CPU

Central Processing Unit

CP

Compression Ratio

RGA

Relative Gain Array

10

CHAPTER 1
INTRODUCTION TO NONLINEAR OPTICS AND
CRYSTAL GROWTH

This chapter emphasize the significance and characterization of

liquid mixtures using ultrasonic method. A brief review of literature pertaining
to the present work is also presented.
1.1

INTRODUCTION
Matter exists in three different forms which are solid, liquid and

gas. The most striking difference between a liquid and solid is that a liquid
does not permanently resist the forces tending to change its shape. A liquid
possesses neither the rigidity of a solid nor the fluidity of a gas and so it
exhibits properties intermediate to both the states. (Temperly and Trevena
1978)produced definite evidence that liquids can withstand tensions of at least
tens of atmospheres. Thus, forces between molecules are attractive at large
distances and a liquid resists changes of density and cannot resist changes of
shape.
Matter exists in three different forms which are solil iquid and gas.
The most striking difference between a liquid and solid is that a liquid does not
permanently resist
1.1.1

Theories of Liquid State

A number of theories of the liquid state are based on the concept of

lattice structure in a liquid. A liquid may be considered as a disordered solid.

Liquids are sometimes classified like crystals based on the kind of cohesive

forces that hold them together. Ionic liquids consist of ions and electrons.
Water molecules are held together by Hydrogen bonds. In many molecular
liquids, cohesion is due to Vander Waals forces between essentially saturated
molecules. Even when other forces are present contribution due to Vander
Waals force is always large, which was studied by (Morrison and Nelson
2001)The well ordered arrangement of units in solids is the key difference
between solids and liquids. In a liquid, the orderly arrangement extends over a
short range of around five to six molecular diameters and there is long range
disorder. Near the melting point, the densities of the crystal and its liquid are
nearly the same. The structure of a liquid is continuously changing because of
thermal motions of the individual molecu (Allington 2009)les, that was
reported by (Moore 1965). So the properties of the liquid are determined by
the time average of a large number of arrangements. During recent years, the
theory of the liquid state has attracted a considerable attention and several
working models for liquid state have been proposed which consist in
idealizing a liquid to make it amenable to statistical treatment.
1.2

TYPES OF MOLECULAR INTERACTIONS

When materials mix together to form solutions, the mixing happens

at the molecular level and depends on intermolecular bond types. Suppose A &
B are mixed. In the process the bonds holding A together (A-A) and bonds
holding B together (B-B) are broken. New bonds holding A & B are formed. In
some ways this is like elements combining to form a compound. It is not
necessary for there to be a fixed ratio here. In this case, there can be any
number of As mixed in with the Bs. This process can be exothermic or
endothermic depending on the strength of the bonds involved and whether
more or less energy is released in making A-B bonds than is used in breaking
A-A and B-B bonds. The interaction that exists in a liquid or solution is of two
types viz., the long range and the short range. The highly directional long

range interact include characteristic induction and dispersion forces which

arise without overlap of electron clouds due to the closer approach of
interacting molecules. In the long range interaction, London forces or Vander
Waals forces may be included. The short range interactions such as dipoledipole interactions, dipole- induced dipole, charge transfer, complex formation
and hydrogen bonding arise when molecules come closer together resulting in
significant overlapping of electron clouds.
1.3

LITERATURE
The relay feedback test for process control practitioners as a

closed loop tool for system identification and control (Astrom and Hagglund
1984). A systematic approach to derive the analytical expressions for limit
cycle oscillations of

various benchmark SISO

processes (Panda and Yu

2003). The progress in the relay feedback auto tuning is comprehensively

documented in the book by Yu (1999). (Panda et al 2011) formulated an
identification algorithm to estimate the model parameters of SOPDT and
several integrating using landmark points information on relay responses.
Relative Gain Array (RGA) is the most discussed method for analyzing
interactions and it is based on steady state gain information of MIMO
processes Bristol (1966).

A different approach for investigating channel

interaction was employed by (Conley and Salgado 2000), when considering

observability

and controllability

gramians

in so called Participation

Matrices (PM). In a similar approach (Witten mark and Salgado 2002)

introduced the Hankel Interaction Index Array (HIIA). (Luyben 1986)
proposed a simple, easily implemented procedure for controller tuning in
multivariable systems and it was successfully tested on 10 different systems
taken from the distillation literature.

The

automatic

tuning

of

multivariable systems based on the concept of sequential identification design

and proved that MIMO auto tuner works well for very difficult processes in a

transparent manner (Shen et al 1994). In the present work, an attempt is made

to identify the process and disturbance model parameters using the
mathematical modeling of undesired relay response and then to

retune the

controller parameters using optimization method and extending IMC-PI

controller tuning using Laurent series to MIMO systems.
Early

landmarks

included Pierces quartz-driven

ultrasonic

interferometer (Blitz 1967) and the discovery in 1932 by Debye and Sears and
also by Lucas and Biquard of the ultrasonic diffraction grating. Ever since, the
field has grown enormously with wide applications in science, medicine and
other areas. (Graff 1982) investigated physical, chemical and biological effects
of ultrasounds on macromolecules, microorganisms and cells (Stokes 1845)
made the first attempt in medical imaging using ultrasonics.
Select this option to allow reviewers to use restricted styles when
automatically formatting text such as hyperlinks or automatic bullets. For
example, if you select this check box, Word will automatically format
hyperlinks, even if the Hyperlink style is locked.

CHAPTER 2
EXPERIMENTAL TECHNIQUES AND THEORY OF SOME
ACOUSTICAL PARAMETERS

A detailed experimental procedure adopted in this investigation is

presented in this chapter. In addition, the theoretical formulations involved in the
computation of various acoustic parameters are also discussed.
2.1

SCOPE AND OBJECTIVE

The experimental techniques adopted in the present work for the

measurement of density, viscosity and ultrasonic velocity are presented in this chapter.
Using the density, viscosity and Ultrasonic velocity measurements, the basic theories
involved with special reference to the behavior of various acoustical parameters like
adiabatic compressibility, free length, free volume, internal pressure and their excess
parameters have also been presented. Further, Gibbs free energy, acoustic impedance,
Classical absorption coefficient, relaxation time and Cohesive energy are also
outlined.
2.2

PURIFICATION OF CHEMICALS
The correctness of any physical and chemical quantity depends mainly on

two factors, one is the accuracy of the instrument and the other is the purity of the
substances used. As purity takes a major role in accuracy, presence of impurities
changes (Albert 1975) the behaviour of the liquids and liquid mixtures considerably.
The chemicals used in this present work are analytical regent (AR)
obtained from E- Merck, Qualigens and Sd fine chemicals. The purity of the samples

6
was checked by comparing with literature values. Fresh doubly distilled water whose
specific conductivity 3.6 10-6/ Cm is used throughout the investigation.
2.3

TEMPERATURE CONTROL
An electronically operated constant temperature bath was used to circulate

water through the double walled measuring cell made up of steel containing the
experimental solution at the desired temperature. The accuracy in the temperature
measurement is 0.01K.
2.4

ULTRASONIC VELOCITY MEASUREMENT

2.4.1

Ultrasonic Interferometer Measurement

Techniques used for the measurement of Ultrasonic velocity are classified

into two categories. They are Continuous wave methods and Pulse techniques.
The interferometer method is the most widely used technique for the
measuring of sound velocity with high accuracy (Temperly and Trevena 1978)
developed a simple and accurate interferometer method by modifying the fixed path
type to determine the temperature coefficient of sound velocity. Stationary waves are
produced in this method and the effect of varying path length is investigated. A
reversible crystal transducer is used in a variable path interferometer to both generate
and detect the sound waves. The frequency of vibration of transducer crystal is
adjusted such a way that the crystal vibrates at its natural frequency. As the crystal
attains resonance it vibrates with maximum amplitude. The sound waves generated by
the crystal travel through the liquid medium to a plane reflector that is maintained
accurately parallel to crystal surface. When the resistance between transducer and
reflector is an integral multiple of half wavelength of sound, standing waves are set up
between reflector and the crystal. The reflected sound wave arriving back to crystal
surface after being reflected by reflector is 180 out of phase with the motion of the

7
crystal. This results in the drop of current through the crystal due to decrease of
amplitude of vibration.
The superiority of this technique is well documented by (Sarbjeet singh and
Seema Bawa 2010) and designed an acoustic interferometer for simultaneous velocity
and attenuation measurements in liquids over a wide range of frequencies and a
temperature range from room temperature to cryogenic temperatures. (Morrison and
Nelson 2001)configured an acoustic interferometer capable of measuring ultrasonic
velocity with an accuracy of 0.03%. Theory and performance of differential optical
interferometer for measuring velocities of both surface acoustic waves and bulk waves
is described by (Morrison and Nelson 2001)(Wright & Campbell 1977) developed an
ultrasonic interferometer for a range of frequencies 0.1 to 1.5 GHz. Scattering
technique developed by (Brillouin 1922) is useful in the frequency range of 1 to 10
GHz.
The ultrasonic interferometer is a versatile instrument used for the
measurement of ultrasonic velocity in liquids. It is simple and direct device to
determine the ultrasonic velocity in liquids with a high degree of accuracy. The
working principle of this technique is presented in the following section.
An ultrasonic interferomete (Error: Reference source not found) supplied
by M/s. Mittal Enterprises, New Delhi with a high degree of accuracy, having the
frequency of 3 MHz has been used for velocity measurements.

Figure 2.1
Experimental arrangement of ultrasonic
velocity
measurement in the liquid

Figure 2.2
Experimental arrangement of
ultrasonic
velocity measurement
in the liquid

2.5

ULTRASONIC
INTERFEROMETER
(MODEL
EXPERIMENTAL ARRANGMENT OF WORD

2.5.1

Working Principle Ultrasonic interferometer (Model F-05)

F-05)

The principle used in the measurement of ultrasonic velocity is based on

the accurate determination of the wavelength in the medium. A quartz plate fixed at
the bottom of the measuring cell produces ultrasonic waves of known frequency.
These waves travel through the liquid and are reflected back by a movable metallic
plate kept parallel to the quartz plate. If the separation between these two plates is an
integral multiple of half wavelength, standing waves are setup in the medium. The
reflected waves arriving back at the crystal surface are out of phase. The resulting
decrease in the amplitude of crystal oscillations is accompanied by alternating current
through the crystal. The driving oscillator is loosely coupled to an LC circuit with a
quartz plate in parallel and the same is tuned to the resonating frequency of the crystal.
The acoustic resonance gives rise to an electrical reaction on the generator driving the
quartz plate and the anode current of the generator attains maximum.
When the position of the reflector is changed and the distance is increased
or decreased and the variation is exactly one half of the wavelength or multiple of it,
anode current gain attains the maximum value. Knowing the crystal frequency (f) and
wavelength (), the Ultrasonic velocity (U) of sound in the medium can be obtained
by the relation,
U=

2.5.1.1

2
A= r

(2.1)

Description
The ultrasonic interferometer contains the following main parts viz.,
i) High frequency generator,
ii) The measuring cell,

10

iii) Base to hold the cell and

iv) Shielded cable to connect generator and base.
The high frequency generator is designed to excite the quartz plate, which
is the X-cut crystal that acts on transducer to generate ultrasonic waves. This
transducer is a circular plate of 1cm diameter fixed at the bottom of the measuring cell
2.5.1.1.1 Measuring
The measuring cell is a specially designed double walled cylindrical vessel
for maintaining the temperature of the liquid constant during the experiment. Water
can be circulated through the annular space between the two walls for maintaining the
temperature of the liquid in the cell. Inner wall of the cell is corrugated to prevent wall
reflections. A vertical electrode coming from a solid base makes the electrical contact
to the lower face of the crystal. The side screw makes the fitting of the cell in solid
base. The reflector is connected with the cylindrical plunger. A fine digital micrometer
screw, having a least count of 0.001 mm is employed at the top, which can lower or
raise the reflector plate in the cell through known distance. Hence, the position of the
reflector can be accurately measured with the help of digital micrometer. The distance
of 25mm is available for the movement of the micrometer screw.
2.5.1.1.1.1 Experimental Procedure
Ultrasonic velocities in aqueous/non-aqueous liquid mixtures at different
temperatures have been measured in the present investigation at a frequency 3 MHz.
The detailed method of measurement of ultrasonic velocity using ultrasonic
interferometer is described below. The interferometer cell is cleaned with acetone and
then dried using an air blower. The cell is filled with experimental liquid. The reflector
assembly is coupled to the cell tightly by screwing the knurled cap. The cell is inserted
into the base socket and clamped rigidly with the help of side screw provided to the
base. The inlet and outlet of the double walled construction are connected to constant

11
temperature water bath by means of transparent plastic tubes. Ultrasonic
interferometer with constant temperature water bath setup is shown in Figure 2.1.
Water is pumped into the double walled cell with the help of an electrical
motor provided with the constant temperature water bath. Water of constant
temperature is circulated at least for 30 minutes so that the temperature in the cell
stabilizes. After the required temperature is attained in the interferometer cell, high
frequency oscillator assembly is connected to the base of the cell using shielded coaxial cable. The high frequency oscillator assembly is switched on. The reflector is
gently moved towards the crystal with the help of micrometer screw. Variation of
current through the crystal transducer due to the motion of the reflector is observed
with the help of micro-ammeter provided with high frequency oscillator assembly.
Readings of positions of micrometer screw corresponding to successive maxima (or
minima) of current in the micro-ammeter are noted. From this data, wavelength of
ultrasonic wave is determined. The ultrasonic velocity is determined by multiplying
the wavelength with the frequency of crystal oscillation.
2.5.2

Measurement
The quartz crystal in the measuring cell is connected to the output terminal

of the high frequency generator, through a shielded cable. The cell is filled with the
experimental liquid, before switching on the generator. On exciting the crystal, the
ultrasonic waves traveling through the liquid, are reflected back from the reflector and
standing waves are formed between the crystal and reflector.
The micrometer screw is slowly moved upward till the anode current in
the ammeter attains maximum. Initial reading of the digital micrometer screw is
carefully noted. Screw is then moved further upwards and the reading on the
micrometer screw is noted again for the successive maxima. The total distance (d)
through which the reflector shifted is thus found out for n maxima. The wavelength
is calculated using the relation, Knowing the values of and the frequency f for
the quartz crystal, the ultrasonic velocity U can be calculated

12
d=n /2

2.5.3

(2.2)

Study with the Variation of Temperature

If the variation in the velocity with temperature is to be studied, water at

various desired constant temperature is made to circulate through the double walled
jacket of the cell. The nipples are provided at the cylindrical portion of the cell for
circulating water around the experimental liquid through the water bath.
The following precautions have to be taken while measuring the sound
velocity.
i. The Generator should not be switched on without filling the
experimental liquid in the cell.
ii. The experimental liquid should be removed immediately and the cell
should be kept clean and dry.
iii. Sudden rise or fall in temperature of circulated liquid should be avoided
to prevent thermal shock to the quartz crystal.
iv. While cleaning the gold plating on the quartz crystal it should not be
scratched.

v. The Generator is allowed for 15 seconds for warming up before the

observation.

2.5.4

Salient Features
i.

It is simple in design and gives very accurate and reproductive results.

ii.

Experiments may be performed over a wide range of temperature on

all liquids except those, which reacts, with the plating of the cell and
crystal.

13

iii.

Nearly 12cc of experimental liquid is required.

iv.

Readings can be viewed directly with the help of digital micrometer

fitted at the top of the movable screw.

v.

2.5.5

A very small amount of ultrasonic energy is required.

Trial Ultrasonic Velocity for Known Liquids

In order to verify the sensitivity and accuracy of the instruments, the values

of the ultrasonic velocities have been measured at 303.15, 308.15 and 313.15 K for the
pure liquids chosen for the present investigation and compared with literature values
as shown in Table 2.1

Table 2.1 Ultrasonic velocity(U ) in liquids at 303.15K

Ultrasonic velocity U (ms-1)
Observed
Literature
Reference
Value
Value
Vasantharani et al
1230.33
1230.30
(2009)
1193.40
1194.00
Thirumaran &
1230.15
1237.10
Thenmozhi (2010)

S.No.

Liquid

1.

Cyclohexane

2.
3.

1-Propanol
1-Butanol

4.

1-Pentanol

1252.90

1258.20

Palani et al (2009)

5.

1-Hexanol

1288.49

1289.10

Kannappan et al
(2009)

14

REFERENCES

1. Aghion, P & Durlof, S 2005, Handbook of Economic Growth, Elsevier books,

Amsterdam.
2. Albert, Le 1975, Nuclear Model, Hoxen, New York.
3. Alishahi, K.L , Marvasti, F & Aref Lee Mathew 2009, Bounds on the sum
capacity of synchronous binary CDMA channels, Journal of Chemical
Education, Vol.55, no.8, pp.pp.3577-3593.
4. Allington Bennett Lementon 2009, How to write, PHI, New York.
5. Allington 2009, How to write Bibliographies, How to write Bibliographies,
Vol., no.
6. Australian Securities. 2009. Market information. Available from :
<http://www.asx.com.au/professionals/market_information/index.htm>
[05
July 2009].
7. Fon Gordan William 2009, Mechanics, Mcgraw Hill, Mumbai.
8. Morrison, RT & Nelson, BR 2001, Organic Chemistry, Prentice Hall of India
Pvt. Ltd., New Delhi.
9. Riley, D 1992, 'Industrial relations in Australian Education', in Contemporary
Australasian industrial relations : proceeding of the sixth AIRAANZ
conference , ed. Blackmur, AIRAANZ, Sydney, pp.124-140.
10. Samuel, S 2006, Inorganic Chemistry, Oxford, NewDelhi.
11. Sarbjeet singh & Seema Bawa 2010, Enabling Trust and Privacy based Access
for grid services.
12. Temperly & Trevena, DH 1978, Liquids and their properties, John Wiley and
Sons, New York.

15

LIST OF PUBLICATIONS

International Journals
1. Jeffrey, M, Samy, L, Domnick, R & Karunya, G, 2012,
Experimental liquid mixtures of alcohols, Benzene and
Isohexanes at Varying Temperatures, Eurasian Journal of
Chemical and Petroleum Engineering, vol.223, no.16, pp. 514514, ISSN : XXXX-XXXX (Annexure I). IF 0.5.