Development and Characterization of Self-Cleaning Silver

Doped PTFE/Zinc Thin Films

Senior Design Project

By
SYED SAAD AHMED 2018469
MUHAMMAD ZOHAIB HASSAN 2018363
ASADULLAH 2018081

Advisor
Dr. Rashid Ali
Dr. Ramzan Abdul Karim

Submitted in partial fulfilment of the requirements for the degree of

Bachelor of Science in Materials Science & Engineering

Faculty of Materials & Chemical Engineering

Ghulam Ishaq Khan Institute of Engineering Sciences & Technology,
Topi, Swabi, Pakistan
Spring 2022
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Acknowledgements
I would like to start by expressing our deepest gratitude to our professors who have
helped us by sharing their knowledge and expertise. We also would like to show our
sincere appreciation for the defence committee for giving us feedbacks and their time.

We are also thankful to our friends for the moral support that they have provided us
during this whole term. Also, we are grateful to all the lab engineers who have helped
us in making samples and collecting results.

Lastly, we would also like to mention our parents as it was their belief that helped us
stay motivated during the entire course of this project.
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ABSTRACT
In everyday life the glass has become one of the most used good. It requires regular
cleaning and maintenance as well as, it is also one of the major sources of bacteria
infestation, because of the suitable environment it provides for their growth. Therefore,
the aim of this project is to develop self-cleaning thin films which is both hydrophobic
as well as oleophilic in nature with anti-microbial properties. The theory of Dual-Scale
roughness Mechanism was applied where coating is done on two different scales. One
is Macro scale, and the other is Nano scale. This is like Lotus leaf surface structure
found in nature.

First, we prepared a Zinc Oxide layer which served as Macro Scale Layer (a layer with
thickness in 10^-3). Zinc Oxide purpose is to provide a hydrophobic layer with strong
adhesive properties on soda-lime glass due to its strong bonding and the micro-sized
peaks. The coating is performed via magnetron sputtering in oxygen environment with
Zinc as target material. After which characterization using EDX and AFM was
performed to infer element presence and surface topography. Next Teflon (PTFE)
which has nano-size peaks for super-hydrophobicity along with Silver for anti-
microbial properties target was used to coat Silver doped PTFE thing film on top of
Zinc Oxide layer. The silver doped PTFE layer scale was kept on Nano Scale.
Characterization using EDX and AFM were performed moreover, test for wettability
contact angle and durability were performed. Various samples were prepared for
comparison with different parameter. The macroscale coating on Zinc Oxide layer
resulted in 1.2 um and nanoscale coating of Silver doped PTFE layer resulted in 600nm.
The WCA of overall combined layer was found to be 92 degrees. This indicates close
to superhydrophobic nature. The AFM results showed the pits and spike like
structure indicating a Wenzel state. The roughness average (Ra) calculated was 1.852
nm and root mean square roughness (Rq) was 2.204 nm.

The EDX result showed the presence of Elements used for coating i.e., Silver, Zinc
oxide and PTFE. The dual scale roughness mechanism sample placed in left in open
air compared with one scale roughness mechanism sample showed higher coating
durability and timespan. With this it was deduced that the dual scale roughness
mechanism showed better characterization results when compared to normal
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hydrophobic only film and superhydrophobic only film. It was concluded that the dual
scale roughness mechanism allowed for greater hydrophobicity and greater durability
in aggressive environment.
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TABLE OF CONTENTS

Contents

CHAPTER 1 8

INTRODUCTION 8
1.1 Background 8
1.2 Aims and Objectives 9
1.3 Problem Statements 9

CHAPTER 2 10

LITERACTURE 10
1.1 Introduction to thin film coating 10
2.1.1 Thin film coating 10
2.1.2 Thin film coating Properties 10
2.1.3 Hydrophobicity and Oleophilic 10
2.1.4 Anti-Microbial properties 11
2.2 Applications 11
2.2.1 Anti-Fogging Surfaces 11
2.2.2 Anti-bacterial surfaces 11
2.2.3 Self Cleaning Surfaces 12
2.2.4 Optical Devices 12
2.5 Thin film coating Characterization 14
2.6 Literature Review 15

CHAPTER 3 18

METHODOLOGY 18
3.1 Overview 18
3.1.1 Mechanism 18
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3.2 Experimental Details 19

3.2.1 Materials and Apparatus 19
3.2.2 Preparation for coating Zinc Oxide 20
3.2.3 Preparation for coating Poly-tetrafloro-ethylene (PTFE)+
Silver 21
3.2.4 Characterization Techniques 22
3.2.4.1 Atomic Force Microscopy 22

CHAPTER 4 25

RESULTS AND DISCUSSION 25

4.1 Surface Properties 25
4.2 EDX Result Analysis 26
4.3 Wettability Angle test 28
4.4 Water drop Test 29

CHAPTER 5 30

CONCLUSION 30

CHAPTER 6 31

FUTURE SCOPE 31
6.1 Corrosion Resistance 31
6.2 Anti-Icing Surface 31
6.3 Oil and Water Separation 31
6.4 Drag Resistance 32
6.5 Batteries Manufacture Technology 33
6.6 Sensors 33

REFERENCES 35
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TABLE OF FIGURES

FIGURES

Figure 1:- Wettability Contact Angle 11

Figure 2:- Different wetting models 15
Figure 3:- Scanning Electron Microscopy Machine 18
Figure 4:- Sputtering Mechanism 19
Figure 5:- Zinc deposition 20
Figure 6:- AFM Machine 22
Figure 7:- Angle Measurement 23
Figure 8:- Scanning Electron Microscopy Machine 24
Figure 10:- AFM image of Zn Dip Coated 25
Figure 9:- AFM image of Zn Dip Coated 25
Figure 11:- AFM image of Zn sputtered 25
Figure 12:- 3-D AFM of Zn+PTFE+Ag 25
Figure 13:- Graphical representation of Elements 26
Figure 14:- Elemental Table 27
Figure 15:- Elemental Mapping Zn 27
Figure 16:- Elemental Mapping of a) Carbon and b) Flourine 27
Figure 17:- Elemental Mapping of Silver 27
Figure 18:- Wettability Contact Angle Test 29
Figure 19:- Water Droplet on sample surface 29
Figure 20:- Surface Comparison 31
Figure 21:- Hydrophobic and Hydrophilic surface reaction to oil 32
Figure 22:- Strip Size Expansion Test 32
Figure 23:- Hydrophobic surface 33
Figure 24:- Silver Nano-particles on Hydrophobic surface for sensor
development 34
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1 CHAPTER 1

INTRODUCTION
1.1 Background

The hydrophobic concept is something which have interested scientist and researcher
from a long time. The effect scene in nature of “Lotus Leaf” where water droplet would
roll off the leave without smearing on leaf structure is something quite extraordinary.
Based on that scientist have worked to develop artificial hydrophobic surfaces which
will resist water or solvent on the coating surface. These surfaces have brought into
application like self-cleaning windows, windscreens, and mobile phones.[1]

However, the problem with these coating have remained that they are not chemically
and mechanically stable in the environment. There are prone to chemical reaction with
the environment which fade away their “special structure” which allow for its
hydrophobic properties. Moreover, mechanical force for instance vigorous tapping on
windows our mobile phone screen result in damage to coating structure. Hence, there
is a need for more chemically and mechanically stable hydrophobic and
superhydrophobic coatings.[2]

As the covid hit peoples were forced to wear mask and take necessary prevention
methods to stop the spread of the virus. Moreover, many institutes, and business were
closed, so that people will stay and work from home. This allowed them to use their
mobile phones excessively. A study was done by the University of Arizona to find out
the number of germs on a mobile and it was shown to have more than 10x the germs
than a toilet seat.

Now as we know the people would always share their phones with each other for what
soever reasons and this allows their germs to be transmitted to them and when they
receive it back, they have been given the other persons germs. Exchange of mobile
phones causes millions of germs to be transmitted from one person to another. The
reason, the germs inhibit a mobile screen is that it provides an optimum
environment(warm) for them to grow without any hindrance.
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1.2 Aims and Objectives

The objectives of the thesis are shown as following:

• The Aim of this project is to achieve a Self-Cleaning Silver Doped

PTFE/Zinc Oxide Thin film for Mobile Phone Applications

• To achieve a Zinc Oxide (ZnO) Micro Scale Coating via Magnetron

Sputtering on Glass Substrate resulting in Hydrophobic Surface

• To achieve a PTFE (Teflon) + Silver Nanoparticles (Ag) on Nano Scale

coating via RF CO-Sputtering on Zinc Oxide (ZnO) glass surface

resulting in Super-Hydrophobic surface

• To achieve Hydrophobic/Oleophobic and Anti-Microbial Properties on

resulted surface.

1.3 Problem Statements

To increase the hydrophobic/superhydrophobic coating timespan and durability in

environment and as many peoples using their phones and exchanging them with others
allows various germs to be exchanged between people without them knowing it. To
prevent the germs to be transmitted a coating is to be developed which has anti -
microbial properties to be coated on mobile screen panels.
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1 CHAPTER 2

LITERACTURE
1.1 Introduction to thin film coating

In this we will discuss what are thin films. The various properties of thin films and the
techniques involved for making thin films. We will discuss the problems associated
with thin films as well.

2.1.1 Thin film coating

Thin film coating is a type of coating which is deposited on the materials in-order to
enhance the surface properties of a material and protect the materials from various
harmful conditions like corrosion, wear etc. They are made up of metals, alloys,
ceramics, or polymers or it can be a combination of different materials as well.
Nowadays, they have various application ranging from household uses like for mirror
which has its back coated with silver to industrials application like wear and corrosion
resistance coatings on the machines to increase their service life and efficiency to work
at high temperature.

2.1.2 Thin film coating Properties

Thin film properties are dependent on their morphology. Therefore, it is very important
to be clear of the surface morphology required for specific application. The surface
morphology includes grain size, shape, orientation etc. The main properties of the thin
films are the mechanical, electrical, optical.

2.1.3 Hydrophobicity and Oleophilic

The hydrophobic effect is said that when water has a contact angle with the surface
which is greater than 90 degrees. When the contact angle is greater than 150 degrees
than it is said to be Super-Hydrophobic (figure 1).
The same is true for Oleophobic but it is for non-polar solvent.
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Figure 1:- Wettability Contact Angle

2.1.4 Anti-Microbial properties

Anti-microbial means is to kill the microbes which can be bacteria or virus. And an
anti-microbial coating is a coating which prevents the germs to be accumulate on a
surface. This makes the devices to be used for safe and prevents any harmful germs to
be transmitted from one person to another.

2.2 Applications

2.2.1 Anti-Fogging Surfaces

Most of the time, the vapour is made on mirrors, glass, and other surfaces, which could
cause unknown risks and problems in everyday life and in industrial settings. This
problem can be fixed by controlling how the substrate and liquids react with each other.
In short, these strategies include Superhydrophilic layers (with a contact angle of 0),
SHS layers with a contact angle of more than 150, and hydrophilic/oleophobic
layers.[3][4]

2.2.2 Anti-bacterial surfaces

The pollution of the environment by materials and equipment is a big problem in many
fields, including the medical field. In the case of hospital infections, the growth of
biofilms, which happens naturally and on its own, can become a problem. Bacteria-
killing surfaces and surfaces that stop biofilms from sticking together are two ways to
get rid of biofilms or make them stick less. SHS are also used for this purpose.
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2.2.3 Self Cleaning Surfaces

Self-cleaning surfaces can be used in many ways in everyday life, farming, industry,
and the military. Self-cleaning surfaces have been made in many ways in recent years.
Many things, like glasses, tiles, and tissues, have been made with coatings that make
them easy to clean. Superhydrophobic surfaces could be used to make surfaces that
clean themselves.[5]

2.2.4 Optical Devices

To make superhydrophobic films, the surface must have a certain structure. The
surface structure affects how things look. Superhydrophobic films and surfaces have
different structures, and other properties like self-cleaning, anti-dust, anti-mist, etc.
have also been studied in terms of their optical properties. Surface structure can reduce
clarity, depending on how rough it is and how much light it scatters. However, this
property is needed in many places, such as glasses, optics, and cameras. For a
superhydrophobic film that is also clear, the surface roughness must be less than the
wavelength of visible light. So, most superhydrophobic films with high clarity are
made with nanoparticles (SiO2, TiO2, zinc oxide, C, polymer) through electrospinning,
sol-gel process, vapour deposition, or cloud lithography.
Superhydrophobic films are used to improve the performance of other optical
applications, like photon crystals and light brightness.[6]

2.3 Requirement Of Hydrophobic and Superhydrophobic Surfaces

2.3.1 Wettability
Wetting, or getting liquids to stick to solid surfaces, is an important part of materials
science and surface chemistry, and it can also be used in real life and in industry. When
a drop of water is put on a surface, it should form a sphere or cover the whole surface
with water. The first case is called "anti-wetting," and the second is "super-wetting."
In most wetting studies, the contact angle is one of the most important pieces of
information because it shows how much a liquid and a solid stick together when they
are in contact. Think about a drop of liquid put on a flat surface.
The contact angle is the angle that is made when a solid, a liquid, and a solid-gas
interface meet. Figure 1 shows that the contact angle is small when the liquid is spread
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out over the surface and large when the area of contact between the solid and liquid is
small.[7]

2.3.2 Surface Roughness

For a surface to be superhydrophobic, it must have a rough surface. Since air bubbles
get caught in the surface's ups and downs, when water is put on it, it doesn't touch all
of the surface's points. Because the surface energy is low and there is air there, water
doesn't get into the valley. As a result, the surface area is smaller, which makes the
friction less. This makes it easy for droplets to slide across the surface. There are two
ways to make an uneven surface: from the bottom up and from the top down. In the
bottom-up method, nanoparticles are usually the main building blocks. In the top-down
method, the cover is made with techniques like etching and lithography, with or
without a mask. Recently, there has been more interest in processes that might combine
these two methods.[8][9][10]

2.3.3 Surface Energy

It is very common for superhydrophobic surfaces to be made by lowering the surface
energy. The surface energy is lowered with the help of surfactants. There are many
kinds of compounds and ways to use them. People think a lot about silane groups when
they want to lower the surface energy. Fluoroalkyl silanes get the most attention in
silane groups because, of the compounds that have been found, they have the biggest
effect on lowering the surface energy. Because both CF2 and CF3 groups are present
at the same time, these compounds work very well.
On the other hand, researchers are looking for alternatives to fluorocarbons, such as
stearic acid and polymers, because fluorocarbons are expensive and can be bad for the
environment.[11][10]

2.4 Thin film coating Techniques

There are various ways to deposit a thin film coating so that it can have the properties
that is desired due to the advancement of the coating techniques. The coating
techniques is mostly divided into two types:
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1. Physical Deposition
PVD short for Physical Vapor Deposition is a method in which we use a target
source which is the one we want to be coated is used that has its atoms removed
from itself and then have it deposited on the substrate which is the material we
want to be coated. The atoms move slowly towards the substrate and solidifies
itself on the substrate making a coating. There are various parameters to
consider when PVD is done like temperature of substrate and target, pressure,
vacuum etc. The PVD methods are of various types: -
a) Sputtering
b) Cathodic Arc Deposition
c) Electron Beam PVD
d) Laser Ablation
e) Vacuum Deposition

2. Chemical Deposition
CVD short for Chemical Vapor Deposition is a method in which we use
reactive gases as source which contains elements or compounds that will react
to form the coating of the desired composition we want on the substrate. The
reactive gases are carried by the carrier gas towards the substrate so that the
reaction can occur on the top of the substrate and the desired coating is
deposited and the by-products are taken away by the carrier gas. There are
various parameters to consider when CVD is done like speed of carrier gas,
pressure, vacuum etc. The CVD methods are of various types: -
a) Thermally Activated CVD
b) Plasma-enhanced CVD
c) Metal-organic CVD
d) Low-pressure CVD
e) Photo-initiated CVD

2.5 Thin film coating Characterization

Characterization tells us about the features of a thin film which will help us to know
that if the desired surface morphology is achieved and if not, what could be the possible
reasons.
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There are various types of characterization techniques which gives us various results.
Some give us the surface morphology, some the granular structure, some give us the
elemental composition while some give us the cross-section of the thin film coating
and the substrate. While some techniques allow us to see how it will react at various
temperatures, their optical and electrical properties as well. Types of characterisation
techniques which are mostly use:
a) X-Ray Diffraction (XRD)
b) Scanning Electron Microscopy (SEM)
c) Atomic Force Spectroscopy (AFM)
d) Ultra-Violet Light Spectroscopy
e) Energy Dispersive X-Ray Spectroscopy (EDX)
f) Fourier Transform Infrared Spectroscopy (FTIR)

2.6 Literature Review

Before talking about the SHS, wetness and different theoretical models are first talked
about. Here, the original models for wetting are shown and their basic ideas are talked
about. Young made the first one, which came out in 1805.[12]

Figure 2:- Different wetting models

In this model, for a drop of liquid on an ideal flat surface (Figure 2), wetting is defined
by the surface free energy of a solid, which is found by using Eq. (1) and Young's
equation:

where gamma is the surface tension, which shows how much energy is being used per
unit area. This equation shows that the contact angle is related to the surface energy.
You could say that the Young angle is made by the thermodynamic equilibrium of free
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energy surfaces at the interface between a solid, a liquid, and a gas. Since most real
surfaces have different surface conditions and the roughness of a solid's surface has a
big effect on how wet it is, Young's equation can't fully explain most of the contact
angle states in real life. In 1936, Wenzel came up with an equation, Eq., that linked the

surface roughness and surface energy to the contact angle Eq(2) :-

Where theta(w) is Wenzel’s contact angel affected by surface roughness and r is a

roughness parameter. Modified Wenzel’s equation is:

Wenzel's equation is based on the idea that liquid flows into the surface's grooves, so
it is related to the homogeneous wetting regime. The Wenzel equation can't also
explain how superhydrophobic properties can be found in materials that are
hydrophilic, or how superoleophobicity properties can be found in materials that are
oleophilic. Wenzel's equation shows that the roughness changes how wet or dry a
surface is, depending on what it is made of. So, when the contact angle of a flat surface
is more than 90 degrees, the roughness of the surface increases the angle, and when
the angle is less than 90 degrees, the roughness of the surface decreases the angle.
Wenzel's model only works for areas where the two surfaces are the same. It can't be
used on surfaces that aren't the same. In this way, Cassie and Baxter's model from 1944
for heterogeneous surfaces is also useful. Their plan is made up of two parts. The first
part has the surface fraction, f1, and the contact angle, theta1. The second part has f2
and theta2. So, in the equation by Cassie and Baxter, the contact angle is given by Eq.
(4):
where h is the contact angle in Cassie and Baxter's model and fi is the fraction of
surface area with a contact angle of hi (f1 + f2 = 1). In Cassie and Baxter's model, it is
assumed that the liquid only touches the solid at the roughness tips and that air pockets
are trapped below the liquid. In this case, you could say that the liquid doesn't reach
the part of the surface where the air is trapped. If there is only air between the solid
and the liquid, theta2 is 180. So, Equation 4 can be written as Equation 5:

where fs is the fractional solid surface with a contact angle of thetas. In addition to the
models listed, more improved models have been provided in references to predict the
specific modes of wetting.[13]
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By putting together silica microspheres and nanospheres, two easy ways were found
to make a super-hydrophobic film with two different sizes of roughness. Electrostatic
adsorption and template-directed self-assembly were both used in this case. The
topology of the dual-size surface is like that of lotus leaves. It has both micro-scale
and nano-scale roughness. After the roughened surface was chemically changed with
a layer of fluoroalkylsilane, super-hydrophobicity with a water contact angle higher
than 160° and a sliding angle as low as 0.5° can be achieved. Because this method is
easy and cheap, this super-hydrophobic film could be used in many ways.
Radio frequency magnetron sputtering was used to put thin layers of zinc oxide on
silicon and silicon that had been oxidised by heat. The films that were made were
studied based on how much oxygen and argon flowed as process gases. Stoichiometric
films were made in a process with a lot of oxygen, which makes them better for p-type
doping. When zinc oxide films grew on top of thermally oxidised substrates, the
structure got better.
Superhydrophobic surfaces (SHS) are important in a lot of ways, which makes
studying them very interesting. One of the main uses of these SHS is to make surfaces
that are exposed to corrosive environments more resistant to corrosion and to keep
their superhydrophobic properties over a long period of time. Deep knowledge of how
to make SHS more resistant to corrosion is important for coming up with ways to make
these surfaces more resistant to corrosion and chemically stable over time. Mechanical
stability is another important property of superhydrophobic surfaces that makes it hard
to use them in real life. This review article gives a general overview of SHS and then
talks about how they are made.
Also looked at are the different ways these SHS can resist corrosion, as well as their
chemical stability and mechanical stability. - In the next section, we'll look at some
recent ways to improve corrosion resistance, chemical stability, and mechanical
stability.[14][15]
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1 CHAPTER 3

1 METHODOLOGY

3.1 Overview
3.1.1 Mechanism
The physical mechanism which was used for the preparation of the hydrophobic thin
film was the “Engineering Dual Scale Mechanism”. In this we first apply a coating of
higher thickness (micro-scale) as base and then we apply a second coating of lower
thickness (nano-scale). This allows for greater timespan of the thin film despite the
rough environment usage which is because if nano-layered coating has worn off there
is still a micro-layered coating beneath it. Moreover, it increase the adhesion properties
of a nano scale coating. Compared to glass substrate nano scale coating adhere more
strongly with the micro level coating as it forms secondary bonds like wander val
forces.

Figure 3:- Scanning Electron Microscopy Machine

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3.1.2 Deposition Technique

The deposition technique used for the thin film deposition is the magnetron sputtering.
It was due to higher precision and uniform distribution of the targets. As well as it
allows for greater control over the thickness of the thin films. And lastly it is the fastest
process as it requires no sample preparation.

Figure 4:- Sputtering Mechanism

3.2 Experimental Details

3.2.1 Materials and Apparatus
Zinc target was secured from the Sputtering Lab. The Teflon target was purchased
from QS Advanced Materials Inc., Michigan United States. Silver target was secured
from the Sputtering Lab. Scanning Electron Microscopy (SEM) photographs were
taken by Scanning Electron Microscopy (HITACHI, S-300N) with an operating
voltage of 30 kv. Contact angle of water was measured by Contact Angle Measurement
System (KSV Cam-200, KSV instrument LTD.), under a room temperature.
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3.2.2 Preparation for coating Zinc Oxide

Zinc Oxide of micro-thickness of about 1.2 micro-meter was sputtered onto the glass
slides using the magnetron sputtering machine and following parameters were used: -

Parameters Values

Power 120 Watts

Stage Rotation 100 rpm

Pressure 2.8 × 10 −1 Pa

Cleaning 330/10

Argon Flow Rate 50 sccm

Figure 5:- Zinc deposition

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3.2.3 Preparation for coating Poly-tetrafloro-ethylene (PTFE) + Silver

PTFE + Silver of nano-thickness of about 600 nano-meter was sputtered onto the glass
slides using the magnetron sputtering machine and following parameters were used: -

Paramters Values

Power 100 Watts for PTFE and 100 Watts for

10 seconds after every 250 Armstrong
(10^-10) for Silver

Stage Rotation 90 rpm

Bias Voltage -150 V

Temperature 25 Degree Celsius

Pressure 6.8 × 10 −3 Pa

Time 25 minutes

Argon Flow Rate 50 sccm

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3.2.4 Characterization Techniques

3.2.4.1 Atomic Force Microscopy
The atomic force microscope (AFM) was created to address a fundamental limitation
of STM: it can only image conducting or semiconducting surfaces. The AFM can
image almost any surface, including polymers, ceramics, composites, glass, and
biological samples.

A sharp tip is raster-scanned over a surface using a feedback loop to adjust parameters
needed to image a surface, similar to how a Scanning Tunnelling Microscope works.
The Atomic Force Microscope, unlike Scanning Tunnelling Microscopes, does not
require a conducting sample. To map the tip-sample interaction, atomic forces are used
rather than the quantum mechanical effect of tunnelling.

Atomic Force Microscopy (AFM) techniques exist for almost any measurable force
interaction, including van der Waals, electrical, magnetic, and thermal interactions.
Modified tips and software adjustments are required for some of the more specialised
techniques.

In addition to Angstrom-level positioning and feedback loop control, Atomic Force

Microscopy typically includes two components: Deflection and Force Measurement.

Figure 6:- AFM Machine

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3.2.4.2 Wettability Contact Angel Test

The contact angle, (θ), is a quantitative measure of a solid's wetting by a liquid. The
geometrical definition of the contact angle is the angle formed by a liquid at the three-
phase boundary where a liquid, gas, and solid intersect. Three forces act on this three-
phase contact point between solid, liquid, and gas, or solid, liquid, and liquid in some
cases. Contact angles are classified as static, dynamic, or roughness corrected.

Angle of static contact

When the droplet is resting on the surface and the three-phase boundary is not shifting,
static (also known as sessile drop) contact angles are recorded. The majority of
wettability values are measured for static contact angles. It works best with generally
uniform, smooth surfaces. The surface free energy of the substrate—also known as
surface tension of solid—can be calculated using static contact angles. The wettability
can be quickly, simply, and quantitatively measured using static contact angle. Young's
equation, which is the foundation for measuring static contact angles, assumes that
interfacial forces are thermodynamically stable.

Optical tensiometer for measuring static contact angle

The most popular contact angle measurement method is sessile drop measurement. In
actuality, a droplet is positioned on the stable surface, and an image of the drop is
captured. The Young-Laplace equation is then fitted around the droplet to determine
the static contact angle, though other fitting techniques such a circle or polynomial can
also be utilised.

Figure 7:- Angle Measurement

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3.2.4.3 Scanning Electron Microscopy

A concentrated stream of high-energy electrons is utilised by the scanning electron
microscope (SEM) to produce a range of signals at the surface of solid specimens. In
addition to the sample's exterior morphology (texture), chemical composition, and
crystalline structure and orientation of its constituent materials, the signals resulting
from electron-sample interactions also provide information about the sample.

Most often, a portion of the sample's surface is chosen for data collection, and a 2-
dimensional picture is created to show the spatial variations in these attributes.
Conventional SEM methods can be used to image areas with widths of roughly 1 cm
to 5 microns in a scanning mode (magnification ranging from 20X to approximately
30,000X, spatial resolution of 50 to 100 nm). The SEM is also able to analyse specific
point locations on the sample; this method is particularly helpful in detecting chemical
compositions (using EDS), crystalline structure, and crystal orientations in a
qualitative or semi-quantitative manner (using EBSD). The SEM and EPMA have a
lot in common in terms of function and design, and the two instruments' capabilities
are highly overlapping.

Figure 8:- Scanning Electron Microscopy Machine

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CHAPTER 4

RESULTS AND DISCUSSION

4.1 Surface Properties

Figure 9:- AFM image of Zn Dip Coated Figure 10:- AFM image of Zn Dip
Coated

Figure 11:- AFM image of Zn sputtered

Figure 12:- 3-D AFM of Zn+PTFE+Ag

The Structure in figure 9 and figure 10 shows low roughness (small spikes) surface
where it can be inferred the degree of uniform deposition is high average spike height
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is < 0.1 um. The abrupt solvents evaporation allowed structural relaxation which
resulted in a relative uniform and smooth film. The levelled structure like nature
indicates positive relation with hydrophilicity for Zinc oxide + PTFE + Silver film.
The Needle like structure in figure 10, figure 11 indicate the Hydrophobic nature of
ZnO+PTFE+Ag film where it can be inferred the degree of uniform deposition is low,
resulting in pits and spike structure. The results show average spike heigh of 0.2 um
i.e., 200nm. This Needle like nature indicate positive relation with hydrophobicity for
Zinc oxide which full fills the intended function. The roughness average (Ra)
calculated was 1.852 nm and root mean square roughness (Rq) was 2.204 nm.

4.2 EDX Result Analysis

The EDX results (figure 7) provide clear evidence of deposition of Zinc Oxide, PTFE
and Silver on Soda-Lime glass along with minute impurities like Sn, Al and Mg
possible reason can be in glass manufacturing process our sample preparation. Zn is
present with a weight proportional of 48.98% (figure 13). The elemental mapping on
zinc in Figure 10 shows the uniform distribution of zinc throughout the scanned region.
The resulted thin film thickness is 1.2 micro-meter. PTFE is present with a weight
proportional of 29.30% and Silver has a weight proportional of 1.16%. The elemental
mapping of PTFE + Silver in Figure shows the uniform distribution throughout the
scanned region. The resulted thin film thickness is estimated to be between 600 nm.
The elemental mapping of PTFE in Figure 16 and Silver in Figure 17 shows the
uniform distribution throughout the scanned region.

Figure 13:- Graphical representation of Elements

 P a g e | 27

Figure 14:- Elemental Table Figure 15:- Elemental

Mapping Zn

Figure 16:- Elemental Mapping of a) Carbon and b) Flourine

Figure 17:- Elemental Mapping of Silver

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4.3 Wettability Angle test

Which state in this case has a minimum surface free energy determines whether a water
droplet stably exists in Wenzel state or Cassie-Baxter state. If a Wenzel drop forms, it
completely moistens the rough surface. In a dual-size-rough structure, when the
surface only possesses micron-level roughness, the nano-scale protruding’s increase
the actual contact area, increasing the roughness factor value.

The computed CA value rises when the roughness factor is increased, according to the
Wenzel equation. The surface with organised nano-spheres in the shape of protruding
micron papillae plainly gives a larger surface area in a three-dimensional manner,
which increases the value of roughness factor, in a similar manner to the surface on
which the silica nano-spheres were randomly deposited, thus that the CA on the surface
with dual-size roughness is higher than it is on the surface with only nano-level
roughness. A solid protuberance and air combine to form a composite surface on which
a Cassie-Baxter drop rests.

The high CA is caused by a significant replacement of liquid-solid interface by liquid-

gas interface. It goes without saying that surfaces with two levels of roughness trap
more air fractions than those with only one. Along with surface structure, the impact
of surface chemistry on CA must also be taken into consideration. Often, coating with
low-surface-energy materials like FAS is required to achieve super-hydrophobic
surfaces. If no low-free-energy compounds are applied to silica sphere-based surfaces
with dual-size roughness, they are not extremely hydrophobic.

The WCA angle is found to be 92.4 degrees which indicate the coating is hydrophobic.
This also mean that the structural state of coating is in Wenzel state where a drop
falling in coating will form a semi-round shape and will tend to fall of the surface with
 P a g e | 29

interacting with the lower substrate. This semi-round drop makes an angle of greater
than 90 degrees with the surface coating.[2]

Figure 18:- Wettability Contact Angle Test

4.4 Water drop Test

The water drop test is a visible test for the naked to see the result of hydrophobic
coating resisting the water drop from settling on its surface. The water is dropped from
the dropper unto the coating surface and water falls of in form of drops rather than
smearing and settling on the surface.

Figure 19:- Water Droplet on sample surface

 P a g e | 30

CHAPTER 5

CONCLUSION

By using the sol-gel method and magnetron sputtering method we fabricated a Zinc
oxide layer of 1200 nm and when compared to each other magnetron sputtering was
shown to have a more uniform deposition, transparent and higher adhesive properties.
The second layer was deposited using co-sputtering which had Teflon (PTFE) and
silver (Ag) with a combined thickness of 600 nm. This allowed for the of a thin film
with the physical mechanism of dual scale roughness.

The thin film fabricated now had a micro-layer of hydrophobic Zinc Oxide and a nano-
layer of super-hydrophobic Teflon and anti-microbial silver. The thin film was seen to
have a WCA test angle of 92.4 degrees which shows the hydrophobic Wenzel state
which state allows for water droplet to be held close leading to interaction with the
surface and taking with it the impurities that has been accumulated on the surface. The
is due to the rounded and uniform height of the peaks which is seen in the AFM results
which shows a very low amount of roughness present on the surface of the thin films.

Overall, the choice of elements in in line with the more chemical stability as Teflon is
highly chemically stable in environment. Addition of silver is to increase coating
resistance to microbial species. Silver atom doped inside the Teflon chain provide a
environment where silver nanoparticles coming in contact with bacteria will result in
silver nanoparticles penetrating their cell walls and changing the structur e of cell
membrane resulting in the death of cells.
 P a g e | 31

CHAPTER 6

FUTURE SCOPE
6.1 Corrosion Resistance
Increase the resistance to corrosion. Corrosion is known to be one of the most
important problems in our societies. Since this happens a lot and does a lot of damage,
people are interested in making surfaces more resistant to corrosion. Several ways have
been used to stop or slow the rate of corrosion on surfaces. But recently,
superhydrophobic coatings have been made to stop corrosion on all metals, including
aluminium, copper, steel, and zinc.[16], [17]

6.2 Anti-Icing Surface

When ice forms on surfaces that are exposed to the environment, it can make it hard
for many things to work, like highways, planes, ships, and communications equipment.
Many of the ways to solve this problem involve getting rid of the ice in its physical or
chemical form, which is hard and takes a lot of energy. Recently, the problem has been
fixed by putting SHS on aluminium substrates. Because SHS have such unique
properties, they can stop ice from forming and building up on surfaces.[18][19]

Figure 20:- Surface Comparison

6.3 Oil and Water Separation

Because there is more oil in industrial water, separating oil from water has become one
of the world's biggest problems. To separate oil and water, you can use a combination
of superhydrophobic and superoleophilic, superhydrophilic and superoleophobic
under water, or superhydrophilic and superoleophobic. Several materials, such as
membranes, tissues, foams, and sorbents, have been made to separate water and oil by
using different methods.[20][21]
 P a g e | 32

Figure 21:- Hydrophobic and Hydrophilic surface reaction to oil

6.4 Drag Resistance

Drag is one of the biggest problems that planes, submarines, and ships have to deal
with. We can learn a lot from nature about how to reduce and improve drag value.
Methods for making coatings that reduce drag are basically based on the leaves of the
lotus plant. At the SHS, the water-repellent properties can help reduce drag. When
water hits the surface, a gas film forms between the water and the surface, which makes
it less likely that water will touch the solid substrate.[22]

Figure 22:- Strip Size Expansion Test

 P a g e | 33

6.5 Batteries Manufacture Technology

Due to the low capacity and short life of batteries, battery manufacturing technology
is one of the most important areas of research in electronics.
Figure 19 is a diagram of how superhydrophobic surfaces are used in important ways.
batteries to keep up with the progress made in semiconductor technology. When it can
hold its charge for a long time, a battery may be able to give off the right amount of
power and work well enough. In most batteries, the electrolyte and electrode are
separated by a simple mechanical separator. This makes batteries bigger than they need
to be.[23]

Figure 23:- Hydrophobic surface

As Separator

6.6 Sensors
Because of how they are made, superhydrophobic films can interact with different
materials in liquid and gas media in different ways. Also, because they are rough,
sensors with superhydrophobic properties are very accurate. In many cases, this aspect
was looked into. Saito et al. used a superhydrophobic quartz crystal balance to find
volatile organic compounds, for example. By adding a superhydrophobic CVD coating
to SHS made of trimethylmethoxysilane, the weight of a number of organic substances
like toluene and formaldehyde goes up. Other research groups have also looked into
SHS made by mixing carbon dioxide with amine agents. In metallic nanostructures,
coherent fluctuations in the conduction band of electrons can cause extreme plasmon
resonance in the local electromagnetic field. This effect, called surface enhanced
raman scattering (SERC), is used to find metallic particles in a solution. Scientists
studied the effect of increasing SERS in SHS made of ZnO nanobars coated with silver
nanoparticles. It was seen that the signal got three times stronger than on a normal
surface.[24][25]
 P a g e | 34

Figure 24:- Silver Nano-particles on Hydrophobic surface for sensor

development

People know that most biological systems have complicated bonds, like specific
hydrogen bonds. For example, the interaction between proteins and carbohydrates is a
big problem in many important biological processes, such as signalling, recognising,
and breaking down. On the other hand, it is very important for medicine, diagnosis,
and treatment to develop sensors based on carbohydrate testing. Lee et al. reported that
it is possible to get SHS with variable wettability when saccharide is present. N-
isopropylacrylamide and a phenyl acid derivative made up the co-polymer that was
used. The micro and nanostructures became superhydrophobic because of
polymerization. When the polymer was put in glucose, its super hydrophobicity
changed to super hydrophobicity because of how the polymer and glucose interacted.
A lot of research has been done on how superhydrophobic surfaces can help improve
the performance of different types of sensors. [26][27]
 P a g e | 35

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