SYNTHESIS OF HOLLOW SILICA NANOPARTICLES AND

THEIR STRUCTURE CONTROL FOR OPTICAL PROPERTIES

中空シリカナノ粒子の合成および光学特性付与に向けた構造制御

WALAIPORN SUTHABANDITPONG

ワライポン スタバンディトポン

DOCTOR OF PHILOSOPHY DISSERTATION

FRONTIER MATERIALS

MARCH 2016

NAGOYA INSTITUTE OF TECHNOLOGY

JAPAN
 SYNTHESIS OF HOLLOW SILICA NANOPARTICLES AND

THEIR STRUCTURE CONTROL FOR OPTICAL PROPERTIES

中空シリカナノ粒子の合成および光学特性付与に向けた構造制御

WALAIPORN SUTHABANDITPONG

ワライポン スタバンディトポン

DOCTOR OF ENGINEERING

FRONTIER MATERIALS

NAGOYA INSTITUTE OF TECHNOLOGY

JAPAN

MARCH 2016
 SYNTHESIS OF HOLLOW SILICA NANOPARTICLES AND

THEIR STRUCTURE CONTROL FOR OPTICAL PROPERTIES

中空シリカナノ粒子の合成および光学特性付与に向けた構造制御

WALAIPORN SUTHABANDITPONG

ワライポン スタバンディトポン

23513314

RECOMMENDED FOR ACCEPTANCE

A DISSERTATION SUBMITTED IN PARTIAL FULFILLMENT OF

MARCH 2016
© Copyright by Walaiporn Suthabanditpong 2016.

All Rights Reserved

Silica nanoparticles have many interesting properties; for example, a high surface

area, high mechanical strength, thermal and chemical stability, permeability, and a low

refractive index and especially optical properties. Therefore, these particles are

effectively applied for fillers in light diffuser films as type of volumetric diffuser. The

light diffuser film is an important part of backlight unit of the liquid crystal display

(LCD). The film generally employs fillers as function of distributing the incident light

and contributing the brightness. Therefore, structure of fillers is one of the main roles

for improving performance of light diffuser films. For this reason, hollow structures of

silica nanoparticles have shown a great promise to reduce light absorption of them in

the diffuser films. Meanwhile, morphologies and surface properties of hollow silica

nanoparticles probably affect the formation of good light diffuser film, which requires

for LCDs. According to the assumptions, this work is only used of different structures of

silica nanoparticles to fabricate, investigate, develop and innovative approach in

producing films with high optical properties which are applied for light diffuser film.

All films in the study are fabricated by a bar coating machine and cured by a UV-photo

surface processor. The study is mainly organized as follows

Chapter 1 introduces general background of silica especially silica nanoparticles

and hollow silica nanoparticles. It mainly focuses on optical properties of the particles

to apply for fabricating light diffuser films. Meanwhile, the important of a light diffuser

film in backlight unit of LCDs is briefly introduced. Moreover, light scattering

involving optical properties of particles in the films is described. Based on the attempt

to fabricate light diffuser films with varying morphologies of silica in nanoscale and

I
simplify the coating process, the goal of this study is conceptualized.

Chapter 2 describes a facile method to prepare the highly loaded silica dispersions.

The method was the matching refractive indices of the silica nanoparticles and a UV-

curable acrylate monomer. The obtained dispersions exhibit a long-term stability of

silica dispersions during dark storage. This is due to the reduction of particle-particle

attraction forces. Such dispersions were further coated on cleaned glass substrates for

fabricating the thin solid silica UV-cured films. The amount of silica nanoparticles in

the films was varied from 1 to 30 vol %. The coated films were investigated their

optical properties by a UV-Vis-NIR spectrophotometer. The total transmittances of the

films are close to the bare glass which indicates the films transparency. The increment

of silica nanoparticles in the films does not significantly affect their transmittances but it

improves the diffuse transmittance. The reasonable explanation is an enhancement of

the multiple scattering in the films through the particles. The increased amount of silica

nanoparticles also leads to the formation of the aggregated particles with a larger size

and homogeneous dispersion as evidenced from the FE-SEM images. Remarkably, the

thin solid silica film containing 30 vol% silica nanoparticles exhibits the highest diffuse

transmittance in this experiment, which is about 20%. These indicated that the amount

and distribution of the silica nanoparticles strongly affect the improved optical

properties of the thin solid silica UV-cured film.

Chapter 3 applies spherical silica nanoparticles containing dense structures to

modify UV-cured acrylate films. The films were prepared by coating suspension of

silica-acrylate on cleaned glass substrates. The effect of the particle content on the

optical properties of the modified films was investigated. The light diffusing ability of

the films was also studied using an apparatus equipped with a laser lamp. Based on the

II
visible absorption data, the transmittance of all modified films coated substrates is lower

than that of the unmodified film. The transmittance of the modified films decreases with

the increasing silica content. The increasing silica content also improves the haze and

light diffusing ability of the modified films. The highest haze of about 0.26 and the

largest range of scattered light were achieved using the film modified with 30 vol%

particles. These nanoparticles show a good potential to improve the optical properties of

the UV-cured acrylate film, especially the light diffusing property that may be utilized

in electronic display technologies.

Chapter 4 uses silica nanoparticles containing hollow structures to improve optical

properties and light diffusing ability of UV-cured acrylate film. The hollow particles

calcined at temperature of 400 °C were dispersed in a UV-curable acrylate monomer

solution. The obtained dispersion was then coated on a cleaned glass substrate. The

amount of the particles in the coated films was varied from 5 to 20 vol%. The optical

properties and the light diffusing ability of the films were studied and then compared to

those of the cleaned glass. As a result, the films become opaque when the amount of the

particles increases. Although the opacity of the films was observed, the total

transmittance of those was still high and close to that of cleaned glass substrate.

Interestingly, a film based on 20 vol% hollow silica nanoparticles gives the highest total

transmittance (93%) and diffuse transmittance (40%) when comparing to other films in

this experiment. Meanwhile, the increased amount of the particles leads to the formation

of aggregated particles with a larger size and homogenous dispersion as evidenced from

the FE-SEM images. It also improves the optical properties of the films; for instance,

diffuse transmittance and light diffusing ability. According to these results in the study,

it can be concluded that the films based on the hollow silica nanoparticles as fillers have

III
potentially in application as light diffuser films in the LCD industry.

Chapter 5 controls the morphologies and surface properties of hollow silica

nanoparticles with varying pH of HCl in the core-template removal process. The

obtained particles were then dispersed in a UV-curable acrylate monomer. The

dispersions containing different hollow particles were employed to fabricate silica/UV-

cured polymer composite films. The high pH of HCl produces the thinner shell and

larger window cavities of the hollow silica nanoparticles. Moreover, it provides the

higher specific surface area of those. Meanwhile, the film embedded with hollow silica

nanoparticles, which contain larger size of hollow interiors, thinner shells, larger

window cavities and high specific surface area, exhibits higher total transmittance

(∼80%), higher diffuse transmittance (∼80%) and better light diffusing ability when

comparing to other composite films. Its properties still maintain at longer wavelength.

Therefore, the distinct morphologies and surface properties of the hollow silica

nanoparticles significantly affect the optical properties and the morphologies of the

resulting films. In addition, the hollow silica nanoparticles with hierarchical structures

are one of the effective inorganic fillers for light diffuser films which probably reduce

the number of backlight unit in the LCD industry leading to energy saving and

subsequently light-weight LCD screens.

Finally, Chapter 6 presents the overall concluding remarks of the present work and

the directions for the future research. The techniques presented in all studies of this

dissertation provide an informative foundation for the structures of silica nanoparticles,

which affect optical properties of silica films. It is a template and a saving energy

approach for the various future applications in the field of optical materials, especially

light diffuser films for backlight unit in the LCD industry.

IV
 TABLE OF CONTENTS

LIST OF FIGURES ....................................................................................................X

LIST OF TABLES ................................................................................................... XV

NOMENCLATURES ..............................................................................................XVI

CHAPTER 1 GENERAL INTRODUCTION

1.1 Silica .................................................................................................................. 3

1.1.1 Silica nanoparticles ................................................................................... 4

1.1.2 Hollow silica nanoparticles ....................................................................... 5

1.2 Light diffuser film .............................................................................................. 6

1.3 Light scattering .................................................................................................10

1.3.1 Rayleigh scattering ..................................................................................10

1.3.2 Mie scattering ..........................................................................................12

1.4 Objective of this work and thesis organization ...................................................13

References .................................................................................................................15

CHAPTER 2 PREPARATION OF HIGHLY LOADED SILICA

NANOPARTICLE DISPERSIONS BY MATCHING

REFRACTIVE INDICES OF THE SILICA AND A

BINDER RESIN FOR FABRICATING SILICA FILMS

WITH HIGH OPTICAL PROPERTIES

2.1. Introduction ......................................................................................................25

2.2. Experimental procedures ...................................................................................30

2.2.1 Materials ..................................................................................................30

V
 2.2.2 Instrumentation ........................................................................................32

2.2.3 Preparation of silica UV-curable acrylate monomer dispersion ................33

2.2.4 Fabrication of thin solid silica UV-cured films on glass substrate .............35

2.3 Results and Discussion......................................................................................36

2.3.1 Physical properties of silica UV-curable acrylate monomer

dispersion ................................................................................................36

2.3.2 The optical properties of the thin solid silica UV-cured films ...................42

2.3.2.1 Optical transmittance of the thin solid silica UV-cured

films ...........................................................................................42

2.3.2.2 Diffuse transmittance of the thin solid silica UV-cured

films ...........................................................................................45

2.3.2.3 Morphology of the thin solid silica UV-cured films ....................48

2.4 Conclusion ........................................................................................................50

References .................................................................................................................51

CHAPTER 3 MODIFICATION OF UV-CURED ACRYLATE FILMS

BY SPHERICAL SILICA NANOPARTICLES FOR

IMPROVING THEIR LIGHT DIFFSUING ABILITY

3.1 Introduction ......................................................................................................58

3.2 Experimental procedures ...................................................................................59

3.2.1 Materials ..................................................................................................59

3.2.2 Fabrication of UV-cured acrylate films modified with

spherical silica nanoparticles ....................................................................60

3.2.3 Characterization .......................................................................................60

VI
3.3 Results and Discussion......................................................................................63

3.3.1 Morphologies of UV-cured acrylate films modified with

spherical silica nanoparticles ....................................................................63

3.3.2 Optical properties of UV-cured acrylate films modified with

spherical silica nanoparticles ....................................................................69

3.4 Conclusion ........................................................................................................76

References .................................................................................................................76

CHAPTER 4 CHARACTERIZATION OF HOLLOW SILICA

NANOPARTICLES AND THEIR APPLICATION IN

LIGHT DIFFUSER FILMS

4.1 Introduction ......................................................................................................82

4.2 Characterization of HSiNPs ..............................................................................84

4.2.1 Thermogravimetric analysis of HSiNPs ...................................................84

4.2.2 Morphologies of HSiNPs .........................................................................85

4.2.3 Density of HSiNPs ...................................................................................87

4.3 Experimental procedures ...................................................................................89

4.3.1 Facile fabrication of optical diffuser films with HSiNPs ...........................89

4.3.2 Characterization of optical diffuser films with HSiNPs ............................90

4.4 Results and Discussion......................................................................................91

4.4.1 Morphologies of the light diffuser films based on the HSiNPs

as fillers ...................................................................................................91

4.4.2 Optical properties of the optical diffuser films with the HSiNPs ...............94

VII
 4.4.2.1 Total transmittance of the light diffuser films based on

the HSiNPs as fillers ..................................................................94

4.4.2.2 Diffuse transmittance of the light diffuser films based on

the HSiNPs as fillers ..................................................................95

4.4.2.3 Light diffusing ability of the light diffuser films based on

the HSiNPs as fillers ..................................................................97

4.5 Conclusion ......................................................................................................100

References ...............................................................................................................101

CHAPTER 5 CONTROLLING STRUCTURE OF HOLLOW SILICA

NANOPARTICLES THROUGH CORE-TEMPLATE

REMOVAL PROCESS WITH ACID AND APPLYING

THEIR STRUCTURE FOR LIGHT DIFFUSER FILMS

5.1 Introduction ....................................................................................................108

5.2 Experimental procedures ................................................................................. 111

5.2.1 Materials ................................................................................................ 111

5.2.2 Synthesis of hollow silica nanoparticles ................................................. 112

5.2.3 Fabrication of silica/UV-cured polymer composite films........................ 113

5.2.4 Characterization ..................................................................................... 114

5.3 Results and Discussion.................................................................................... 115

5.3.1 Morphologies and surface properties of hollow silica

nanoparticles .......................................................................................... 115

5.3.2 Optical properties and morphologies of the silica/UV-cured

polymer composite films ........................................................................123

VIII
 5.3.2.1 Optical properties of the silica/UV-cured polymer

composite films ........................................................................123

5.3.2.2 Morphologies of the silica/UV-cured polymer composite

films .........................................................................................133

5.4 Conclusion ......................................................................................................136

References ...............................................................................................................137

CHAPTER 6 CONCLUDING REMARKS AND POTENTIAL

DIRECTION FOR FUTURE RESEARCH

6.1 Concluding remarks .................................................................................144

6.2 Potential directions for future research .....................................................147

RESEARCH ACTIVITIES....................................................................................148

ACKNOWLEDGEMENTS ........................................................................................

IX
 LIST OF FIGURES

CHAPTER 1

Fig. 1.1 Interaction of light and silica with:

(a) dense structure and (b) hollow structure ............................................ 5

Fig. 1.2 Typical configuration of the backlight unit .............................................. 7

Fig. 1.2 Rayleigh scattering from air molecules .................................................. 11

Fig. 1.3 Schematic diagram of the direction of light scattering based on

Mie scattering ........................................................................................12

CHAPTER 2

Fig. 2.1 Chemical formulas of the compounds used ............................................31

Fig. 2.2 FE-SEM image of the SiNPs as received ...............................................31

Fig. 2.3 Refractive indices of the modified UV-curable acrylate monomers

for different amounts of SiNPs ..............................................................37

Fig. 2.4 Stability of silica UV-curable acrylate monomer dispersions

at different times such as (a) 0 h, (b) 1 h and (c) 24 h .............................38

Fig. 2.5 Influence of silica loading on the viscosity.............................................40

Fig. 2.6 The cumulative size distributions curve of SiNPs

dispersed in 20 wt% UV-curable acrylate monomer ..............................41

Fig. 2.7 Comparison of thicknesses of wet and dry films

with different SiNPs contents.................................................................43

Fig. 2.8 Total transmittance of the modified UV-cured films with SiNPs

coated on glass substrate ........................................................................44

X
Fig. 2.9 Influence of silica quantity on the diffuse transmittance spectra

of the thin solid silica UV-cured film coated on glass substrate .............46

Fig. 2.10 FE-SEM surface image of the silica UV-cured film with

different amounts of SiNPs (a) 5 vol%, (b) 10 vol%, (c) 20 vol%

and (d) 30 vol%..........................................................................................48

CHAPTER 3

Fig. 3.1 Schematic illustration of the apparatus for achieving

a scattered light image ...........................................................................62

Fig. 3.2 Influence of silica content on the film thickness .....................................63

Fig. 3.3 CLSM images of the UV-cured acrylate films modified with

the SSiNPs.............................................................................................65

Fig. 3.4 FE-SEM images of the UV-cured acrylate films modified with

various amounts of SSiNPs: (a) 5 vol%, (b) 10 vol%,

(c) 20 vol% and (d) 30 vol% ..................................................................67

Fig. 3.5 FE-SEM image of the SSiNPs as received .............................................68

Fig. 3.6 Transmittance spectra of all films coated on the glass substrate..............70

Fig. 3.7 Haze value of the UV-cured acrylate films modified

with various silica contents ....................................................................72

Fig. 3.8 The scattered light images of the UV-cured acrylate films

containing various silica contents such as

(a) 0 vol% (UV-cured acrylate film), (b) 1 vol%,

(c) 5 vol%, (d) 10 vol%, (e) 20 vol% and (f) 30 vol% ............................74

XI
CHAPTER 4

Fig. 4.1 TGA curve of the raw HSiNPs ...............................................................84

Fig. 4.2 FE-SEM images obtained from SEI and TED modes of HSiNPs

before calcination for (a) and (d) and after calcination at

temperature of 400 °C for (b) and (e), including to

at temperature of 600 °C for (d) and (f) ..................................................86

Fig. 4.3 Optical images of the light diffuser films containing different

amounts of the HSiNPs such as (a) 5 vol%, (b) 10 vol%,

(c) 15 vol% and (d) 20 vol% ..................................................................91

Fig. 4.4 FE-SEM images with (inset) high magnification of the light

diffuser films containing different amounts of the HSiNPs

such as (a) 5 vol%, (b) 10 vol%, (c) 15 vol% and (d) 20 vol% ...............92

Fig. 4.5 Total transmittance spectra of the cleaned glass (a) and the light

diffuser films containing different amounts of the HSiNPs

such as (b) 5 vol%, (c) 10 vol%, (d) 15 vol% and (e) 20 vol% ...............94

Fig. 4.6 Diffuse transmittance spectra of the cleaned glass (a) and the

light diffuser films containing different amounts of the HSiNPs

such as (b) 5 vol%, (c) 10 vol%, (d) 15 vol% and (e) 20 vol% ...............96

Fig. 4.7 The scattered light images of the cleaned glass (a) and the light

diffuser films containing different amounts of the HSiNPs

such as (b) 5 vol%, (c) 10 vol%, (d) 15 vol% and (e) 20 vol% ...............98

Fig. 4.8 Schematic illustration of applying the light diffuser film

based on the HSiNPs as fillers in the LCD ...........................................100

XII
CHAPTER 5

Fig. 5.1 Schematic illustration of light scattering occurred by

(a) dense particles and (b) hollow particles ..........................................109

Fig. 5.2 FE-SEM image of the raw CaCO 3 nanoparticles.................................. 111

Fig. 5.3 XRD patterns of (a) raw CaCO 3 nanoparticles, (b) HSiNPs-1,

(c) HSiNPs-2 and (d) HSiNPs-5........................................................... 116

Fig. 5.4 FE-SEM images of (a) HSiNPs-1, (b) HSiNPs-2 and

(c) HSiNPs-5 and their TEM images as following shown in

(d), (e) and (f) ...................................................................................... 117

Fig. 5.5 Schematic illustration of silica growth around CaCO 3

core-template at pH of (a) 1, (b) 2 and (c) 5 ......................................... 119

Fig. 5.6 N 2-adsorption isotherm with (inset) pore size distribution of

(a) HSiNPs-1, (b) HSiNPs-2 and (c) HSiNPs-5 ....................................121

Fig. 5.7 Total transmittance spectra of the UV-cured polymer film (a)

and the silica/UV-cured polymer composite films embedded

with (b) HSiNPs-1, (c) HSiNPs-2 and (d) HSiNPs-5 ............................123

Fig. 5.8 The cumulative size distribution pattern of the HSiNPs

in UV-curable acrylate monomer dispersions prepared by

(a) HSiNPs-1, (b) HSiNPs-2 and (c) HSiNPs-5 ....................................125

Fig. 5.9 Diffuse transmittance of the UV-cured polymer film (a)

and the silica/UV-cured polymer composite films embedded

with (b) HSiNPs-1, (c) HSiNPs-2 and (d) HSiNPs-5. ...........................127

XIII
Fig. 5.10 The scattered light image of the UV-cured polymer film (a)

and the silica/UV-cured polymer composite films embedded

with (b) HSiNPs-1, (c) HSiNPs-2 and (d) HSiNPs-5 ............................130

Fig. 5.11 schematic illustration of utilizing the hollow silica nanoparticles

to be fillers in light diffuser films in the LCD ......................................132

Fig. 5.12 The FE-SEM images of the UV-cured polymer film embedded

with (a) HSiNPs-1, (b) HSiNPs-2 and (c) HSiNPs-5. ...........................134

XIV
 LIST OF TABLES

CHAPTER 1

Table 1.1 General properties of fused silica ............................................................ 3

CHAPTER 2

Table 2.1 Amount of SiNPs in the dispersion and in the thin solid silica

UV-cured film .......................................................................................34

CHAPTER 4

Table 4.1 Densities of HSiNPs before and after calcination ...................................88

Table 4.2 Amount of the calcined HSiNPs in light diffuser films ...........................89

XV
 NOMENCLATURES

BET Brunauer-Emmett-Teller method

BJH Bareett-Joyner-Halenda method

CLSM Confocal Laser Scanning Microscope

DLS Dynamic Light Scattering

FE-SEM Field Emission Scanning Electron Microscope

HSiNPs Hollow silica nanoparticles

SiNPs Silica nanoparticles

SSiNPs Spherical silica nanoparticles

LCD Liquid Crystal Display

TEM Transmission Electron Microscope

TGA Thermogravimetric analysis

UV-Vis UV-Vis spectrophotometer

XRD X-Ray Diffraction

XVI
 CHAPTER 1

GENERAL INTRODUCTION

1
 Nowadays, nanotechnology is extensively applied for various major scientific and

technological fields; for example, electronic, medication, environment, agriculture, and

energy [1-3]. This involvement includes the structure of particles on the nanometer

scale. The nanoparticles often exhibit novel physical, chemical, biological and other

properties, which are different from individual atoms and bulk samples of the same

material. Therefore, nanoparticles are one of the new tasks to develop new classes of

advanced materials for supporting future technologies.

The variety of inorganic nanoparticles including silica, silicon nitride, silicon

carbide, alumina, titania, zinc oxide and etc., have been extensively applied for diverse

electronics to enhance mechanical, thermal, electrical and optical properties, and new

functionality [4-7]. Among these nanoparticles, silica nanoparticles are much

attractively considered as fillers in light diffuser films of backlight unit in the liquid

crystal display (LCD) industry [8, 9]. This is due to their good light transmittance and

diffusion capacity. While the structure of silica nanoparticles is one of the important

factors for achieving high optical properties of light diffuser films which is suitable for

the LCD industry. With these reasons, this study had mainly focused on the synthesis

hollow silica nanoparticles and their structure control for optical properties.

In this chapter, general properties of silica and light diffuser films are basically

introduced. Until now many researchers have reviewed or published the synthesis,

properties and applications in the LCD industry of silica. The work has briefly reviewed

some recent developments in preparation, and properties of silica nanoparticles and

hollow silica nanoparticles, including application of them for light diffuser films.

2
1.1 Silica

Silica, also known as silicon dioxide (SiO 2 ), is a chemical compound of the two

most abundant elements in the Earth’s crust, which are silicon and oxygen [10]. Its

appearance is both in the form of an amorphous and a variety of crystalline. There are

three main crystalline forms of silica; for instance, quartz, tridymite and cristobalite.

Silica with a high purity grade is called as fused silica and is primarily used in the

electronic industry [1, 11-13]. It is also applied as a refractory material and a substance

in casting industry. This is due to its properties that are very high refractive index, good

electric insulation, thermal stability and abrasion resistance. Some general properties of

fused silica are shown in the table below [10].

Table 1.1 General properties of fused silica

Properties

Density (g/cm3) 2.2

Thermal conductivity (Wm-1 K) 1.4

Melting point (°C) 1600

Some of its properties are usually size dependent because a number of atoms

residing on silica surface will increase while the particle size of silica will decrease [14].

When the size is smaller than 5 nm, more than half of the Si atoms are present on the

surface [15]. Therefore, the surface should have one or more silanol groups (≡Si-OH)

leading to increase silanol groups per grams of silica. The number of silanol groups is

interrelated to the specific surface area of silica. According to these reasons, the

3
decrease in the nano-sized silica probably provides distinctive properties, which are

different from its basic properties. Meanwhile, morphologies of silica nanoparticles are

also controlled to tune them for diverse applications.

1.1.1 Silica nanoparticles

Silica nanoparticles have many interesting properties, including a high surface area,

high mechanical strength, thermal and chemical stability, permeability, and a relatively

low refractive index [1-3, 12, 16-18]. They also contain unique features: low light

absorption in the ultraviolet-visible (UV-vis) and near-infrared (NIR) regions, dielectric

electrons, and low toxicity. Therefore, the nanoparticles are of great interest to various

applications in many major chemical fields; for example, electronic, optic, sensing,

insulating, sorption, separation, catalysis, solar cell and medication. One of the

prominent applications of silica nanoparticles is filler or reinforcement in advanced

composite materials [1]. The most important feature of silica-polymer nanocomposite is

the ability to attain homogeneous filler dispersion, which affects the overall

performance of the nanocomposite. The type of used polymer matrix is also one of the

main roles for the performance of a nanocomposite. Recently, many approaches have

been developed for preparing silica-polymer nanocomposite for wide applications in

adhesion, biomaterial, protective coatings, microelectronics, optical materials, and

especially light diffuser films [19- 30]. The incorporation of silica nanoparticles in

polymer films not only enhances mechanical properties of the film but also reduce its

thermal degradation at high temperature [31]. Furthermore, it can improve insulation

properties of the film.

4
1.1.2 Hollow silica nanoparticles

Hollow silica nanoparticles compose of hollow interiors and solid shells [32]. The

hollow interiors act as storage basin or micro-reactor while the solid shells provide

controlled release pathways or substantial reaction [33]. According to their advanced

structures, these nanoparticles have a great promise for various applications such as

adsorbents, delivery carriers, catalysts, biomedical detectors, building blocks for

photonic crystals, and optical displays [34-36]. Moreover, silica containing a hollow

structure probably allows light penetration through it hollow interior that result in a

lower light absorption as compared to silica with a dense structure. This can be

illustrated by Fig. 1.1.

Fig. 1.1 Interaction of light and silica with: (a) dense structure and (b) hollow structure.

Moreover, the light is nonspecifically adsorbed by pore on a solid shell of silica and

may occur light scattering and refraction latterly [36]. This is due to the difference

refractive index between the air in the hollow interior and the solid shell. Therefore,

large hollow interiors of hollow silica nanoparticles are probably required for light

5
penetration and scattering. Meanwhile, thinner shells of the hollow silica nanoparticles

are necessary for low light absorption and more light refraction. These can improve

optical properties of the hollow silica nanoparticles and subsequently provide advanced

functional materials. The design of shell structures of hollow silica nanoparticles,

including diameter, shape, thickness, surface roughness, morphology, and pore size, is

precisely controlled by numerous synthesis processes. Therefore, many approaches have

been exploited to synthesize hollow silica nanoparticles with respect to meso-structure

shells, which exhibit unique properties of both macroporous and mesoporous structures

in one single piece [33]. The well-known approaches are sol-gel and template methods

[32, 33]. The template method can be typically divided into two types; for example,

hard (e.g. polymer, silica or carbon spheres) [37-40] and soft templates (e.g. micelles or

vesicles) [41, 42]. Comparing to sol-gel method, the template method has attracted

much attention because the diameter and shape of hollow silica nanoparticles are simply

controlled by those of used templates [43-46]. It can also design shell thickness of the

hollow silica nanoparticles by ratio of silica source and template, reaction time, and etc

[47, 48]. Therefore, both hollow interior size and shell thickness of hollow silica

nanoparticles being two independent variables in optical designs of the optical displays

can be tuned by the essible choices from the template method.

1.2 Light diffuser film

A light diffuser film or plate, also known as optical diffuser, plays key optical

component in backlight unit of various LCD devices, such as TVs, overhead projectors,

handheld game consoles, and mobile phones [30, 49-52]. The backlight unit supply light

6
to LCD panels since they cannot emit the light themselves [50]. A typical configuration

of the backlight unit comprises of a light emitter (usually cold cathode fluorescent

lamps (CCFLs) or a light-emitting diode (LED) matrix), a light guide plate (LGP), a

reflection film, one/two diffuser film(s) and one/two brightness enhancement film(s)

(BEFs) [50, 53, 54]. All those mentioned components are shown in Fig. 1.2. The light

diffuser film has a function of scattering and homogenizing the incident light from

sources over a wide angle. As a result, the images are suitable and wide view-angle

images to displays [28-30].

Fig. 1.2 Typical configuration of the backlight unit [54].

Generally, there are two main types of light diffuser films that achieve the high

efficient light diffusers used in backlight unit of LCDs. The first type is surface-relief

diffuser film, which relies on microstructures of the surface layers to scatter light [49].

The second type is called volumetric diffuser film, which mainly depends on the

difference in refractive indices between light diffusing particles (LDPs) or fillers and

7
binding resin. The surface-relief diffuser film commonly contains higher light

transmittance than the volumetric diffuser film because of no light absorption by

particles. However, the most methods used for fabricating the microstructures on the

surface-relief, including microlens [55, 56], pyramids [57, 58], hemisphere [59] and

other microstructures [60, 61], require complicated processes using expensive

equipments [29, 30, 49, 50]. Since the volumetric diffuser film is not only fabricated by

a versatile method but also capable of distributing the incident light and contributing the

brightness in the viewing, this kind of diffuser film currently dominate the diffuser

market [50].

The volumetric diffuser film comprises of three major components which are light

diffusing particles (LDPs) or fillers, binding resin, and a transparent substrate [29, 50].

It is basically fabricated by coating a mixture of fillers and binder resin on a substrate.

After solvent evaporation, the surface of coating layer becomes rough due to the fillers

[62]. The surface roughness affects an outer haze while the difference in refractive

indices between the fillers and the binder resin has an influence on an inner haze. The

haze values are defined as the ratio between diffuse transmittance and total

transmittance (Haze = T diffuse/T total ). A summation of the outer haze and the inner haze

is total haze. This diffuser film is more possible to scatter and homogenize the incident

light from sources to avoid the occurrence of local concentrated light when either the

outer or the inner haze of the film increases. Accordingly, fillers have significantly

influence on optical performance and light diffusing ability of the film. Many efforts

have been developed on optical materials to fabricate volumetric diffuser films. One of

the dominant researches is the study of Wang et al [28] who worked on the fabrication

of volumetric diffuser films using silicone emulsions as a substrate and micro-scale

8
water drop as fillers. Another interesting study is from Guo et al [29] who presented

organic-inorganic hybrid materials as fillers to achieve good light diffusing film with

high both of transmittance and haze. The organic-inorganic fillers were prepared via the

electrostatic attraction between positively charged polymethyl methacrylate (PMMA)

spheres and negatively charged SiO 2 nanoparticles before blending with polyacrylate

latex to produce strawberry-like PMMA/SiO 2 composite microspheres. This previous

study is similar to the research of Hu et al [52] who also prepared the PMMA

microspheres incorporated with a small amount of inorganic nanoparticles to prepare

fillers used in multifunctional optical diffuser films. The multifunctional optical

diffusers based on hybrid polysiloxane@CeO 2 @PMMA microspheres were

successfully prepared by UV curing process. The hybrid microspheres improved

properties of the diffusers; for example, heat resistance, mechanical, UV-shielding,

fluorescence, well NIR absorption and anti-aging ability, which had a potential

application in absorbing materials and night vision LCD monitor products. Moreover,

Ahn and co-worker [30] used hemispherical PMMA as filler for fabricating an optical

diffuser with electrospray coating process. Meanwhile, Zhao et al [63] enhanced the

light diffusion property of polycarbonate composites by TiO 2 coated silicate micro-

spheres for light diffusion applications.

In addition, diverse applications of light diffuser films, Li et al [50] had conducted a

study of the correlations of optical properties of light diffuser films as functions of the

coating thickness/particle diameter ratio and beads/resin weight ratio. These correlations

were empirically developed as a power law model and an exponential model,

respectively. The developed correlations may effectively reduce the time required for

designing light diffuser films in the backlight unit. Moreover, the group of Mingyan et

9
al [64] presented a mathematical model of direct type LED backlight. The model was

the optimization and was designed as the micro-structures on the surface of the diffuser

plate, which were the critical factors in manufacturing diffuser plates of good optical

properties. Meanwhile, mechanical and thermal properties of light diffuser films are

essential for their application. The research works done by Sun et al [30] prepared nano-

silica reinforced hybrid light-diffusing films. The films prepared by light-diffusing

agent (organosilicone resin, KMP-590) and nano-silica exhibited the excellent optical,

thermal stability and mechanical properties, which might be suitable for anti-glare LED

application.

1.3 Light scattering

The nature of light interacted with fillers and important features in a light diffuser

film are governed by light scattering in the systems [65, 66]. Therefore, understanding

the occurrence of the light scattering is essential for developing and optimizing the cost

and performance of backlight unit in the LCD industry.

Light scattering is generally occurred when light passes through a material with

different refractive indices. Meanwhile, the difference between particle size and incident

light wavelength also produces the light scattering. Common aspects of light scattering

are basically discussed with the following subject headlines which are Rayleigh

scattering and Mie scattering.

1.3.1 Rayleigh scattering

Rayleigh scattering is named after the British physicist Lord Rayleigh (also known

as John William Strutt). This subject describes the dominant elastic scattering of light or

10
electromagnetic radiation which involves particles much smaller than the incident

wavelength [67]. The particles are individual atoms or molecules. Moreover, this type

of scattering occurs if light passes through a transparent solid and liquid. Remarkably,

the Rayleigh scattering is most seen in gases. The sample of Rayleigh scattering from

air molecules that causes of the blue sky. It can be illustrated in Fig. 1.3.

Fig 1.3 Rayleigh scattering from air molecules [29].

The Rayleigh scattering defines that light scattering depends on size of the particles

and wavelength of the incident light [29, 68]. The intensity of the scattering is inversely

proportional to the fourth power of the wavelength, which can be expressed by the

following formula

1
𝐼∝ (1.1)
λ4

From the above formula, I is an intensity of the light scattering and λ is wavelength of

the incident light. Accordingly, the intensity rapidly drops when the wavelength

increases or the particle diameter decreases.

11
1.3.2 Mie scattering

Mie scattering named after the German physicist Gustav Mie describes for light

scattering, which particle size is similar to or larger than a wavelength of the incident

light [29, 65, 66, 69]. Meanwhile, the intensity of Mie scattering is independent to the

particle size. Moreover, the direction of the light scattering is towards that of the

incident light as illustrated in Fig. 1.4.

Fig 1.4 Schematic diagram of the direction of light scattering

based on Mie scattering [29].

The Mie scattering is prominently of a single or isolated particle, which is called

single scattering or dependent scattering [70]. Since the single scattering is independent

of neighboring particles therefore the total scattering of a material embedded with

isolated particles is calculated by a summation of light scattering by each individual

particle. However, real particles in a film often approach another one. Therefore, the

light scattering of each particle or cluster, being known as dependent scattering or

multiple scattering, is dependent to the other ones. In the case of the multiple scattering,

each particle is more illuminated by both the incident light and the secondary scattering

than from other particles, as a result, the optical properties of the film increases. To

12
understand the complex of the light scattering in an actual film, many efforts have been

devoted to study on the multiple scattering based on Mie scattering. For example,

Kubelka and Munk further investigated the light scattering of the entire paint film

embedded with millions of millions of particles. They reported a simplified form of

multiple light scattering behaviors in aggregated particles, which will be widely applied

for semitransparent materials.

1.4 Objective of this work and thesis organization

The objective of this work is to develop novel and facile method to fabricate light

diffuser films with high optical properties using silica. Meanwhile, the effect of silica

structure on optical properties of the light diffuser films also involves in this study.

The dissertation is organized as follows:

In Chapter 2, the details on preparation of highly loaded silica nanoparticles

dispersions by matching refractive indices of silica nanoparticles and a binder resin for

fabricating silica films are given. The optical properties of the silica films were

analyzed. Based on the results, the effect of the silica loading on the optical properties

of the films was also discussed.

In Chapter 3, it describes the application of spherical silica nanoparticles with dense

structures for modifying UV-cured acrylate films. The aim of this experiment is to

improve optical properties and light diffusing ability of the films. The films were

prepared by coating dispersions of the particles in UV-curable acrylate monomer on

cleaned glass substrates with a bar coating machine. The light diffusing ability is related

to a haze value of the prepared films. The haze value was then measured at the

13
wavelength of 532 nm, which corresponded to the incident wavelength of a laser lamp

used for studying the light diffusing ability. Moreover, the influence of silica content on

optical properties of the films was investigated. The morphologies of the films were

further studied to understand the formation of those.

In Chapter 4, it presents the characterization and utilization of silica nanoparticles

with hollow structures for fabricating light diffuser films. Meanwhile, the quantitative

effect of hollow silica nanoparticles on optical properties and light diffusing ability of

the films is also given. A facile method to prepare the films was coating dispersions of

the particles in a UV-curable acrylate monomer on a cleaned glass substrate by a bar

coating machine. The effect of silica content on optical properties of the fabricated films

was disscussed. The light diffusing ability of the films was also characterized. The

results can be implied the performance of the films for being a light diffuser film.

Then Chapter 5 explicates a method for controlling structure of hollow silica

nanoparticles that is varying of pH of acid in the core-template removal process. The

hollow particles were firstly synthesized using calcium carbonate as an inorganic core-

template and tetraethoxysilane as silica sources. The obtained particles which have

different structures (e.g. shell thickness, hollow interior) were applied for fabricating

light diffuser films. The optical properties of the films were characterized. The effect of

hollow silica structure on morphologies of the films was studied because it related to

light diffusing ability of those.

Finally, in Chapter 6, the concluding remarks of the present work were stated and

the future directions of this research work were recommended.

14
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23
 CHAPTER 2

PREPARATION OF HIGHLY LOADED SILICA NANOPARTICLE

DISPERSIONS BY MATCHING REFRACTIVE INDICES OF THE

SILICA AND A BINDER RESIN FOR FABRICATING SILICA FILMS

WITH HIGH OPTICAL PROPERTIES

24
2.1 Introduction

The diversity of UV-curable monomers and oligomers, including acrylates,

acrylated urethanes, epoxies and vinyl ethers, allow the UV-coating formulator many

choices in achieving the desired properties [1]. A liquid resin rapidly transforms into a

solid material under intense UV illumination within seconds at ambient temperature by

the formation of a highly crosslinked polymer [2]. Due to its high crosslink density, the

UV-cured polymer exhibits a better adhesive property [3], hardness [4, 5], mechanical

property [5, 6], elastic property [6] and excellent abrasion resistance [5]. Consequently,

the UV-cured polymer has been used in various industries as adhesive materials [3], jet-

printed ink [7] and hard transparent coatings for optical materials [5, 8].

So far, optical materials have been extensively used in our daily life for various

applications such as lens, automobile parts, and screen panel displays in many

electronic devices [9-12]. The brightness and resolution are needed for achieving highly

effective images. However, the issues of contrast ratio, resistance capacitance (RC) time

delay, pixel resolution, reflection, glare, and transmittance (or brightness) are crucial

problems especially when the liquid crystal display (LCD) panel size is enlarged. Due

to the low quality of the final image, the transmittance and glare of the LCD panel must

be improved in order to achieve both a higher brightness and better resolution. To solve

these problems, the coating technology using various materials has been developed to

increase the transmittance and reduce the glare of the LCD. Recently, a light diffusing

film, a material with a high transmittance and light diffusivity [13], has been extensively

investigated. This type of film has also an excellent anti-glare property so it is widely

applied in LED light systems. The organic/inorganic hybrids have been extensively

used for fabricating light diffusing films because of their unique and enhanced

25
mechanical, thermal, electrical and optical properties [14, 15]. A variety of inorganic

colloidal particles including titanium dioxide, copper oxide, aluminum hydroxide,

alumina and silica have been combined with an organic polymer [15, 16] to produce the

hybrid materials. Among these materials, organic-silica hybrid materials are of great

interest due to their high transmission, low refractive index, easy preparation and low

cost [14, 17-18]. Konjhodzic et al. were able to produce a low refractive index film

using mesoporous silica and a nonionic triblock copolymer,

HO(CH 2 CH 2 O) 20 (CH 2 CH(CH 3 )O) 70 (CH 2 CH 2 O 20 )H [19]. This hybrid film with a

sufficient thickness showed an ultralow refractive index and birefringence. Yu et al.

prepared a polyimide-silica hybrid thin film using a soluble fluorine-containing

polyimide and monodispersed colloidal silica [20]. This film had an excellent optical

transparency in both the UV and visible regions. Its refractive index and thermal

stability were controlled by the silica content. Early attempts to fabricate an optical

coating using nanoparticles resulted in fragile surfaces [21], but researchers recently

tried to develop optical thin film coatings using nanoparticles and a UV-cured polymer

to enhance the abrasion resistance. Krogman et al. studied the refractive index of sub-

100 nm thin films by varying the metal oxide nanoparticle loading in an aqueous

colloidal solution and UV-curable monomer [22]. The mechanical and optical

performances of the resulting anti-reflective films coated on the plastic substrates were

investigated. The results revealed that the thin films prepared by silica and ceria

nanoparticles dispersed in a UV-curable monomer exhibited an optical transparency and

anti-reflective property. Similarly, a high quality image through the light diffusing film

of a display requires a quantitative description of light scattering in a high amount of

dispersed particles in the colloid [15]. It is due to the polymer matrix that is assumed to

26
be transparent and homogeneous [23]. Therefore, the light scattering is assumed to be

only due to the particles. When the light travels through a large amount of particles, the

light scattering more readily occurs [23]. However, the particles usually tend to appear

in aggregated cluster forms. The particles also do not have enough separation, thus the

scattered light of each particle or cluster is dependent on the other ones, and multiple

scattering occurs. The multiple scattering affects the increasing diffuse transmittance in

the film. It should be concluded that the enhanced optical properties of the polymer film

with particles is attributed to the amount, dispersibility and aggregated size distribution

of the particles [14]. Especially, preparation of an optical film using a colloid of

dispersed particles in a polymer must control the stability of the dispersant to force the

particles to remain separated and, in turn, on the sign and magnitude of the total

interparticle potential energy, V T [24]. The general equation for describing V T can be

expressed as [25]:

𝑉𝑇 = 𝑉𝑣𝑑𝑊 + 𝑉𝑒𝑙𝑒𝑐𝑡 + 𝑉𝑠𝑡𝑒𝑟𝑖𝑐 (2.1)

where V vdW is the attractive potential energy due to long-range van der Waals

interactions between the particles, V elect is the repulsive potential energy resulting from

electrostatic interactions between the like-charged particle surfaces, and V steric is the

repulsive potential energy resulting from long-chain molecules adsorbed onto the

particle surface. The stability of the dispersion is achieved when the repulsive forces are

high enough to overcome the attractive van der Waal attractive forces [24]. The

parameters involved in the electrostatic repulsion are well described by the DLVO

theory (as developed by Derjaguin, Landau, Verwey and Overbeek). The electrostatic

repulsion between the particles depends on the dielectric constant of the medium,

27
therefore it is less effective in the majority of nonaqueous media than in water because

of the lower ionic concentration and the lower dielectric constant [24]. Steric barriers

between particles and dispersing medium are also another way to induce a colloidal

stability [25]. The long-range van der Waals interactions between particles must be

mitigated during colloidal processing to achieve the dispersion stability [26]. One

approach is to render this force negligible by matching the refractive index of the

dispersed particles and media. This has been previously demonstrated for nanosilica and

UV-curable acrylate monomers [25]. The results show that minimization of the Van der

Waals forces and affinity of the monomer end group for the silica surface (for example

hydrogen bonding) are the main parameters allowing high loading dispersions in the

appropriate monomer and highly transparent dispersions having curing depths on the

order of 10 mm in the UVA range. According to the V vdW attraction, the interparticle

attraction for two spherical particles of radius r separated by the distance h can be

expressed by the effective Hamaker constant (A) [25]:

−𝐴𝑟
𝑉𝑣𝑑𝑊 = (ℎ ≪ 𝑟) (2.2)
6𝜋ℎ

The effective Hamaker constant is given by

2 2 −𝑛 2 )2
𝜀 −𝜀 (𝑛𝑚
𝐴 = 𝑎 �𝜀𝑚 +𝜀𝑝 � + 𝑏 𝑝
2 +𝑛 2 )3�2
(2.3)
𝑚 𝑝 (𝑛𝑚 𝑝

where ε is the dielectric constant, n is the refractive index and a and b are constants

[25]. The subindices m and p refer to the dispersing medium and the dispersed particles,

respectively. Equation (2.3) reveals that the dielectric constant and refractive index

differences contribute to the Hamaker constant. Meanwhile, the dielectric constant

depends on the complex refractive index (n C ) through Equation (2.4). Hence, the

28
refractive indices of the interacting media are matched, i.e., when n m = n p , the second

term in Equation (3) vanishes as a result of reducing the Hamaker constant to a

minimum.

𝜀 = 𝑛𝐶2 (2.4)

The complex refractive index is defined by Equation (5) [27].

𝑛𝐶 = 𝑛 + 𝐾𝑖 (2.5)

The real part of n C , namely n, is the same as the normal refractive index [27]. The

imaginary part of that, namely κ, is called the extinction coefficient. κ is directly related

to the absorption coefficient α of the medium which is very low in a transparent

material. The first term in Equation (3) may also become negligible when both the real

and imaginary parts of the complex refractive indices (n C ) are matched [27] leading to a

zero value of the Hamaker constant. Thus, the result of matching the refractive index in

a colloidal system is effectively a minimization of the Van der Waals attraction. These

form the base of our research which pertains to the possibility of silica nanoparticles

(SiNPs) dispersion in a UV-curable monomer and its optical properties after the UV-

cured film process.

In this chapter, highly loaded silica dispersions by matching refractive indices of

the silica and a binder resin were prepared. A UV-curable acrylate monomer was chosen

as the binder resin because its refractive index is close to that of SiNPs at the

wavelength of 500 nm [22]. The dispersion of the SiNPs was coated on the glass

substrate using a bar coater to prepare a thin solid silica-UV-cured film. The optical

properties of the resulting films were then analyzed by a UV-visible spectrophotometer

29
and compared with the uncoated substrate in the range of 300-800 nm. The effect of the

silica loading on the optical properties of the films was also investigated.

2.2 Experimental procedures

2.2.1 Materials

All solvents and chemicals were of reagent grade and used without further

purification. The chemical formula of the used compounds are shown in Fig. 2.1. Silica

nanoparticles, SO-C1, were purchased from Admatechs, Japan. An SEM image of the

SiNPs used in this study is shown in Fig. 2.2. The particles have a spherical shape, and

their size is in the range of 150-300 nm. The bulk density of SiNPs is 2.1 g/cm3 as

measured by a helium pycnometer. The UV-curable acrylate monomer was composed

of two major components, dipentaerythritol penta-/hexa acrylate as an acrylic monomer

and Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) as a photo initiator supplied by

the JSR Corporation, Japan. Methyl isobutyl ketone (MIBK; 99.5%) was purchased

from Wako Pure Chemical Industries, Japan. The density of the MIBK is 0.802 g/cm3.

It was used as a reactive diluent in the composite monomer to adjust the viscosity and

dispersibility.

30
Fig. 2.1 Chemical formulas of the compounds used.

Fig. 2.2 FE-SEM image of the SiNPs as received.

31
2.2.2 Instrumentation

An Ultrapycnometer 1000T (Quantachrome Instruments) was used for measuring

the bulk density of the SiNPs. Helium gas was used to precisely control the pressure of

the pycnometer. The helium pycnometer was run in the multimode with a standard

deviation of 0.05%. A Branson digital sonifier 450DA (Branson Ultrasonic Corp., JP)

was used to disperse the SiNPs in the monomer solution. The digital sonifier was

carried out using an ultrasonic horn. A planetary centrifugal deaeration mixer (ARE-930

Twin THINKY Mixer, JP) at a revolution speed of 1000 rpm under a vacuum of 20 kPa

was used for removing air bubbles from the dispersions after the ultrasonic process. The

particle size distribution of the SiNPs dispersions was determined by dynamic light

scattering performed using a Malvern Zetasizer nano (Sysmex Company, JP). A VIBRO

Viscometer SV-10 (A&D Co., JP) using the tuning fork vibration method equipped with

small sample cup was used for measuring the viscosity of the dispersions. A 30 cm3

volume of the dispersion was placed in the cup for measuring at 25°C. A refractometer

(Multi-wavelength Abbe refractometer DR-M2; ATAGO Co., JP) with a 589 nm

interference filter was used to determine the refractive index of the dispersions. The

refractometer is capable of measuring in the range of 1.3000-1.7100 with a precision of

± 0.0002. A bar-coating machine (K101 Control Coater; RK PrintCoat Instruments,

Ltd., UK) with a standard meter bar having the wire diameter of 0.76 mm and a constant

speed of 2.0 cm/s was used to prepare the wet silica film. The wet silica film was cured

by a UV-photo surface processor (PL16-110D; SEN LIGHTS Corp., JP) with a UV

emission wavelength in the range of 254 nm and output of 110 W. The thicknesses of

the wet and dry films were measured by a confocal laser scanning microscope (CLSM;

LEXT 3D Measuring Laser Microscope CLS-4000; Olympus, JP) at a magnification of

32
5X. The surface morphology of the silica UV-cured films was examined using a field

emission scanning electron microscope (FE-SEM; JSM7600F; JEOL, JP) equipped with

COMPO detectors. The silica UV-cured films were directly dried on a hot plate at the

temperature of 150°C for 2 h before being coated with osmium tetroxide in order to

eradicate any unclear images caused by some residual solvent. A thin layer of the

osmium tetroxide was coated on the dried sample by an osmium plasma coater

(OPC60A; Filagen) prior to the imaging. It should be noted that the films were observed

in the COMPO mode which uses back-scattered electrons [28]. They are a reflection

from the sample due to elastic scattering. The intensity of the back-scattered electrons

corresponds to the atomic number (Z) of the specimen. The optical properties of the

prepared silica UV-cured films were measured by a UV-Vis-NIR spectrophotometer

(UV3150; SHIMADZU, JP). The measurements were made in the wavelength range of

300-800 nm.

2.2.3 Preparation of silica UV-curable acrylate monomer dispersion

Dispersions containing 0.2-8.0 vol% of SiNPs were prepared by ultrasonication of

the mixtures between the known masses of the silica powder and 20 wt% UV-curable

monomer solutions by a digital sonifier at the amplitude of 40% and pulse on/off of 1

sec for 10 min in an ice bath to prevent polymerization throughout the dispersion

process. The desired volume percentage of the SiNPs in the dispersion can be calculated

by dividing the measured volume of the 20 wt% acrylate monomer solution (V sol ) by

the volume of SiNPs (V s ). The calculated value is then converted to a percentage by

multiplying by 100 and appending a percentage sign to the result.

𝑉
𝑉𝑜𝑙% 𝑜𝑓 𝑆𝑖𝑁𝑃𝑠 𝑖𝑛 𝑑𝑖𝑠𝑝𝑒𝑟𝑠𝑖𝑜𝑛 = 𝑉 +𝑉𝑠 × 100 (2.6)
𝑠 𝑆𝑜𝑙

33
Using the average density of SiNPs and Equation (2.7), the volume of the SiNPs can be

calculated.

𝑀𝑠
𝑉𝑠 = (2.7)
𝜌𝑠

where M s is the mass of the SiNPs and ρ s is the average density of the SiNPs,

which was determined by the helium pycnometer. The calculated values are shown in

the first column of Table 2.1.

Table 2.1 Amount of SiNPs in the dispersion and in the thin solid silica UV-cured film.

Amount of SiNPs in 20 wt% Amount of SiNPs in thin solid silica UV-

UV-curable acrylate monomer (vol%) cured film (vol%)

0.20 1

1.04 5

2.17 10

3.41 15

4.76 20

6.25 25

7.89 30

The second column of Table 2.1 lists the percentage volume content values of the

SiNPs in the UV-cured films. The dry film basically consists of SiNPs dispersed

throughout the continuous UV-cured acrylate film. The percentage volume content of

34
the SiNPs in the UV-cured films can be calculated by dividing the volume of the SiNPs

by the total volume of all the solids. The calculated value with a decimal point is

converted to a percentage by multiplying by 100 and appending a percentage sign to the

result.

𝑠 𝑉
𝑉𝑜𝑙% 𝑜𝑓 𝑆𝑖𝑁𝑃𝑠 𝑖𝑛 𝑈𝑉 − 𝑐𝑢𝑟𝑒𝑑 𝑓𝑖𝑙𝑚 = 𝑉 +𝑉 × 100 (2.8)
𝑠 𝑀

To know the volume of the acrylate resin (V M ) in the monomer solution, the

measured volume of the acrylate monomer solution is multiplied by its density (ρ sol =

0.855 g/cm3) and then divided by the density of the acrylate monomer (ρ M = 1.18

g/cm3). It can be expressed as

𝜌𝑆𝑜𝑙
𝑉𝑀 = 𝑉𝑆𝑜𝑙 × (2.9)
𝜌𝑀

The air bubbles in the dispersions were removed by a planetary centrifugal

deaeration mixer for 5 min in order to eliminate their effects on the optical properties of

the resulting films. Dynamic light scattering (DLS) studies were conducted to measure

the particle size distributions of the SiNPs in the dispersions. The viscosities of the

dispersions were then measured by a viscometer. A refractometer was used to determine

the refractive index of the dispersion. All the measurements were performed at 25°C.

2.2.4 Fabrication of thin solid silica UV-cured films on glass substrate

A clean glass substrate was coated by the silica dispersion using a commercial bar-

coating machine to obtain a wet silica film. The glass substrate was ultrasonically

cleaned successively in DI-water, ethanol and acetone for 10 min in each solvent. The

wet silica film was initially dried at room temperature in the dark for 24 h before being

35
further cured by the UV-photo surface processor for 5 min to remove any organic

compounds. The thin solid silica UV-cured film was then obtained with the solid

content yield shown in Table 2.1. The thickness of both the wet and dry films was

measured by the CLSM. The quantitative effect of the SiNPs on the optical properties of

the thin solid silica UV-cured films was studied using the UV-Vis-NIR

spectrophotometer. The transmittances of the coated substrates were then compared to

that of the uncoated substrate in the wavelength range of 300-800 nm. The particle

distributions on the film surfaces were also observed by the FE-SEM.

2.3 Results and Discussion

2.3.1 Physical properties of silica UV-curable acrylate monomer dispersion

The dispersions of the SiNPs in UV-curable acrylate monomer were successfully

prepared. The amounts of the SiNPs in the dispersions were varied and the refractive

indices of all the dispersions are illustrated in Fig. 2.3.

36
 1.420
Refractive index of SiNPs = 1.4584

1.415
Refractive index

1.410

1.405

1.400
0 2 4 6 8

Amount of SiNPs in 20 wt%

Fig. 2.3 Refractive indices of the modified UV-curable acrylate monomers

for different amounts of SiNPs.

It can be seen that the presence of SiNPs in the UV-curable acrylate monomer

significantly affects the refractive indices of the dispersions. Adding MIBK (n=1.3952

at 589 nm) to the UV-curable acrylate monomer solution makes its refractive index

lower and closer to the refractive index of the SiNPs. The value of the refractive index

of the SiNPs at 589 nm is about 1.4584 [29]. When the refractive indices of the

dispersed particles and dispersing media are matched, it provides a transparent

dispersion and allows a highly loaded dispersion [30-32]. To confirm the stability of the

dispersion from the resultant of the matching refractive indices in a colloidal system,

various amounts of the SiNPs in the dispersions at different times were studied.

37
Fig. 2.4 Stability of silica UV-curable acrylate monomer dispersions

at different times such as (a) 0 h, (b) 1 h and (c) 24 h.

38
 Fig. 2.4 shows images of the dispersions at the different times. The figure clearly

reveals that the colloid dispersions with removed air bubbles (0 h) became turbid

without any precipitation when the amount of the SiNPs increased from 0.20 to 7.89

vol%. Turbidity in the dispersions is caused by a high amount of dispersed particles.

Besides, the stability of these colloidal dispersions during dark storage can be

maintained for several hours by matching the refractive indices of the SiNPs and UV-

curable monomer solution. However, a precipitate in the dispersions can be observed

after 24 h as seen in Fig. 2.4 (c). The results suggest that the amount of MIBK in the

dispersions of the silica UV-curable acrylate monomer may be sufficient to modify the

interaction between the SiNPs resulting in the dispersion stability. This is consistent

with some previous studies, which reported that the selected monomer with refractive

index matching to the dispersed particles reduces the particle-particle attraction forces,

especially the Van der Waals forces [25]. This leads to the dispersion containing a large

amount of particles and having a long-term stability. The dispersion properties (like

viscosity, pH and ionic strength), the dispersed particle properties (like particle size,

particle volume fraction and specific surface area) and the presence of soluble polymers

or surfactants [25] affect the particle interactions in the dispersion. To further

understand the interaction of the particles in the dispersions, the silica loading effect on

the viscosity of the dispersions was investigated. The results are shown in Fig. 2.5.

39
 Fig. 2.5 Influence of silica loading on the viscosity.

The viscosity of the SiNPs dispersion gradually increases as the amount of the

silica dispersed in the UV-curable acrylate monomer is increased corresponding to a

previous study [33]. In a nonaqueous solution, the viscosity of a concentrated colloidal

dispersion significantly depends on the interactions between the particles. Therefore, the

lower the viscosity, the lower the interaction and the better is the given dispersant [34].

This is due to the structure of dipentaerythritol penta-/hexa acrylate that is OH

terminated as shown in Fig. 2.1. This monomer is then able to form hydrogen bonding

with the hydroxyl groups present on the silica surface and thereby increase the surface

compatibility to the monomer which leads to particle aggregation [25, 35]. This is

evident by the cumulative size distribution curve of the SiNPs dispersions as plotted on

a log scale in Fig. 2.6.

40
Fig. 2.6 The cumulative size distributions curve of SiNPs

dispersed in 20 wt% UV-curable acrylate monomer.

41
 A larger size of the particles with a narrow distribution was obtained when the

amount of the SiNPs in the UV-curable acrylate monomer was increased to 3.41 vol%.

However, the larger size with a wider particle distribution was obtained when the

amount of the SiNPs was higher than 3.41 vol%. These may be due to the fact that the

SiNPs used here is hydrophilic and contains excess –OH groups on its surfaces [36].

The SiNPs also has a high surface area to volume ratio and therefore possesses a high

surface energy. Consequently, it tends to aggregate so as to minimize the surface

energies [37].

2.3.2 The optical properties of the thin solid silica UV-cured films

2.3.2.1 Optical transmittance of the thin solid silica UV-cured films

The dispersion of SiNPs in the UV-curable acrylate monomer was coated on a

cleaned glass. The coated glass was then kept in the dark at room temperature for 24 h

to prevent any premature polymerization. The wet silica film was exposed to 254 nm

UV light for 5 min to induce the crosslinking polymerization. A thin solid silica UV-

cured film was eventually obtained. The silica content in the films related to the final

dry mass is shown in Table 2.1 To confirm the solvent removal by the UV-curing

process, the thickness of the wet and dry silica films were measured by CLSM. The

results are shown in Fig. 2.7 which shows that the average thicknesses of the UV-cured

acrylate films doped and undoped with SiNPs are lower than those of the wet films. It

indicates that the UV-curing process is capable for removing the solvent corresponding

to the results from the COMPO mode in the FE-SEM characterization as will be shown

later in Fig. 2.10. Besides, the increase in the amount of the SiNPs produces both

thicker wet and dry films. This is due to the increasing amount of the particles that

42
affects the increasing viscosity of the dispersion (as seen in Fig. 2.5) corresponding to

more formed silica aggregates [33].

Fig. 2.7 Comparison of thicknesses of wet and dry films

with different SiNPs contents.

43
 Therefore, the dispersion having high silica loading possibly contains a high

number of particles with a bigger size and various shapes leading to the increased film

thickness. In terms of the total transmittance, all the hybrid films were examined by

UV-VIS in the wavelength range of 300-800 nm and the result is shown in Fig. 2.8.

Fig. 2.8 Total transmittance of the modified UV-cured films with SiNPs

coated on glass substrate.

44
 In the visible region, the total transmittance of every coated glass is about 90%

which is close to that of both the bare glass substrate [16] and the UV-cured acrylate

film. These results confirmed that the highly transparent silica UV-cured films on the

glass substrate were produced. A sharp absorption edge in the ultraviolet region due to

the absorption of the glass substrate [16] was also observed. Interestingly, the edge

shifts to a longer wavelength (red shift) for the pure UV-cured film. This behavior was

also found in the UV-cured films containing SiNPs. This indicates that the UV-cured

acrylate film may absorb light at a wavelength longer than the uncoated substrate.

2.3.2.2 Diffuse transmittance of the thin solid silica UV-cured films

The total light transmittance (T t ) and diffuse light transmittance (T d ) are usually

used as indicators for estimating the light diffusing properties of diffuser plates in an

LCD system [38]. The films with a high total transmittance and high diffuse

transmittance tend to achieve a relatively excellent anti-glare and other optical

properties [13]. They are thus suitable for a higher performance LCD in order to obtain

the better final images. In this study, the thin solid silica UV-cured films with both a

high total transmittance and high diffuse transmittance were prepared with various

amounts of SiNPs.

45
 Fig. 2.9 Influence of silica quantity on the diffuse transmittance spectra

of the thin solid silica UV-cured film coated on glass substrate.

The diffuse transmittance spectra of the films containing different amounts of

SiNPs are shown in Fig. 2.9. They were measured using a spectrophotometer equipped

with an integrating sphere. When compared to the bare glass, the samples containing

SiNPs lower than 15 vol% showed slight increases in their diffuse transmittances, while

those with 20 and 25 vol% SiNPs showed moderate increases. The highest diffuse

transmittance of 20% was obtained at the 30 vol% level of SiNPs. However, the red

shift was observed when the amount of SiNPs was greater than 20 vol%. The diffuse

transmittance at a longer wavelength is decreased due to a lower interaction between the

46
light and particles when the wavelength is greater than the particle size. These results

reveal that the diffuse transmittance of the film is attributed to the particle loading.

When the polymer matrix is assumed to be transparent and homogeneous, the only

scattering entity is then assumed to be the particles [39]. Therefore, the high number of

particles in the film possibly provides a greater light scattering leading to a high diffuse

transmittance. The refractive index of the film is evidence to confirm the light scattering

occurrence. The average refractive index for cleaned glass substrates and UV-cured

acrylate films is about 1.5232 and 1.5198, by, respectively. However, the refractometer

cannot measure the refractive index of the UV-cured acrylate film containing the SiNPs

due to the significant refractive line. The refractive line is quite difficult to visually

focus the light as a result of an error in visual acuity. Thus, the refractive index for the

thin solid silica UV-cured films cannot be defined. These results also support that a

large amount of SiNPs in the UV-cured acrylate film may provide light scattering

leading to the light refraction. Based on the Mie theory, when the light interacts with the

high amount of particles with a size smaller than or comparable to the wavelength of the

light, each particle is more illuminated by both the incident light and the secondary

scattering than from other particles resulting in the increased diffuse transmittance of

the film. This behavior is called multiple scattering which usually occurs in the film

containing aggregated particles. If the aggregated particles in the media do not have a

sufficient separation, the scattered light of each particle or cluster is assumed to be

dependent on each other. At longer wavelengths, the diffuse transmittance drops

because the interaction of the light with the particles decreases when the wavelengths

become greater than the particles [40].

47
2.3.2.3 Morphology of the thin solid silica UV-cured films

To gain a better understanding of the quantitative effect of the SiNPs on the optical

properties of the thin solid silica-UV-cured films, the surface morphology of the films

were analyzed by FE-SEM.

Fig. 2.10 FE-SEM surface images of the silica UV-cured film with different amounts

of SiNPs (a) 5 vol%, (b) 10 vol%, (c) 20 vol% and (d) 30 vol%.

48
 Fig. 2.10 illustrates the polymer surfaces containing carbon (C) atoms with a lower

atomic number (as compared to silicon atom in silica) exhibit a dark background

emission. This evidence confirms the existence of the SiNPs in these films. The films

containing 5 and 10 vol% SiNPs as shown in Fig. 2.10 (a) and Fig. 2.10 (b) have low

amounts of particles on the surface and have a random distribution. The observed

particle size of the SiNPs is approximately 150 nm which is similar to that of the

received particles (as seen in Fig. 2.2). These results suggest that only a small

aggregation of particles occurs. However, the number of particles is increased in the

film when the amount of SiNPs is increased to 20 vol% as illustrated in Fig. 2.10 (c).

The size of the aggregates is in the range of 300 to 400 nm. It may be attributed to the

strong interaction and strong adhesion between the particles [13]. The size of the

aggregates corresponds to the cumulative size distribution of the SiNPs nanoparticles

dispersed in the UV-curing resin as shown in Fig. 2.6. Interestingly, the thin solid silica

UV-cured film with 30 vol% SiNPs exhibits a high particle distribution. The

distribution is homogeneous and the particles form a greater aggregation as seen in Fig.

2.10 (d). Its diffuse transmittance is the highest (about 20%) as shown in Fig. 2.9 This

indicates that the increased amount of SiNPs effectively improves the particle

dispersion in the polymer film, and influences the morphology of the films

corresponding to the increased optical properties of the films [13]. The reasonable

explanation is the influence of multiple scattering. The multiple scattering occurs if the

particles in the media are not sufficiently separated, thus the scattered light of each

particle or cluster is dependent on each other [39]. In this case, both the incident and the

secondary scattered light cause the illumination of each particle. Thus, the higher

number of aggregated particles on the substrate more continuously traps the scattered

49
light resulting in both high total and diffuse transmittances. In addition, the increased

SiNPs in the film exhibits a wide particle size distribution which improves the diffuse

transmittance of the film at the longer wavelengths. The larger size of the aggregates

allows the light with longer wavelengths to pass through.

2.4. Conclusion

A thin solid silica UV-cured film was successfully prepared by coating the SiNPs

dispersion on a glass substrate, followed by UV exposure to induce crosslinking

polymerization. The total transmittances of the films are close to the bare glass

indicating the films transparency. Although the increased amounts of the SiNPs in the

UV-cured films do not significantly affect their transmittances, the presence of SiNPs in

the UV-cured films produces a significant difference in the diffuse transmittance. The

thin solid silica UV-cured film containing 30 vol% SiNPs exhibits the diffuse

transmittance of 20% which is higher than other films and the uncoated glass substrate.

This is due to the increase in the multiple scattering by the particles in the film. The

increased SiNPs in the UV-cured films also provides a good compatibility and good

dispersion of the particles which is one of the main roles to improve the optical

properties of the films. Therefore, the optical property of the thin solid silica UV-cured

film depends on the amount and distribution of the silica nanoparticles.

50
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56
 CHAPTER 3

MODIFICATION OF UV-CURED ACRYLATE FILMS BY

SPHERICAL SILICA NANOPARTICLES

FOR IMPROVING THEIR LIGHT DIFFUSING ABILITY

57
3.1 Introduction

There are two types of UV-curing resins, which are categorized by the curing

mechanism, such as an acrylate radical polymerization and an epoxy cationic

polymerization. Among these types, the UV-curable acrylate resin has a high UV-

sensitivity and provides good mechanical and elastic properties such as modulus, strain

hardening, tear strength, creep, and glass-rubber transition temperature after the UV-

radiation curing [1-2]. For the UV-radiation curing, light hits the acrylate radical then

stimulates a bonding process between molecules leading to the polymerizations.

Consequently, the high cross-linked acrylate material is obtained by rapidly

transforming a liquid resin into a solid material [3-4] called a UV-cured acrylate. The

UV-cured acrylate is extensively used in many applications, for example, printed

materials, optical surface protections, paints, durable ink, and acrylic sheets used for

electronic display technologies [5-8]. In the case of the acrylic sheet, it exhibits a good

transparency in the visible light range but it has a very low light diffusivity. The

property of the light diffuser film is its homogeneous brightness by spreading the light

that is essential for electronic display technologies to form excellent final images [9].

Many efforts have been devoted to increasing the light transmittance of the UV-cured

polymer films along with increasing their light diffuse transmittance [8-10]. A variety of

inorganic particles including titanium dioxide, copper oxide, aluminum hydroxide,

alumina and silica are extensively used for the fabrication of light diffuser films due to

their unique and enhanced mechanical, thermal, electrical and optical properties [8-11].

Among these materials, silica nanoparticles are very attractive to improve the optical

properties of the polymer film because of their good light transmittance and diffusion

58
capacity, which may be promising candidates for light diffuser films in the electronic

display industry [12-13].

In this chapter, spherical silica nanoparticles (SSiNPs) with dense structures were

applied for modifying UV-cured acrylate films in order to improve their optical

properties and light diffusing property. The films were coated on cleaned glass

substrates using a bar coating machine. The transmittance and haze of all the modified

films were analyzed by a UV-visible spectrophotometer and compared to the

unmodified film coated on a glass substrate in the visible range (400-800 nm). The film

having a higher haze value normally exhibits a better light diffusing ability [12].

Therefore, the light diffusing ability of the films was examined by an apparatus

equipped with a 532 nm laser. The influence of silica content on the optical properties

of the films was also investigated.

3.2 Experimental procedures

3.2.1 Materials

The spherical silica nanoparticles (SSiNPs) were purchased from Admatechs,

Japan. The UV-curable acrylate monomer was supplied by the JSR Corporation, Japan.

Methyl isobutyl ketone (MIBK; 99.5%), ethanol and acetone were purchased from

Wako Pure Chemical Industries, Japan. All the glass substrates used in this study were

ultrasonically cleaned in deionized water, ethanol and acetone for 10 min in each

solvent to remove any contaminants. All solvents and chemicals were of reagent grade

and used as received.

59
3.2.2 Fabrication of UV-cured acrylate films modified with spherical silica

nanoparticles

The UV-curable acrylate monomer used in this study was composed of two major

components such as dipentaerythritol penta-/hexa acrylate that acted as an acrylic

monomer and Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) that acted as a photo

initiator. The monomer was diluted in the MIBK to 20 vol%, then mixed with a certain

amount of the SSiNPs by the ultrasonic method. The suspension was coated on the

cleaned glass substrates using a K101 control coater (RK PrintCoat Instruments, Ltd.,

United Kingdom). The coater using a standard meter bar having a 0.51 mm wire

diameter was set at the constant speed of 2.0 cm/s. The obtained wet silica-acrylate film

was stored in the dark at room temperature for 24 h to evaporate the solvent contained

in the film. The dry silica-acrylate film was exposed to a 110 W UV lamp (254 nm) in a

UV-photo surface processor (PL16-110D; SEN LIGHTS Corp., Japan) at ambient

temperature. A variety of silica contents in the UV-cured acrylate films was fabricated

by mixing different amounts of the SSiNPs in the 20 vol% UV-curable acrylate

monomer. The silica contents of the UV-cured acrylate films were 1, 5, 10, 20 and 30

vol%.

3.2.3 Characterization

Thicknesses of all the dry and cured films were measured by a confocal laser

scanning microscope (CLSM; LEXT 3D Measuring Laser Microscope CLS-4000;

Olympus, Japan). Dispersibility of the SSiNPs on the surface of the UV-cured acrylate

films with the various silica contents was also observed by the CLSM. A field emission

scanning electron microscope (FE-SEM; JSM7600F; JEOL, Japan) was employed to

60
observe the morphologies of the SSiNPs. The FE-SEM was also used to observe the

morphologies of the films. Prior to imaging by the FE-SEM, the films were directly

dried on a hot plate at a temperature of 150°C for 2 h in order to eradicate any unclear

images caused by some residual solvent. The dry samples were then coated by a thin

layer of osmium tetroxide using an osmium plasma coater (OPC60A; Filagen). The

coated samples were subjected to FE-SEM in order to observe their morphologies in the

COMPO mode. The transmittance and haze of the films were measured by a UV-Vis-

NIR spectrophotometer (UV3150; SHIMADZU, Japan). The haze value is defined as

the ratio between the diffuse transmittance and total transmittance (Haze = T diffuse/T total )

[14]. The haze value of the films was calculated at 532 nm corresponding to the

wavelength of the laser used in the light diffusing study. The film having a higher haze

value exhibits a better light diffusing ability [12]. The light diffusing ability of the films

was examined by an apparatus equipped with a light source. The light source is a laser

lamp with an emission of 532 nm (Z1M18B-F-532-PZ, Z-Laser, Germany). The films

were placed in front of the laser light and the scattered light by the particles in the

different films was obtained by a digital camera. The apparatus is illustrated by the

schematic diagram in Fig. 3.1.

61
Fig. 3.1 Schematic illustration of the apparatus for achieving

a scattered light image.

62
3.3 Results and Discussion

3.3.1 Morphologies of UV-cured acrylate films modified with spherical silica

nanoparticles

The UV-cured acrylate films modified with the SSiNPs were successfully

fabricated after subjecting the dry films to UV illumination for 10 min to induce the

crosslinking polymerization. The film thicknesses of the cured films were then

measured by the CLSM and compared to the dry films.

Fig. 3.2 Influence of silica content on the film thickness.

63
 Fig. 3.2 shows the influence of the silica content on the film thickness. It can be

seen that the average thickness of all the cured films is lower than that of all the dry

films. Therefore, the time used for the UV-curing process is probably sufficient to

transform the dry silica-acrylate films into the hardened UV-cured acrylate films.

According its components, the UV-cured acrylate polymer is a high reactivity UV-

curable resin, such as short reaction times on the order of seconds, offers a variety of

monomers, and oligomers with functional end groups [15-16]. In addition, the UV

intensity of the UV lamp used in this study was fixed at 110 W. Consequently, no more

shrinkage of the UV-cured acrylate film was detected though the UV-curing time was

longer than 10 min [17-18]. Interestingly, the thickness of both the dry and cured films

gradually increased when the silica content was increased. This is due to the increased

amount of particles that produces more aggregates on the film surfaces [19]. This was

confirmed by the results from the CLSM images at the magnification of 100x. The

middle in position of the UV-cured acrylate films modified with the SSiNPs was

selected for observing the film surface.

64
 Fig. 3.3 CLSM images of the UV-cured acrylate films modified with the SSiNPs.

Fig. 3.3 shows the CLSM images of the UV-cured acrylate films modified with the

SSiNPs. It was found that all the films coated on the glass substrates were uniform

throughout the bar coating process. The unmodified film is smooth and no particles

present. On the other hand, on the surface of all the modified films, it was observed that

particles were clearly present. There is a low amount of particles on the film modified

with 1 vol% SSiNPs. The particles have a random dispersion. When the silica content

was increased from 5 and 10 vol%, the amount of the particles on the surface of the

films moderately increased. Dispersibility of the particles on both films was quite good.

The surface of these films seems to be rougher than the film modified with the 1 vol%

SSiNPs. Nonetheless, the surface roughness of the films was still less than that of the

65
films modified with the 20 and 30 vol% SSiNPs. The result of the thickness and

roughness analyses of all the modified films are consistent with some previous studies,

which reported that the increased silica content produces films with a high thickness and

roughness [20-21]. The observed particles on the films modified with the 20 and 30

vol% SSiNPs have a larger size and more aggregates.

However, visualization of the particles on all the modified films from the CLSM

cannot accurately provide useful information about the size and form of the particles. It

is due to some particles embedded in the films. Also, the magnification of the CLSM

may be too low and insufficient to characterize when considering the original size of the

SSiNPs. The image reveals that all particles are totally spherical and the particle size is

in the approximate range of 100-250 nm.

An attempt to overcome these problems was made using the FE-SEM and the

results are shown in Fig. 3.4. The SSiNPs containing silicon (Si) atoms with a higher

atomic number as compared to the carbon (C) atom in the polymer surface exhibit

bright spot emissions. These are due to the COMPO mode that provides the image

contrast as a function of the elemental composition [22]. The results clearly confirm the

existence of the silica particles in the films.

66
 Fig. 3.4 FE-SEM images of the UV-cured acrylate films modified with various

amounts of SSiNPs: (a) 5 vol%, (b) 10 vol%, (c) 20 vol% and (d) 30 vol%.

Figs. 3.4 (a) and (b) illustrate the FE-SEM images of the film surfaces modified with 5

vol% and 10 vol% SSiNPs; they show small amounts of the particles with random

dispersions. The size of the observed particles is approximately 200 nm corresponding

to the size of the received particles as shown in Fig. 3.5.

67
 Fig. 3.5 FE-SEM image of the SSiNPs as received.

In addition, some of the particles on these film surfaces are close together as

aggregates. When the silica content was increased to 20 vol%, the size of the aggregates

is in the range of 300-500 nm as seen in Fig. 3.4 (c). This may be due to the fact that the

SSiNPs used here are hydrophilic and contains silanol groups on their surface leading to

the formation of hydrogen bonds between them [23]. The distances between the

aggregates decrease that is caused by the loss of the liquid carrier during the UV-curing

process [19]. This behavior is also found in the FE-SEM image of the surface of the

film modified with 30 vol% SSiNPs as illustrated in Fig. 3.4 (d). The image shows the

smallest distances between the aggregates and the best dispersion of particles when

compared to the other images of the film surfaces with the lower silica content.

Moreover, it exhibits the highest amount of the particles and aggregates. These results

indicate that the increased silica content possibly provides a high number of particles

68
and a greater aggregation with a good dispersion leading to the increased thickness and

roughness of the film. The increasing thickness and roughness of the films are

responsible for the light diffusing ability of the films resulting in the enhanced haze

value [24-25]. In addition, the presence of silica nanoparticles on the films can

dramatically improve the optical properties of a polymer film because of their good

light transmittance and diffusion capacity, which may be promising candidates for light

diffuser films in the electronic display industry [12-13]. Thus, the optical properties of

the UV-cured acrylate films modified with the SSiNPs were studied and further

discussed in the following section.

3.3.2 Optical properties of UV-cured acrylate films modified with spherical silica

nanoparticles

The transmittance of the UV-cured acrylate films modified with the SSiNPs was

measured by the UV-Vis spectrophotometer in the visible region and compared to the

unmodified film.

69
 Fig. 3.6 Transmittance spectra of all films coated on the glass substrate.

Fig. 3.6 illustrates the transmittance spectra of all films coated on the glass

substrate as a function of the wavelength. The transmittance spectra of the UV-cured

acrylate film modified with 1 vol% overlap with the spectral characteristic of the

unmodified film. Thus, the low silica content has no effect on the transmittance of the

UV-cured acrylate film. In contrast, the transmittance of the modified films slightly

decreases from 85 to 75 % when the silica content was increased from 5 to 20 vol%.

The lowest transmittance obtained in the visible region was 60%, which is observed

from the film modified with the highest SSiNPs (30 vol%). These results suggest that

the films become more opaque when the silica content was increased [26]. When light

70
passes through heterogeneous films, the light scattering occurs due to the difference in

the refractive indices between the heterogeneous phase (particles) and matrix [12].

Thus, the intensity of the light transmittance was attenuated. In principal, this type of

light scattering is related to the size of the particles in the matrix [13]. If the size of the

particles is much smaller than the wavelength of the incident light, the intensity of the

light scattering is inversely proportional to the fourth power of the wavelength. This

light scattering type is called Rayleigh scattering. On the other hand, if the size of the

particles is independent of the wavelength of the incident light, the light scattering is

classified as Mie scattering. Based on the Mie scattering, the intensity of the light

scattering is independent of the wavelength of the incident light. In addition, the

direction of the light scattering goes toward that of the incident light. Interestingly, the

transmittance of the films modified with the SSiNPs slightly rises at a wavelength

longer than 500 nm, thus the intensity of the light scattering during the SSiNPs is

probably independent of the wavelength of the incident light. Therefore, the Mie

scattering occurs in the films, and it can be inferred that the size of the particles or

aggregated particles present inside the films is possibly larger than that of the

wavelength of the incident light. Meanwhile, as received the particles are of various

sizes with a high distribution (Fig. 3.5), and consequently, the various sizes of the

observed particles on the film surfaces (Fig. 3.4) are almost smaller than 500 nm thus

the Rayleigh scattering probably occurs on the film surfaces. These results are

consistent with some previous studies [12]. It should be noted that the light scattering of

the films corresponds to the Mie scattering interfering with the Rayleigh scattering.

71
 The particle content in the films also plays a key role in their haze value, which is

one of the main factors affecting the optical properties of the light diffuser films [12].

Therefore, the haze value of the UV-cured acrylate films modified with the SSiNPs was

measured by a UV-Vis spectrophotometer and then calculated in order to investigate the

effect of the silica content on the haze value.

Fig. 3.7 Haze value of the UV-cured acrylate films modified

with various silica contents.

72
 Fig. 3.7 illustrates the haze value of the UV-cured acrylate films modified with

various silica contents. The haze value slightly decreases as a result of the modification

of the UV-cured acrylate film with 1 vol% SSiNPs. On the other hand, the haze

gradually increases when the silica content was greater than 5 vol%. The film modified

with 30 vol% SSiNPs has the highest haze value of about 0.26 although its

transmittance is the lowest (as seen in Fig. 3.6). This might be due to the haze value that

is considered using the light diffusion that depends on the light scattering from the

particles. When the light interacts with the high number of particles with a size

comparable or larger than the wavelength of the light, it is more possible that the

scattered light leads to the high light diffusing ability of the film [27].

The light diffusing ability of the UV-cured films modified with the SSiNPs can be

implied by their scattered light images. The scattered light images were visualized by

the apparatus and subsequently taken by a digital camera.

73
 Fig. 3.8 The scattered light images of the UV-cured acrylate films containing

various silica contents such as (a) 0 vol% (UV-cured acrylate film),

(b) 1 vol%, (c) 5 vol%, (d) 10 vol%, (e) 20 vol% and (f) 30 vol%.

The scattered light images of all the samples are displayed in Fig. 3.8. Fig. 3.8 (a)

shows the scattered light image of the unmodified film, which seems to be slightly

lower than that of the film modified with 1 vol% SSiNPs (Fig. 3.8 (b)). The range of the

scattered light by the particles in the film modified with 1 vol% SSiNPs is somewhat

smaller by about five times than that of the films modified with silica of about 10 and

20 vol% as seen in Figs. 3.8 (c) and (d). The largest range of the scattered light by the

particles is clearly observed in Fig. 3.8 (f),which shows the scattered light image of the

film modified with the highest silica content (30 vol%). Based on the above mentioned

results, it can be inferred that the light diffusing ability of the UV-cured acrylate film

74
increased when the silica content increased. This is due to the large number of silica

nanoparticles that probably produce a high light scattering resulting in the enhancement

of their light diffusing ability that corresponds to the haze value [12]. When the polymer

matrix is assumed to be transparent and homogeneous, the particles are only assumed to

produce the light scattering [27]. Moreover, the observed particles on the film surface as

evidenced from the FE-SEM images (Fig. 3.4) seem to be close to each other. Thus, it

can be implied that each particle is more illuminated by both the incident light and the

secondary scattering than from other particles when the light interacts with the large

amount of particles of a size comparable or larger than the wavelength of light. This

behavior is called multiple scattering based on the Mie theory. The multiple scattering

usually occurs when an aggregate is obtained in the film. Moreover, the aggregate does

not have enough separation thus the scattered light of each particle or cluster is assumed

to be dependent on each other. In addition, the scattered light continuously occurs in a

film with a homogeneous dispersion of particles corresponding to the morphology of

the UV-cured film with the high silica loading of 30 vol% presented in Fig. 3.4 (d). It is

noteworthy that the image of the unmodified film (UV-cured acrylate film) in Fig. 3.8

(a) showed no light scattering effect. Furthermore, a more uniform distribution of

scattered light was obtained with the UV-cured acrylate films modified with the

SSiNPs. These results further prove the advantage of the SSiNPs for improving the

light diffusing property of the UV-cured acrylate films. Thus, the films prepared in this

study are promising candidates for light diffuser films.

75
3.4 Conclusion

The UV-cured acrylate films modified with the SSiNPs was successfully fabricated

by coating suspension of silica-acrylate on cleaned substrates. The increasing silica

content in the films reduces the transmittance of the films. The increasing silica content

also provides a good compatibility and good dispersion of the particles which are some

of the main ways to improve the optical properties of the films. The modified films have

both a high haze and large range of scattered light. The largest range of the scattered

light (transmittance 60% and haze 0.26) was obtained from the film modified with 30

vol% SSiNPs. The spherical silica nanoparticles may be utilized in the polymer films to

obtain a high diffusing ability that is useful in the field of electronic display

technologies.

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80
 CHAPTER 4

CHARACTERIZATION OF HOLLOW SILICA NANOPARTICLES

AND THEIR APPLICATION IN LIGHT DIFFUSER FILMS

81
4.1 Introduction

Light diffuser films have both a high total and a diffuse transmittance since they are

able to diffuse a point or line of light; for instance, adjusting the angle of incident light

[1-2]. Consequently, the light diffuser films have homogeneous light penetration.

Therefore, light diffuser films have attracted a lot of interest during recent years for

applying in the backlight systems of several liquid crystal display (LCD) devices [2-5].

At present, two types of the light diffuser films are widely achieved as good optical

diffusion in the LCDs. The first type is called surface-relief diffuser films, which are

mainly dependent on the microstructures of the surface layers [6-9]. Most of the

microstructures are fabricated by complicated processes using expensive equipment [2-

3]. Another type, namely volumetric diffuser films, is simply prepared by coating a

mixture of filler and binder resin on optical material. According to the production of

those two light diffuser film types, the study of the volumetric diffusers has been

conducted by many researchers. Moreover, the volumetric diffusers provide a uniform

light scattering throughout the fillers, which play an important role in the optical

properties of the volumetric diffusers [1, 4-5, 10-12]. There are many kinds of fillers;

for example, organic particles [1], inorganic particles [2, 5, 13-14] and

organic/inorganic composite particles [3-4, 15]. Principally, the filler-diffuser type films

are related to the difference of refractive indices between the filler and the resin. When

light passes through the interfaces of the filler and the resin, the refraction occurs as

resulting in light scattering [2, 4-5].

In particular, polymer-inorganic hybrid nanocomposite materials are considered as

excellent option for multifunctional materials [16-17]. This can be attributed to the fact

82
that they possess both polymers and inorganic nanoparticles. Moreover, such hybrid

materials are capable of enhancing dispersion, which is advantageous for mixing fillers

and binder resins [18]. In addition, an aggregation of a small number of inorganic

particles is able to improve the bulk performance of polymer matrix for thermal,

mechanical, and especially optical properties [2, 5, 13-14, 19-20]. Those properties

significantly have an influence on the application of the filler-diffuser films [2].

Meanwhile, the microspherical structure of fillers is widely exploited in optical diffuser

films in the LCD industry [3, 21-22]. However, using fillers which have a cubic

structure in the fabrication of polymer-inorganic hybrid light diffuser films has not been

reported in any involved research. Hollow silica nanoparticles (HSiNPs) comprise of a

nano-sized hollow interior and a solid shell with the unique properties of low density, a

high specific surface area, thermal insulation, and optical properties; for instance, light-

weight filler [1, 5, 23-24]. Due to these properties, the HSiNPs have been much used as

fillers light diffuser films. Their hollow structures can be expected to have a critical

importance for light scattering as more light can penetrate into their hollow interior

resulting in increasing light scattering [25].

In this chapter, silica nanoparticles with hollow structures (or hollow silica

nanoparticles) were characterized. They were dispersed in a UV-curable acrylate

monomer. The dispersion was coated on a cleaned glass substrate to fabricate a light

diffuser film. The UV-curable acrylate monomer was used in this study because it has

good mechanical and thermal properties; for instance, excellent optical properties [2,

26-28]. The composition of HSiNPs was initially investigated in order to eradicate any

unexpected result, which may affect optical properties of the light diffuser films. The

optical properties of the films containing different number of the particles were then

83
analyzed by a UV-visible spectrophotometer and compared to those of the cleaned glass

in the visible region (400-800 nm). The quantitative effect of the particles on the optical

properties of the films was also investigated.

4.2 Characterization of HSiNPs

4.2.1 Thermogravimetric analysis of HSiNPs

The thermogravimetric analysis (TGA, Thermo Plus TG-8120; Rigaku) was used to

study the composition of HSiNPs. The sample was placed in a platinum crucible for

each analysis and then heated in air to 800 °C at a heating rate of 10 °C/min.

Fig. 4.1 TGA curve of the raw HSiNPs.

84
 Fig. 4.1 shows the thermal decomposition of the raw HSiNPs. It reveals two

regions of weight loss. The first region of weight loss is observed in the range of 40-150

°C because of the removal of bound water (5%). Another region of weight loss about

25% (300-520 °C) can be ascribed to the dehydration of Si-OH on the silicates or the

loss of some residual reagent such as surfactant, which is used to produce the HSiNPs

[29-30]. Moreover, the incombustible residue can be assumed to be silica as the results

are consistent with other previous studies involving TGA for silica nanoparticles [31].

According to its TGA result, the raw HSiNPs was further calcined at temperature of

400 and 600 °C in order to eliminate some contamination which could lead to a

flocculation of the HSiNPs. This formation is an undesirable in the preparation of

highly loaded HSiNPs suspensions for a resulting film [32].

4.2.2 Morphologies of HSiNPs

The morphologies of HSiNPs before and after calcination were observed using a

field emission scanning electron microscope (FE-SEM, JSM-7600F, JEOL Ltd.) at an

acceleration voltage of 15 kV with secondary electron image (SEI) and transmission

electron diffraction (TED). The samples were dispersed in ethanol (EtOH, 99% Wako

Pure Chemical Industries, Ltd.) by an ultrasonication. Then, the suspensions were

dropped on a microgrid (STEM150Cu, Oken Shoji) and dried in the air. The FE-SEM

results are shown in Fig. 4.2.

85
 Fig. 4.2 FE-SEM images obtained from SEI and TED modes of HSiNPs before

calcination for (a) and (d) and after calcination at temperature of 400 °C for (b) and (e),

including to at temperature of 600 °C for (d) and (f).

86
Fig. 4.2 (a) shows the morphologies of the particles before calcination (raw) that clearly

exhibits cubic shapes. The cubic shapes are also observed from the FE-SEM image

obtained from SEI mode of the particles after calcination temperature at 400 °C as seen

in Fig. 4.2 (b). However, no cubic shape is obtained from the particles after calcination

temperature at 600 °C that is visibly shown in Fig. 4.2 (c). Meanwhile, the FE-SEM

images obtained from TED mode of all particles were presented in Fig. 4.2 (d-f). The

calcined particles at temperature of 400 °C (Fig. 4.2 (d)) contain a hollow interior the

same as in the raw particles (Fig. 4.2 (e)). On the other hand, the morphologies of the

calcined particles at temperature of 600 °C (Fig. 4.2 (f)) contain few hollow structures.

These results indicate that the calcination temperature of 600 °C possibly changes

hollow forms of the particles to dense forms. This is due to the mesoporous particle

growth that increases condensation of silicon [33]. It results in a larger degree of Si-O-

Si bonds and fewer Si-OH groups involving to typical nonporous Stöber particles.

Therefore, the calcination temperature of 600 °C is not appropriate for preserving cubic

shapes with hollow interiors of the HSiNPs. Consequently, the particles calcined at

temperature of 400 °C were used to prepare a light diffuser film because they still

exhibit the morphologies of the HSiNPs.

4.2.3 Density of HSiNPs

To get a better understanding of the effect of the calcination temperature on the

morphologies of HSiNPs, the density of the powder samples was futher measured by a

helium pycnometer (Ultrapycnometer 1000T, Quantachrome Instruments). The helium

pycnometer was run in the multimode with a standard deviation of 0.05%. The samples

87
were dried under vacuum at temperature of 180 °C for 3 days in order to eradicate any

error caused by some remaining air.

Table 4.1 Densities of HSiNPs before and after calcination.

Sample Density (g/cm3)

Raw HSiNPs 1.67

HSiNPs calcined at 400 °C 1.66

HSiNPs calcined at 600°C 1.78

Table 4.1 illustrates the densities of the HSiNPs before and after calcination. It

reveals that the density of the HSiNPs calcined at 400 °C is considerably lower than that

of the raw HSiNPs which is attributed to the contaminant removal. Meanwhile, the

density of the HSiNPs calcined at 600 °C is obviously higher than that of the raw

HSiNPs. Interestingly, the density of the HSiNPs at 600 °C is close to that of fumed

silica nanoparticles (2.2 g/cm3) [34-35]. Therefore, the temperature of 400 °C is much

more suitable than 600 °C for removing the contamination in HSiNPs.

88
4.3 Experimental procedures

4.3.1 Facile fabrication of optical diffuser films with HSiNPs

Based on the results from the previous section, the calcined HSiNPs at temperature

of 400 °C were used to prepare light diffuser films because the particles still maintain

the original raw material morphologies. The number of the desired HSiNPs in the light

diffuser films was studied as listed in the first column of Table 4.2.

Table 4.2 Amount of the calcined HSiNPs in light diffuser films

Amount of the calcined Calcined HSiNPs MIBK 10 wt% UV-curable acrylate

HSiNPs in light diffuser in MIBK (g) monomer solution

films (g) (g)

(vol%)

5 0.415 20 36.05

10 0.830 20 33.10

15 1.245 20 30.15

20 1.660 20 27.20

89
 The concentration of the suitable HSiNPs in the suspensions can be calculated

using the equations on our previous study [26]. The calculated values are shown in the

second column of Table 4.2. The known masses of the HSiNPs were dispersed in

methyl isobutyl ketone (MIBK, 99.5% Wako Pure Chemical Industries, Ltd.) by the

ultrasonication for 10 min. Meanwhile, UV-curable acrylate monomer supplied by the

JSR Corporation was diluted by MIBK to 10 wt% UV-curable acrylate monomer

solution. After that, each of the HSiNPs dispersions was combined with the 10 wt%

monomer solution. Suspensions of the HSiNPs were obtained and then coated on

cleaned glass substrates using a commercial bar coating machine (K101 Control Coater;

RK PrintCoat Instruments, Ltd.) to obtain wet films. The cleaned glass substrates were

obtained after successively cleaning in DI-water, EtOH, and acetone for 10 min in each

solvent. The wet films were kept in the dark and then cured by a UV-photo surface

processor (PL16-110D; SEN LIGHTS Corp.) for 5 min so as to induce

photopolymerization. Consequently, the light diffuser films with different numbers of

the HSiNPs as shown in the first column of Table 4.2 were obtained.

4.3.2 Characterization of optical diffuser films with HSiNPs

The morphologies of the obtained films were observed with the FE-SEM. Before

the FE-SEM observation, the films were directly dried on a hot plate at the temperature

of 150 °C for 2 h since some residual solvent containing in the films may cause of

unclear images. The dried samples were further coated by a thin layer of osmium

tetroxide using an osmium plasma coater (OPC60A; Filagen). The films were also

studied for their optical transmittances in the visible region (400-800 nm) using a UV-

Vis-NIR spectrophotometer (UV3150; SHIMADZU). The transmittance results of the

films were then compared to those of a cleaned glass substrate. The light diffusing

90
ability of all films was inferred by their scattered light image. The scattered light image

was recorded by a digital camera performed on the apparatus together with a 532 nm

laser (Z1M18B-F-532-PZ; Z-Laser). The apparatus was invented based on our previous

reports. A film coated on cleaned glass substrate was placed in front of the laser lamp in

about 15 cm lengths from each other. Subsequently, a scattered light image of the film

exhibits on the dark background, which has the distance between them about 26 cm.

4.4 Results and Discussion

4.4.1 Morphologies of the light diffuser films based on the HSiNPs as fillers

The HSiNPs calcined at 400 °C were used to fabricate the light diffuser films by

coating their suspension on the cleaned glass substrates, then curing with the UV-photo

surface processor. The optical images of obtained films were presented in Fig. 4.3.

Fig. 4.3 Optical images of the light diffuser films containing different numbers of the

HSiNPs such as (a) 5 vol%, (b) 10 vol%, (c) 15 vol% and (d) 20 vol%.

91
 It distinctly shows that the obtained films were uniformly fabricated by the bar

coating machine. Apparently, the films became slightly opaque when the number of the

HSiNPs was increased from 5 to 20 vol%. The opacity in the films is attributed to a

high number of fillers [36]. Moreover, the aggregated particles on the film surfaces

possibly occur because of the solvent removal during the photopolymerization [37].

The FE-SEM with SEI mode was used to observe the morphologies of the light

diffuser films based on the HSiNPs as fillers in order to study an effect of those

particles.

Fig. 4.4 FE-SEM images with (inset) high magnification of the light diffuser films

containing different numbers of the HSiNPs such as (a) 5 vol%, (b) 10 vol%,

(c) 15 vol% and (d) 20 vol%.

92
 Fig. 4.4 shows the FE-SEM images with (inset) high magnification of the light

diffuser films containing different numbers of the HSiNPs. The film surface containing

5 vol% the HSiNPs shown in Fig. 4.4 (a) has a small size of aggregated particles with a

random dispersion. The size of about 1 µm of the aggregated particles can be roughly

estimated by the high magnified FE-SEM image of the film as shown in inset Fig. 4.4

(a). From the enlarged FE-SEM image shown in the inset Fig. 4.4 (b), the film surface

containing 10 vol% the HSiNPs exhibits a larger size of aggregated particles (∼2 µm).

Moreover, this film surface observed from the low magnified FE-SEM image (Fig. 4.4

(b) shows a good dispersion of the aggregated particles. Fig. 4.4 (c) shows the film

surface containing 15 vol% the HSiNPs that exhibits a high number of aggregated

particles. The aggregated particles observed are quite larger than 2 µm (as seen in inset

Fig. 4.4 (c)) with a better dispersion as compared to the films containing lower number

of the HSiNPs. Meanwhile, the film surface containing 20 vol% the HSiNPs illustrated

in Fig. 4.4 (d) shows the highest number of aggregated particles as compared to the

other films. The inset Fig. 4.4 (d) further reveals that the aggregated particles closely

contact with the neighboring aggregated particles leading to a larger size (> 3 µm),

which possess the entire film surface. When the film containing 20 vol% the HSiNPs

was compared to the other films containing lower numbers of the HSiNPs, it suggests

that the dispersion of aggregated particles on the film containing 20 vol% the HSiNPs

exhibits the highest number of the particles with a homogeneous dispersion. All the

results of the FE-SEM correspond to an order of the opacity of the film as shown in the

Fig. 4.3. Moreover, the results indicate that the high number of the HSiNPs more

probably provide a high number of those particles on the film surfaces with their high

dispersion [18]. In addition, it can be concluded that both the size and dispersion of

93
fillers are the main factors, which have an influence on the optical performance of light

diffuser films [2, 18].

4.4.2 Optical properties of the optical diffuser films with the HSiNPs

4.4.2.1 Total transmittance of the light diffuser films based on the HSiNPs as fillers

The total transmittance of the light diffuser films based on the HSiNPs as fillers

was measured by the UV-Vis-NIR spectrophotometer in the visible region (400-800

nm), then compared to the cleaned glass substrate, which is demonstrated in Fig. 4.5.

Fig. 4.5 Total transmittance spectra of the cleaned glass (a)

and the light diffuser films containing different numbers of the HSiNPs

such as (b) 5 vol%, (c) 10 vol%, (d) 15 vol% and (e) 20 vol%.

94
It can be found that the transmittance spectra of every coated glass is over 87%, which

approaches that of the uncoated glass (cleaned glass) [38]. The results indicate that the

high transparency of the light diffuser films coated on the glass substrate was fabricated.

Interestingly, the transmittance spectra of the film containing 20 vol% the HSiNPs (Fig.

4.5 (d)) is over than that of the cleaned glass (Fig. 4.5 (a)) at the wavelength longer than

450 nm. Therefore, the film containing 20 vol% the HSiNPs possibly has an anti-

reflection property [38]. Moreover, the total transmittance of the light diffuser films

slightly decreases with the decreasing number of the HSiNPs as fillers in those films.

These results disagree with the optical images of the films as shown in Fig. 4.4. It is due

to the difference in refractive indices between particles and films [10]. Larger

aggregated HSiNPs with a high refractive index possibly result in optical scattering and

opacity of material.

4.4.2.2 Diffuse transmittance of the light diffuser films based on the HSiNPs as

fillers

The diffuse transmittance of the light diffuser films containing different numbers of

the HSiNPs was measured using the spectrophotometer equipped with an integrating

sphere and then compared to that of the cleaned glass.

95
 Fig. 4.6 Diffuse transmittance spectra of the cleaned glass (a)

and the light diffuser films containing different numbers of the HSiNPs

such as (b) 5 vol%, (c) 10 vol%, (d) 15 vol% and (e) 20 vol%.

Fig. 4.6 demonstrates the diffuse transmittance spectra of the films and the cleaned

glass. It was found that the diffuse transmittance of the films is more than that of the

cleaned glass. The results reveal that the films based on the HSiNPs dramatically

improve diffuse transmittance of the glass substrate. Also, the diffuse transmittance of

the films gradually increases with the increasing number of the particles in those films

[3-5]. The enhanced diffuse transmittance relates to the different refractive indices

between particles and homogeneous film, which can be explained by the Rayleigh

scattering [4]. The Rayleigh scattering defined that the light scattering depends on the

96
size of the particles, which is very small in relation to the wavelength of incident light.

And the intensity of the scattering is inversely proportional to the fourth power of the

wavelength. Also, the Rayleigh scattering has a significant influence on the longer

wavelength of the light. This relates to the abrupt reduction of the diffuse transmittance

at the longer wavelength, which can be seen in all diffuse transmittance of the films

(Fig. 4.6 (b)-(e)). The results can be inferred that almost aggregated particles inside the

films are smaller than the wavelength of the incident light and the size of the observed

aggregated particles on the film surfaces (as can be seen in the FE-SEM images of the

film surfaces in Fig. 4.4) [10]. Meanwhile, the aggregated particles on the film surfaces

possibly occur throughout the Rayleigh scattering interfering with the Mie scattering. In

the case of the Mie scattering, the size of the particles is comparable or larger than the

wavelength of the incident light [10, 39]. The intensity of the light scattering is

independent to the size of the particles. Moreover, the direction of the light scattering is

towards that of the incident light. The light scattering on the film surfaces significantly

has an influence on the enhancement of the total and diffuse transmittance of those

films. It is evidently confirmed by the sequence of the diffuse transmittance of the films,

which corresponds to the order of the total transmittance of those films.

4.4.2.3 Light diffusing ability of the light diffuser films based on the HSiNPs as

fillers

The Mie scattering not only play a key role in the transmittances of the films but

also influences on homogenization of the incident light. The homogenization is one of

the main factors in achieving good light diffuser films [2]. The homogenization of the

light penetrated throughout the light diffuser films containing different numbers of the

HSiNPs can be examined using the apparatus. The results are shown in the scattered

97
light image of the films as exhibited in Fig. 4.7, which imply the light diffusing ability

of those films.

Fig. 4.7 The scattered light images of the cleaned glass (a)

and the light diffuser films containing different numbers of the HSiNPs

such as (b) 5 vol%, (c) 10 vol%, (d) 15 vol% and (e) 20 vol%.

In comparison of the scattered light images in Fig. 4.7, they reveal that the size of

the scattered light images of the films is larger than that scattered light image of the

cleaned glass. The films can diffuse the point and the line light source resulting in

homogeneous surface lighting [2]. It can be implied that the films exhibit their high

light diffusing ability. These are due to the production of the scattered light by the

98
particles. The scattered light is caused by the particles only, when the polymer matrix is

assumed to be transparent and homogeneous [40]. Consequently, the high number of

particles loaded in the films probably provides a greater light scattering leading to a

high diffuse transmittance. As could be seen in Fig. 4.7 (b)-(e), the size of the scattered

light image of the film dramatically increases with the increasing number of the

HSiNPs. The scattered light images of the films exhibit fairly uniform pattern. This

suggests that the HSiNPs used as fillers leads to the uniform pattern of the scattered

light [4, 11-12]. In addition, the aggregated particles on the film surfaces (as observed

from the FE-SEM images in Fig. 4.4) do not have a sufficient separation; therefore, they

probably produce multiple scattering based on the Mie scattering [40]. The multiple

scattering usually occurs in the film containing aggregated particles because the

scattered light of each particle or cluster is supposed to be dependent on each other.

Consequently, the film containing the highest number of aggregated particles (20 vol%

the HSiNPs) more continually provides the scattered light leading to both high

transmittances and homogeneous light. These properties play a significant role in a high

performance of a light diffuser film [2]. Therefore, the films containing a high number

of the HSiNPs have a great potential to be light diffuser films, especially manufactured

multifunctional light diffuser films in the LCD industry. A schematic illustration of

applying the light diffuser film based on the HSiNPs as fillers in the LCD is shown in

Fig. 4.8.

99
 Fig. 4.8 Schematic illustration of applying the light diffuser film

based on the HSiNPs as fillers in the LCD.

4.5 Conclusion

The light diffuser films based on HSiNPs as fillers were facilely fabricated by

coating the suspension of the HSiNPs calcined at temperature of 400 °C and the UV-

curable acrylate monomer solution. The number of the particles in the films was varied

from 5 to 20 vol%. The films became opaque when the number of the HSiNPs was

increased. Meanwhile, the films containing different numbers of the particles exhibit

various total transmittances and they are also close to the cleaned glass. The diffuse

transmittance of the films increases as the number of particles increases that are also

obviously higher than that of the cleaned glass. Interestingly, a film based on 20 vol%

HSiNPs gives the highest total transmittance (93%) and diffuse transmittance (40%)

100
when comparing to other films in this study. The film also exhibits the largest size of

the scattered light image which indicates its highest light diffusing ability. In

conclusion, the increased number of the HSiNPs in light diffuser films improves both

transmittances and light diffusing ability; therefore, the HSiNPs are potentially applied

for fillers in light diffuser films of backlight unit in the LCD industry

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106
 CHAPTER 5

CONTROLLING STRUCTURE OF

HOLLOW SILICA NANOPARTICLES

THROUGH CORE-TEMPLATE REMOVAL PROCESS WITH ACID

AND APPLYING THEIR STRUCTURE FOR LIGHT DIFFUSER FILMS

107
5.1 Introduction

Recently, liquid crystal display (LCD) has dramatically become a dominant product

in the display market. Therefore, the backlight unit as an essential part of LCDs has

been gradually developed by many approaches. The backlight unit supplies light for

LCDs, which cannot emit the light by themselves [1]. This unit mainly composes of a

light emitter, a light guide plate, a reflection film, one or two brightness enhancement

film (s), and one or two light diffuser film (s). Remarkably, the light diffuser film has a

function of scattering and homogenizing the light source over a wide angle in order to

achieve comfortable and wide view-angle image from LCDs [2-6]. At present, there are

two types of light diffuser films achieved for applying in LCDs which are volumetric

diffuser type [1, 2] and surface-relief diffuser type [3-6]. Since the surface-relief

diffuser type is fabricated by complicated process using expensive equipment, many

researchers are much attracted to study the volumetric diffuser type which is more

simply fabricated by coating a mixture of filler and binder resin on optical material [7-

12]. The light scattering in this diffuser type is caused by fillers, which are mainly

organic or inorganic particles. Based on the utilization of the light diffuser in LCDs,

inorganic particles are much attractive because of their thermal stability [8, 10].

However, the particles tend to approach each other leading to agglomeration problem. It

is a cause of low transmittance of the light diffuser films. Meanwhile, number of the

particles in the diffusers is one of the main factors of number of backlight unit in LCDs.

This is related to the energy consumption and the weight of screens [7, 8]. To overcome

these problems, hollow structure of the particles has shown a great promise to solve

them.

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 Fig. 5.1 Schematic illustration of light scattering occurred by

(a) dense particles and (b) hollow particles.

Hollow particles fundamentally comprise of hollow interiors and solid shells

surrounding the hollow interiors [13-15]. Due to their unique characteristic, these

particles have many interesting properties; for example, low density [8], high specific

surface area [8, 14], thermal insulation [16, 17], optical properties [7, 8, 18], light-

weight filler [8], and etc. Therefore, the hollow particles are extensively applied for

many applications, such as catalysis [19, 20], bio-technology [21-24] and optical

diffuser [8]. However, the utilization of the hollow particles in the field of light diffuser

films is particularly much more attractive as these particles probably allow light

penetration through their hollow interiors and slightly absorb the light with their solid

shells. It can be illustrated by Fig. 5.1, which implies that the light scattering is more

possibly occurred by hollow particles (Fig. 5.1 (b)) than by dense particles (Fig. 5.1 (a)).

Meanwhile, the power consumption may be reduced when the light pass through hollow

particle [8, 18, 20]. Moreover, the difference of refractive indices between the hollow

109
interior and the solid shell more probably produces more light refraction in the light

diffuser films [8]. According to these reasons, morphologies and surface properties of

hollow particles significantly affect the efficiency of light diffuser films. Therefore, one

of the effective approaches to obtain suitable hollow particles is a synthesis of hollow

silica nanoparticles via inorganic particle template method incorporated with removing

core-template by the acid dissolution [13, 15, 25, 26]. The hollow silica nanoparticles

(HSiNPs) have many essential properties for light diffuser films; for instance, low

density, thermal insulation, prominent optical material, and light-weight filler [9, 17,

18]. Meanwhile, the method is neither additional toxic chemicals nor a calcination

process.

In this chapter, HSiNPs were synthesized using calcium carbonate (CaCO 3 ) as the

inorganic core- template which was removed by HCl. The pH of HCl was varied as 1, 2

and 5. The aim of this process was to control structure (e.g. shell thickness, hollow

interior). The obtained particles were expectedly suitable for fabricating silica-UV-

cured polymer composite films with high optical properties. The morphologies and

surface properties of the synthesized HSiNPs at different pH were characterized. The

silica/UV-cured polymer composite films were fabricated by coating dispersions of each

HSiNPs in a UV-curable acrylate monomer and then cured by a UV-lamp. The optical

transmittances, light diffusing ability and morphologies of the composite films were

then studied. An effect of the morphological HSiNPs on the optical properties of the

composite films was also discussed.

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5.2 Experimental procedures

5.2.1 Materials

Calcium carbonate (CaCO 3 , Homocal D) was obtained from Shiraishi Calcium

Kaisha, Ltd. The appearance of the CaCO 3 is in cubic shapes with the particle size of

about 80 nm, which was determined by field emission scanning electron microscopy

(FE-SEM) observation as shown in Fig. 5.2.

Fig. 5.2 FE-SEM image of the raw CaCO 3 nanoparticles.

111
 Diglyme (Dg, Wako Pure Chemical Industries, Ltd.) was dissolved in deionized

water (DI-water) to obtain 69.0% diglyme aqueous solution (Dg aq.). The 69% Dg aq.

was used as a solvent to prepare HSiNPs. For HSiNPs, tetraethoxysilane (TEOS, Wako

Pure Chemical, Ltd.) as silica sources, ammonia water (NH 3 aq., 25% Wako Pure

Chemical Industries, Ltd.) as a catalyst for sol-gel reaction and hydrochloric acid (HCl,

Wako Pure Chemical, Ltd.) as an acid treatment were used as received.

UV-curable acrylate monomer (JSR Corporation) and methyl isobutyl ketone

(MIBK, 99.5% Wako Pure Chemical Industries, Ltd.) were mixed to be binder resin for

fabricating silica/UV-cured polymer composite films. All glass substrates were

ultrasonically cleaned successively in DI-water, ethanol (EtOH, 99% Wako Pure

Chemical Industries, Ltd.) and acetone (Wako Pure Chemical Industries, Ltd.) for 10

min in each solvent before being used as optical materials for coating the composite

films.

5.2.2 Synthesis of hollow silica nanoparticles

HSiNPs were synthesized based on our previous reports, which used CaCO 3

nanoparticles as the template [25] and HCl as the acid treatment [13]. The synthesized

method was modified so as to get the appropriate morphologies of HSiNPs

morphologies for fabricating silica/UV-cured polymer composite film with high optical

properties. The CaCO 3 , D g aq., TEOS and 25.0% NH 3 aq. were mixed and stirred for

90 min at room temperature in the ratio of CaCO 3 :D g aq.:TEOS:NH 3 aq. =

2:29:1.6:0.45 in order to obtain core-shell particles. After that, the milky white solution

was centrifuged and filtrated. Precipitates were washed with EtOH twice times and then

dried under vacuum. The dried powders were further treated with HCl to remove

112
CaCO 3 template. During the removal template process, pH of HCl was varied as 1, 2,

and 5 in order to modify the morphologies and surface properties of HSiNPs. The

samples removed core-templates were washed several times with EtOH/H 2 O solution

until they became neutral before being dried under vacuum. Consequently, the

synthesized HSiNPs at pH 1, 2 and 5, namely, HSiNPs-1, HSiNPs-2 and HSiNPs-5 by

respectively, were obtained.

5.2.3 Fabrication of silica/UV-cured polymer composite films

Each of the HSiNPs was dispersed in MIBK by a Branson digital sonifier (450DA,

Branson Ultrasonic Corp.) equipped with an ultrasonic horn at the amplitude of 40%

and pulse on/off of 1 sec for about 10 min. The UV-curable acrylate monomer was

diluted in MIBK to 20 vol% UV-curable acrylate monomer solution. Each of the

HSiNPs dispersions was then mixed with the monomer solution at the ratio of 1:1 by the

sonifier for 10 min in the ice bath. After that, a planetary centrifugal deaeration mixer

(ARE-930 Twin THINKY Mixer) at a revolution speed of 1000 rpm under a vacuum of

20 kPa was used for removing air bubbles in the dispersions about 5 min. As a result,

the HSiNPs in UV-curable acrylate monomer dispersions were obtained and coated on

the cleaned glass substrates using a bar-coating machine (K101 Control Coater; RK

PrintCoat Instruments, Ltd.). The wet silica composite films were initially dried at room

temperature in the dark for 24 h before being further cured by a UV-photo surface

processor (PL16-110D; SEN LIGHTS Corp.). The dried films were cured at room

temperature for 5 min to induce polymerization. Consequently, the silica/UV-cured

polymer composite films coated on glass substrate were obtained.

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5.2.4 Characterization

The synthesized HSiNPs were characterized by a X-ray diffraction (XRD, Model

RINT 1100; Rigaku) with Cu Kα radiation (λ = 1.54056 Å). The XRD was operated at

scanning rate of 2 °s-1 (5°-60°, 2θ) with an operating voltage of 40 kV and emission

current 40 mA. The surface morphologies of the samples were observed by a field

emission scanning electron microscope (FE-SEM, JSM7600F; JEOL Ltd.) at an

acceleration voltage of 15 kV. Prior to imaging by the FE-SEM, the samples were

dispersed in EtOH by an ultrasonication. The suspensions were then dropped on a

microgrid (STEM150Cu; Oken Shoji) and dried in the air. The interior morphologies of

the samples were studied using a transmission electron microscope (TEM, JEM-Z2500;

JEOL Ltd.) at 200 kV. The surface properties of the samples were examined by the

Brunauer-Emmett-Teller (BET) method and the Bareett-Joyner-Halenda (BJH) method.

These methods were studied using an automatic surface area analyzer (BELSORP-

miniII-CM) with Nitrogen gas (N 2 ) adsorption desorption isotherm recorded at 77 K.

The optical transmittances of the silica/UV-cured polymer composite films were

measured by a UV-Vis-NIR spectrophotometer (UV3150; SHIMADZU) in the visible

region (400-800 nm). The transmittances of the composite films were then compared to

those of the UV-cured polymer film. For further understanding the effect of the particle

aggregation, the cumulative size distribution of the HSiNPs in UV-curable acrylate

monomer dispersions were studied using a Dynamic light scattering (DLS, Malvern

Zetasizer nano; Sysmex Company). Meanwhile, the light diffusing ability of all films

was examined by an apparatus equipped with a 532 nm laser (Z1M18B-F-532-PZ; Z-

Laser). The films were placed in front of the laser light about 15 cm. Then, a scattered

114
light image of the films shows on a dark background, which is far from them about 26

cm. The surface morphologies of the silica/UV-cured polymer composite films were

studied using the FE-SEM. Before the FE-SEM observation, the films were directly

dried on a hot plate at the temperature of 150 °C for 2 h as some residual solvent

containing in the films may cause of unclear images. The dried samples were further

coated by a thin layer of osmium tetroxide using an osmium plasma coater (OPC60A;

Filagen).

5.3 Results and Discussion

5.3.1. Morphologies and surface properties of hollow silica nanoparticles

The X-ray diffraction patterns (XRD) of the CaCO 3 and the synthesized HSiNPs at

different pH of HCl are shown in the Fig. 5.3.

115
Fig. 5.3 XRD patterns of (a) raw CaCO 3 nanoparticles,

(b) HSiNPs-1, (c) HSiNPs-2 and (d) HSiNPs-5.

116
 The XRD pattern of the CaCO 3 showed in Fig. 5.3 (a) presents the diffraction angle

which is identified as calcite [14]. In contrast, no diffraction pattern of the calcite is

observed in Figs. 5.3 (b), (c) and (d), which show the XRD results of the HSiNPs. It

confirms that the CaCO 3 core-template was completely removed by HCl during acid

treatment [14]. Moreover, all diffraction patterns observed in Figs. 5.3 (b-d) reveal that

the synthesized particles are amorphous [27]. The morphologies of the obtained HSiNPs

after the acid treatment were observed by the FE-SEM.

Fig. 5.4 FE-SEM images of (a) HSiNPs-1, (b) HSiNPs-2 and (c) HSiNPs-5 and

their TEM images as following shown in (d), (e) and (f), by respectively.

117
 Figs. 5.4 (a), (b) and (c) show FE-SEM images of the HSiNPs removed core-

template by HCl at pH of 1, 2, and 5 respectively. They reveal that shape of the HSiNPs

at the different pH still retains cubic and is similar to that of CaCO 3 core-template (as

can be seen in Fig. 5.2). Therefore, the shape of the samples was not modified by the

acid treatment [13, 14, 28]. The surface roughness of the samples gradually increases

with increasing pH of HCl. Meanwhile, window cavities are fragmentary observed on

some cubic particles in each sample. It may be due to a number of silica that may

insufficiently coat on some faces of core-templates [28].

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 Fig. 5.5 Schematic illustration of silica growth

around air produced by removing core-template at pH of (a) 1, (b) 2, and (c) 5.

119
 Moreover, the cubic calcites as the core-template probably have high surface

energy at their vertexes and edges so SiOH may preferentially adsorb on those area to

decrease their surface energy [25]. This behavior can be illustrated in Fig. 5.5. As a

result, the window cavities were produced on faces of the cubic silica nanoparticles. The

results indicate that the different pH of HCl significantly provide the distinctive

morphologies of the HSiNPs. Consequently, it further has an effect on the morphologies

of films that affects the optical properties of those [7].

Figs. 5.4 (d), (e) and (f) respectively illustrate TEM images of HSiNPs-1, HSiNPs-

2 and HSiNPs-5. All the images obviously show hollow interior that completely

confirm the core-template removal and a formation of silica surrounding the core-

templates [13-15, 28]. The silica shell seems to be thicker when the pH of HCl

decreases because the low pH of HCl (high number of H+) more probably induces more

aggregation [14].

120
Fig. 5.6 N 2 -adsorption isotherm with (inset) pore size distribution of

(a) HSiNPs-1, (b) HSiNPs-2 and (c) HSiNPs-5.

121
 Figs. 5.6 (a), (b) and (c) demonstrate the result of nitrogen adsorption isotherm at

77 K with (inset) the pore size distribution of HSiNPs-1, HSiNPs-2 and HSiNPs-5. All

of the adsorption isotherms present the type II isotherm in the IUPAC classification

scheme which is considered as the characteristic of nonporous materials [29]. The

abrupt growth of the adsorptions at high relative pressure (P/P 0 ∼0.9-1.0) is obviously

observed. It is attributed to the adsorption of macropores [29]. The pores existed within

shells and hollow interiors are composed of the HSiNPs [26]. The BJH method was

applied to determine pore size distribution of the various HSiNPs and the results are

demonstrated in inset Fig. 5.6 (a, b and c). The pore of the HSiNPs-1 (inset Fig. 5.6 (a)

is around 39.31 and 53.24 nm. Inset Fig. 5.6 (b) displays the pore of the HSiNPs-2 that

is about 39.31 and 61.52 nm. The pore size distribution of the HSiNPs-2 appears to be

slightly larger than that of the HSiNPs-1. Meanwhile, the pore of the HSiNPs-5 (inset

Fig. 5.6 (c)) is approximately 53.24 and 95.04 nm which is much larger than that of the

HSiNPs-1 and of the HSiNPs-2. This can be explained that the size of the hollow

interior of the HSiNPs-5 is quite larger than that of the HSiNPs-1 and HSiNPs-2, which

corresponds to the TEM results. The pore size of all HSiNPs is slightly different from

the hollow interior size of those. It evidently confirms that the pore and the cavity pore

(window cavity) are probably within the shell of the HSiNPs resulting in the growth of

nitrogen molecules penetration [14]. This explanation is also evidently supported by the

FE-SEM results (as shown in Figs. 5.4 (a), (b) and (c)). The BET specific surface area

of the HSiNPs-1, HSiNPs-2 and HSiNPs-5 is approximately 128.74, 131.65 and 143.15

m2/g, by respectively. It can be inferred that the specific surface area increases when the

pore size increases [30].

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5.3.2 Optical properties and morphologies of the silica/UV-cured polymer

composite films

5.3.2.1 Optical properties of the silica/UV-cured polymer composite films

The total transmittance of the UV-cured polymer film and the silica/UV-cured

polymer composite films embedded with different HSiNPs were measured by the UV-

Vis spectrophotometer in the visible region (400-800 nm). The results are shown in Fig.

5.7.

Fig. 5.7 Total transmittance spectra of the UV-cured polymer film (a)

and the silica/UV-cured polymer composite films embedded with

(b) HSiNPs-1, (c) HSiNPs-2 and (d) HSiNPs-5.

123
 Figs. 5.7 (b), (c) and (d) consecutively display the total transmittance spectra of the

composite films embedded with HSiNPs-1, HSiNPs-2 and HSiNPs-5. They can be seen

that their transmittance spectra is lower than the total transmittance spectra of the UV-

cured polymer film as shown in Fig. 5.7 (a). This is due to the transmitted light that is

less absorbed by silica shell of the embedded particles [20]. Therefore, the intensity of

the transmitted light attenuates. On the other hand, almost the transmitted light can

propagate toward the particles. As a result, the transmittance of the composite films is

still over than 80% indicating their transparency. The transmitted light then interacts

with the particle shell and consequently passes through hollow interior of the particles

leading to inner light scattering [8]. The inner light scattering is possibly increased by

the different refractive indices between the solid shell and hollow interior of the

particles. The light scattering during different refractive indices between materials

relates to Rayleigh scattering [9]. The Rayleigh scattering happens if size of the

scattering particles (heterogeneous phase) is much smaller than the incident light

wavelength [31]. Consequently, the intensity of the light scattering is directly

proportional to 1/λ4 (λ, wavelength of the incident light). In addition, the Rayleigh

scattering affects an enhancement of the transmittance at longer wavelength [9-10, 32].

The enhancement of the transmittance at longer wavelength visibly exhibits in the total

transmittance spectra of the composite films embedded with HSiNPs-1 and HSiNPs-2

as respectively shown in Figs. 5.7 (b) and (c). Nonetheless, the transmittance of the

silica/UV-cured polymer composite film embedded with HSiNPs-5 maintains above

about 80% at longer wavelength. It can be implied that Mie scattering potentially

contributes in the HSiNPs-5 composite film. Based on the Mie scattering, intensity of

the light scattering is independent to wavelength of the light propagation if size of the

124
scattering particles is comparable or larger than the wavelength [9, 33]. The light

scattering greatly penetrates toward direction of the incident light.

To enhance more comprehension of the effect of scattering particle size, the

cumulative size distribution of the different HSiNPs in UV-curable acrylate monomer

dispersions was measured using the DLS. The results are shown in Fig. 5.8.

Fig. 5.8 The cumulative size distribution pattern of the HSiNPs

in UV-curable acrylate monomer dispersions prepared by

(a) HSiNPs-1, (b) HSiNPs-2 and (c) HSiNPs-5.

125
 Fig. 5.8 (a) illustrates the size distribution of the HSiNPs-1, which is around 615.10

nm with a narrow distribution. Fig. 5.8 (b) displays the size distribution of the HSiNPs-

2 that is obviously distinguished to two peaks. Such distinguished peaks are detected

around 458.70 and 5560 nm. Fig. 5.8 (c) presents the size distribution of the HSiNPs-5

and exhibits the distinguished peak. According to the Fig. 5.8, there are three

distinguished peaks that are respectively observed at 190.10, 615.10 and 5560 nm.

When comparing the size distribution of the different HSiNPs, the HSiNPs-5 tends to

provide a larger cumulative size therefore the surface properties of the particles possibly

affect the cumulative size distribution of the particles in the dispersions. Based on the

BET determination, the specific surface area of the HSiNPs-5 is about 143.15 m2/g,

which is the highest surface area to volume ratio as compared to other HSiNPs. The

high surface area to volume expectedly contains high surface energy. The particles with

high surface energy greatly tend to aggregate for minimizing their surface energies [34].

As a result, the cumulative size of the HSiNPs is in order of HSiNPs-1, HSiNPs-2 and

HSiNPs-5 corresponding to the specific surface area results, while the cumulative size

of the HSiNPs is also attributed to the strong interaction and strong adhesion between

the particles [7]. The cumulative size of the HSiNPs can be inferred that almost the

particles in the dispersions should be in aggregation forms. Consequently, the

aggregation has an influence on the film formation with different roughness and

morphologies which leads to distinctive optical properties and light diffusing properties

[7]. Interestingly, the obtained particle sizes correspond to the size of scattering particles

based on both Mie and Rayleigh scatterings. This can be implied that silica/UV-cured

polymer composite films embedded with different HSiNPs probably exhibit both good

light transmittance and good light diffusivity [10].

126
 The diffuse transmittance of the silica/UV-cured polymer composite films

embedded with different HSiNPs was studied using the spectrophotometer equipped

with an integrating sphere. The results are shown in Fig. 5.9.

Fig. 5.9 Diffuse transmittance of the UV-cured polymer film (a)

and the silica/UV-cured polymer composite films embedded with

(b) HSiNPs-1, (c) HSiNPs-2 and (d) HSiNPs-5.

127
 Figs. 5.9 (b), (c) and (d) are consecutively demonstrated the diffuse transmittance

spectra of the composite films embedded with HSiNPs-1, HSiNPs-2 and HSiNPs-5.

They reveal that the diffuse transmittance spectra of the composite films are

significantly higher than that of the UV-cured polymer film (as shown in Fig. 5.9 (a)). It

obviously proves that the presence of the HSiNPs improves the light diffusivity of the

films. The improvement of the light diffusivity could be attributed to the inner light

scattering [7, 9-10]. The inner light scattering is probably occurred by window cavities

with in the shell and hollow interior structure of the HSiNPs [20]. In principle, the inner

light scattering relates to the Mie scattering interfere with the Rayleigh scattering [8-

10]. Meanwhile, the enhancement of the light diffuse transmittance also relates to the

difference of refractive indices between top surface of the composite films and air

(Rayleigh scattering) [9]. The Rayleigh scattering more contributes to longer

wavelength of the light as compared to the Mie scattering [9-10]. Therefore, the

simultaneous reduction of diffuse transmittance at the longer wavelength of the

composite films embedded with HSiNPs-1, HSiNPs-2 as seen in the Fig. 5.9 (b) and (c)

may be attributed to the Rayleigh scattering. Moreover, these results can be inferred that

the diffuse transmittance of those composite films depends on wavelength of incident

light. On the contrary, the characteristic is not detected in the HSiNPs-5 composite film

(as seen in Fig. 5.9 (d)). The HSiNPs-5 composite film still maintains the high diffuse

transmittance at longer wavelength so the wavelength of the incident light slightly

affects it. This can be implied that the Mie scattering more probably occurs in the

HSiNPs-5 film as compared to other composite films. Interestingly, at wavelength of

400 nm, the diffuse transmittance of the composite films embedded with HSiNPs-1,

HSiNPs-2 and HSiNPs-5 (as shown in Fig. 5.9 (b), (c) and (d)) is approximately 84, 91

128
and 87 %, by respectively. They appear to be more than their total transmittance (as

shown in Fig. 5.7 (b), (c) and (d)). It is more possibly that all the composite films have

an anti-reflection property. According to the optical transmittances results, the silica

UV-composite film embedded with HSiNPs-5 exhibits both of the high transparency

and high diffusivity. Meanwhile, the morphologies results from the previous section, the

HSiNPs-5 particles have thinner shell and larger hollow interior size as compared to

other HSiNPs. Therefore, the composite film embedded with the particles which shell

are thinner and the hollow interior are larger is more properly used to be fillers for

optical diffusers in the LCD industry.

The Mie scattering not only supports the transmittance of the light but also

enhances homogenization of the incident light [9]. The homogenization of the UV-cured

polymer film and the silica/UV-cured polymer composite films embedded with different

HSiNPs were studied using the apparatus equipped with the digital camera. The results,

as shown in Fig. 5.10, are further used to be inferred the light diffusing ability of those

films.

129
 Fig. 5.10 The scattered light image of the UV-cured polymer film (a)

and the silica/UV-cured polymer composite films embedded with

(b) HSiNPs-1, (c) HSiNPs-2 and (d) HSiNPs-5.

Fig. 5.10 (a) shows the scattered light image of the UV-cured polymer film that

present a small light spot among the dark area. The image can be inferred that the laser

light propagation forms to small light spot with a little diffusing and other part apart

from light is almost dark. On the contrary, the scattered light image of all composite

films (as seen in Fig. 5.10 (b), (c) and (d)) is obviously larger than that of the UV-cured

film. The images also reveal that the light scattering occurred by the HSiNPs in the

films is able to occur at different angles of the incident light [8] before reforming by

130
itself [7]. The size of the scattered light image of the HSiNPs-1 composite film appears

to be the smallest of the composite films, while the scattered light image size of the

HSiNPs-5 composite film is largest and slightly larger than that of the HSiNPs-2

composite film. However, the appearance of the scattered light image of the HSiNPs-2

resembles to that of the HSiNPs-5 composite film. This is attributed to the surface

morphologies of those films [35]. Meanwhile, the hollow interior size of the HSiNPs-2

and HSiNPs-5 particles is quite similar. Such similar size possibly allows the

penetration of the light scattering to the films with the resemble characteristic. The

sequence of the scattered light image size corresponds to the order of the diffuse

transmittance of the composite films (Fig. 5.9 (b), (c) and (d)) due to the shell thickness

of the HSiNPs. The range of the light scattering emerged from the composite film

embedded with HSiNPs containing thicker shell (HSiNPs-1) is probably smaller than

that with the HSiNPs containing thinner shell (HSiNPs-2 and HSiNPs-5). This is

because the thicker shell can possibly absorb more the light scattering [20].

Consequently, the smaller range of the light scattering assembles to a smaller size of

light spot homogenization [7] corresponding to the scattered light image of the HSiNPs-

1 composite film in Fig. 5.10 (a). The distinct size of the scattered light images can be

implied that the light diffusing ability of the films is significant different. The larger size

of the scattered light image of the composite film should exhibit the higher light

diffusing ability. Additionally, the results visibly confirm that the presence of the

hollow silica nanoparticles existed of window cavities effectively improves the light

diffusing ability of the UV-cured polymer film. Therefore, the hierarchical structure of

the silica is one of the most effective light-weight fillers to apply for production of light

diffuser films, especially in the LCD industry [7-9]. Consequently, the hierarchical

131
silica probably decreases the number of backlight unit in LCD resulting in energy-

saving [8]. A schematic illustration of utilizing the hollow silica nanoparticles as fillers

in light diffuser films in the LCD is shown in Fig. 5.11.

Fig. 5.11 schematic illustration of utilizing the hollow silica nanoparticles to be

fillers in light diffuser films in the LCD.

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5.3.2.2 Morphologies of the silica/UV-cured polymer composite films

A variety of optical transmittances and scattered light image size of the composite

film possibly attributes to the morphologies of composite films [7-9, 32, 35, 36]. The

morphologies of the composite films were therefore studied using the FE-SEM

observation as shown in Fig. 5.12.

133
Fig. 5.12 The FE-SEM images of the UV-cured polymer film embedded with

(a) HSiNPs-1, (b) HSiNPs-2 and (c) HSiNPs-5.

134
 Fig. 5.12 (a) demonstrates the morphologies of the HSiNPs-1 composite film. It

exhibits that the observed size of aggregates on the film surface is uniformly about 1

µm, which is obviously much larger than that of the HSiNPs-1 aggregates in the

dispersion as shown in Fig. 5.8 (a). This result can possibly occur when the solvent has

evaporated through the UV-curing process [37]. Moreover, the size of the aggregates is

a random distribution. On the other hand, the observed size of aggregates obtained from

the HSiNPs-2 composite film (as shown in Fig. 5.12 (b)) is a wide distribution with a

good dispersibility. Fig. 5.12 (c) presents the FE-SEM image of the HSiNPs-5

composite film that reveals a wide distribution of aggregate size. The morphologies of

the film are quite similar to those of the HSiNPs-2 composite film. The similarity of the

morphologies is supported the evidence of the analogous scattered light image pattern

of the HSiNPs-2 and HSiNPs-5 composite film [35]. Furthermore, multiple scattering

probably occurs in all films embedded with HSiNPs because the particles almost appear

in aggregate forms or clusters [38]. Therefore, the light scattering of each particle or

cluster is dependent to each other. Consequently, both the incident light and the

secondary light scattering cause the illumination of each particle. According to these

behaviors, it can be inferred that the higher number of aggregates on the films, the more

of multiple scattering provides. This leads to improve both total and diffuse

transmittances. This reasonable explanation supports the high diffuse transmittance and

larger size of the scattered light image of the HSiNPs-2 and HSiNPs-5 composite films.

According to the film morphologies results, they can be implied that the HSiNPs-2 and

HSiNPs-5 particles are more possibly used to fabricate silica UV-cured polymer

composite film for the appropriate morphologies. Meanwhile, the synthesized HSiNPs

contain window cavities on their shell, which is one of the hierarchical structures.

135
Therefore, it can be concluded that the hierarchical structure of HSiNPs possibly

improves optical properties of the silica UV-cured polymer composite films, while the

hierarchical hollow silica nanoparticles are potentially applied for fillers in optical

diffusers in the LCD industry.

5.4 Conclusion

The morphologies and surface properties of the HSiNPs were successfully modified

by HCl at different pH. The high pH of HCl produces HSiNPs with thinner shells, small

window cavities and high specific surface area. The presence of the hierarchical

structure of HSiNPs within the composite film improves both total and diffuse

transmittances of the UV-cured polymer film. Remarkably, the silica/UV-cured polymer

composite film embedded with HSiNPs-5 containing larger size of hollow interior,

thinner shell and high specific surface area exhibits higher total transmittance (∼80%)

and higher diffuse transmittance (∼80%) when comparing to other composite films. Its

properties still maintain at longer wavelength. Moreover, the film gives the largest size

of the scattered light image indicating its high light diffusing property. This is due to a

good dispersibility of aggregates on the film surface. These results indicate that the

distinct morphologies and surface properties of the HSiNPs are key factors to improve

optical properties of the silica/UV-cured polymer composite films. Furthermore,

HSiNPs-5 is more properly applied for fabricating the silica/UV-cured polymer

composite films in order to achieve high optical transmittances and light diffusing

property. In conclusion, HSiNPs with hierarchical structures are potentially to apply in

the inorganic fillers in light diffuser films of backlight unit of LCDs. The utilization of

136
the hierarchical HSiNPs in LCDs probably reduces number of backlighting unit in the

LCD industry leading to energy-saving and subsequently light-weight LCDs.

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 CHAPTER 6
CONCLUDING REMARKS AND

POTENTIAL DIRECTION FOR FUTURE RESEARCH

143
6.1 Concluding remarks

This work successfully applied silica nanoparticles with a variety of structure for

fabricating high optical properties films. The parameters on silica structure, a

UV-curable acrylate monomer for balancing transmittance and haze of the films were

mainly investigated. The hollow silica nanoparticles were synthesized by inorganic

particle template method before further modifying their morphologies and surface

properties to achieve a proper structure for being fillers in the films. A bar coating

machine and a UV-photo surface processor were used for the film fabrication. The

summary and conclusion of this thesis work are itemized as the following:

Chapter 2, a facile method to prepare the highly loaded silica nanoparticle

dispersions is matching refractive indices of the silica nanoparticles and a UV-curable

acrylate monomer. This method provides a long-term stability of silica dispersions

during dark storage because of the reduction of particle-particle attraction forces.

Therefore, the films prepared by coating these dispersions contain a high number of

silica nanoparticles. Moreover, the total transmittances of the obtained films which are

close to the bare glass indicate the films transparency. Although the multiplication of

the silica nanoparticles in the UV-cured films does not significantly affect their

transmittances, the presence of silica nanoparticles in the UV-cured films produces a

significant difference in the diffuse transmittance. The thin solid silica UV-cured film

containing 30 vol% silica nanoparticles exhibits the highest diffuse transmittance in this

study, which is about 20%. This is due to the increase in the multiple scattering by the

particles in the film. The increase of the silica nanoparticles in the UV-cured films also

provides a good compatibility and good dispersion of the particles which is one of the

main roles to improve the optical properties of the films. Therefore, it can be said that

144
the optical property of the thin solid silica UV-cured film depends on the amount and

distribution of the silica nanoparticles.

In chapter 3, spherical silica nanoparticles containing dense structures were used to

modify UV-cured acrylate films. The films were successfully fabricated by coating

suspensions of silica-acrylate on cleaned glass substrates. The results revealed that the

modified films had a high haze and large range of scattered light. The largest range of

the scattered light was obtained from the film modified with 30 vol% spherical silica

nanoparticles, which exhibited the transmittance about 60% and the haze about 0.26.

The spherical silica nanoparticles may be utilized in the polymer films to obtain a high

diffusing ability which is useful in the field of electronic display technologies.

In chapter 4, silica nanoparticles containing hollow structures which incorporated

with UV-cured acrylate film were successfully done. The films were facilely fabricated

with the suspension of hollow silica nanoparticles calcined at temperature of 400 °C and

a UV-curable acrylate monomer solution was coated. The films become opaque when

the amount of the hollow silica nanoparticles increases. The increased amount of hollow

silica nanoparticles improves both of the optical properties and the light diffusing ability

of the films. Interestingly, a film based on 20 vol% hollow silica nanoparticles gives the

highest total transmittance (93%) and diffuse transmittance (40%) when comparing to

other films in this study. Its total transmittance is also higher than that of the cleaned

glass substrate. Meanwhile, the high amount of hollow silica nanoparticles in the films

provides a larger size of the scattered light image. This can be implied that the films are

able to diffuse the point or the line of the light source. Accordingly, the films based on

the hollow silica nanoparticles as fillers are potentially applied for light diffuser films in

LCDs.

145
 In chapter 5, the morphologies and surface properties of hollow silica nanoparticles

were prosperously controlled by varying pH of HCl in the core-template removal

process. The low pH of HCl produces the thicker shell and larger window cavities of the

hollow silica nanoparticles while the high pH of HCl provides the higher specific

surface area of those. Meanwhile, the presence of hollow silica nanoparticles, which

contain larger size of hollow interiors, thinner shells, larger window cavities and high

specific surface area, in the silica/UV-cured polymer composite film exhibits higher

total transmittance (∼80%) and higher diffuse transmittance (∼80%) when comparing to

other composite films and still maintains at longer wavelength. Moreover, the film gives

the largest size of the scattered light image indicating its high light diffusing property.

Therefore, the distinct morphologies and surface properties of the hollow silica

nanoparticles significantly affect the optical properties and the morphologies of the

resulting films. According to these results of the study, the hollow silica nanoparticles

with hierarchical structure are one of the effective inorganic fillers for light diffuser

films.

Based on the above mentioned results, they can be concluded that the structures and

morphologies of silica, including its aggregation size are main factors to improve

optical transmittances and light diffusing ability of UV-cured acrylate films. These are

due to all silica structures provides more light refraction event inside the films than

orginal UV-cured acrylate films. Meanwhile, the silica containing a hollow structure

more possibly allows light penetration via its hollow interior. It slightly absorbs light on

its solid shell. Furthermore, the hollow structure of silica, which has a window cavity, a

thin shell, a large hollow interior, dramatically improves diffuse transmittance and light

diffusing ability of the films that are better than those of the films embedded with the

146
dense structure of silica. Therefore, the hollow silica nanoparticles with hierarchical

structure are one of the effective inorganic fillers for light diffuser films. The films can

be applied for optical diffusers of the backlight unit of liquid crystal display (LCD)

screens. Consequently, utilizing the hierarchical hollow silica nanoparticles in the field

of optical diffusers probably reduce the number of backlight unit in the LCD industry

leading to energy saving and subsequently light-weight LCD screens.

6.2 Potential directions for future research

The accomplishment of the different structures of silica nanoparticles which

utilized for fabricating high optical properties films has provided opportunities to tune

their morphologies and surface properties. These advantages have in turn exploration of

light interaction in a film with respect to apply as a light diffuser film of back light unit

in the LCD industry. The light diffuser film not only requires high optical performance,

but also need other proper properties; for example, mechanical, thermal, UV-shielding,

fluorescence, well NIR absorption and durability. Therefore, silica surface of both dense

and hollow structures should be developed for further research in order to match with

other binder resins for serving with diverse electronic devices.

147
 RESEARCH ACTIVITIES

Publications

Chapter 2

[1] W. Suthabanditpong, R. Buntem, C. Takai, M. Fuji and T. Shirai, The quantitative

effect of silica nanoparticles on optical properties of thin solid silica UV-cured

films, Surf. Coat. Technol. 279 (2015), 25-31.

Chapter 3

[2] W. Suthabanditpong, C. Takai, M. Fuji, R. Buntem and T. Shirai, Studies of

optical properties of UV-cured acrylate films modified with spherical silica

nanoparticles, Adv. Powder Technol., Article in press, DOI:

10.1016/j.apt.2016.01.022.

Chapter 4

[3] W. Suthabanditpong, M. Tani, C. Takai, M. Fuji, R. Buntem and T. Shirai, Facile

fabrication of light diffuser films based on hollow silica nanoparticles as fillers, Adv.

Powder Technol., Article in press, DOI: 10.1016/j.apt.2016.01.028.

148
 Oral/poster presentation

2015

[1] “Studies on optical properties of UV-cured acrylate films modified by dense silica

nanoparticles” (Oral)

W. Suthabanditpong, M. Fuji, R. Buntem, C. Takai and T. Shirai

The 11th International Conference on Ceramic Materials and Components for

Energy and Environmental Applications (CMCEE), Vancouver, Canada, Jun. 14-

19, 2015.

149
 ACKNOWLEDGEMENTS

This dissertation could not have been accomplished if it had not been contributed

by people surrounding this project. I therefore would like to thank those.

First, I deeply appreciate and admire my supervisor, Prof. Masayoshi Fuji, for his

patience and professional advices throughout the completion of this dissertation. I am

also thankful for his invaluable guidance, kind and moral supports concerning all my

complications apart from the studies during my stay in Japan.

I am thankful to committee members- Prof. Takashi Ida and Prof. Nobuyasu Adachi

for their valuable insights and constructive comments on the earlier version of my work

to make it more scientifically relevant.

I wish to express my deepest gratitude to Assoc. Prof. Takashi Shirai and

Dr. Chika Takai who constant help and generous support with invaluable advice during

the progress of my doctoral studies. They always gave good comments and responded

with great compliments towards my experimental works especially during our end-

report seminar presentation. I also wish to convey my sincere thanks to Dr. Hadi

Razavi-Khosroshahi for his invaluable help for observing my hollow silica particles in

TEM during entire periods of my research.

Many thanks to all the colleagues in Advanced Ceramics Research Center (ACRC)

for their supporting including for the lively and enthusiastic discussions on food, daily

news, the intricacies of the Japanese language and cultures. Those memorable moments

are what made the ACRC my second home.

150
 Also, I cannot forget the kindness of the office secretaries of ACRC, Mrs Shiho

Yoshinaga, Mrs Tomomi Hayashi, Mrs Michiko Michimura and Mrs Kumiko Wakai,

for the supporting during my stay in Japan and for the fast execution and processing of

my pertinent official documents.

I wish to thank the Advanced Low Carbon Technology Research and Development

Program (ALCA) of the Japan Science and Technology Agency (JST), and Research

Assistantship offered in the Processing Group of ACRC for financial support of my

research work. I am also thankful to the JSR Corporation for supplying UV-curable

acrylate monomer, and to the Admatechs, Co. Ltd. for supplying the silica

nanoparticles. Many thanks are extended to the GRANDEX, Co. Ltd. for providing the

hollow silica nanoparticles, and to the Shiraishi Calcium Kaisha, Ltd. for providing the

calcium carbonate.

My deep appreciation is extended to Asst. Prof. Dr. Radchada Buntem for her

encouragement in taking-up further studies. A special thank goes to all of my lovely

friends for their everlasting supports/prayers.

Finally, I am deeply indebted and grateful to my parents, my brothers and my

sisters, for their unconditional love and moral support, and for being the greatest family

on earth. The love and encouragements kept me going during challenging times in

Japan.

Walaiporn Suthabanditpong

151