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A CULLET-KAOLIN CERAMIC FROM RECYCLE GLASS
SAFWAN BIN AHMAD PAUZI
A thesis submitted in fulfillment of the
requirement for the award of the degree of
Master of Science (Physics)
Faculty of Science
Universiti Teknologi Malaysia
FEBRUARY 2011
iii
To my beloved Ayahanda and Bonda: Ahmad Pauzi Mamat and Che Haripah Awg
Kechik and to my sweet brothers and sister
iv
ACKNOWLEDGEMENT
In the name of Allah, Most Gracious, Most Merciful. Praise be to Allah, the
Cherisher and Sustainer of the worlds. For His Mercy has given me the strength and
time to complete this project.
I would like to express my appreciation to my respected supervisor, Professor
Dr Md Rahim Sahar and Associate Professor Dr. Supar Rohani for their supervision,
guidance, enjoyable discussion and motivation throughout this study.
Beside them, I have much pleasure to those who have assisted me in various
ways in carrying out the experimental works. They are my beloved friends, Mutia
Suhaibah Abdullah, Musdalilah Ahmad Salim, Shahira Alias, Suhailah Abdullah,
Aishah Ahmad Fuzi, Shawal Hussin, Nur Hidayah Che Mat and others. Also, I
would like to express my gratitude towards all staff that involve during my research.
My thanks are also due to Universiti Teknologi Malaysia through IRGS grant
vote 78920 for giving financial support for my research. Thanks are also due to
Universiti Teknologi Malaysia for giving me the opportunity to pursue my master.
Last but not least, my appreciations go to my special friends, Nor Ilani Taha
and my family for continuing support, patience throughout the present work and who
have favored me with correspondence, I have much pleasure in expressing my
obligation. May Allah bless those who have involved in this project.
v
ABSTRACT
A series of ceramic based on (x) Cullet – (70-x) Kaolin – (30) Alumina
where 10≤ x ≤ 60 wt% has successfully been prepared by a solid state reaction. The
density has been determined by Archimedes principle while the impact energy has
been obtained by Izod Impact Test. The permeability coefficient has been
determined by Constant Head Permeability test method using distilled water at pH 7
while their porosity and has been estimated using BET analysis method. The phase
occurrence of these ceramic has been determined using X-ray Diffraction (XRD)
method before being confirmed by Energy-Dispersive Analysis of X-rays (EDAX).
The microstructure and surface morphology have been observed using Scanning
Electron Microscopy (SEM) and the existence of water content has been determine
using Infrared Spectroscopy (IR) technique. It is found that the bulk density and
impact energy is in the range of (1.785 - 2.2817) gcm-3
and (2.183 - 6.320) kJm-2
respectively, depending on the cullet content. Meanwhile, the permeability
coefficient is found to be in the range of (5.208x10-4
- 1.812x10-4
) cms-1
, decreases
as cullet content is increased. The porosity is in the range of (13.34 – 14.5) m2g and
analysis shows that samples with 30-35 wt% of cullet exhibit optimum value. It is
also found out that quartz and cristobalite are two major phases that occur in the
ceramic while the minor phases are aluminium oxide, devitrite and sodium silicate.
The structural morphology in the form of lamellar is observed to aggregate in the
matrix with the size become increasingly larger as the kaolin content is increased.
An EDX analysis show that the ceramic composition is mainly consists of Si, Al and
O with a trace of K, Ca, Na and Pt as minor elements. Meanwhile, the IR
Spectroscopy shows that the OH- content decreases as cullet content is increased
vi
ABSTRAK
Satu siri sampel seramik berdasarkan (X) Kulet – (70-X) Kaolin – 30
Alumina di mana 10≤ X ≤ 60 peratus berat telah berjaya disediakan dengan kaedah
tindakbalas keadaan pepejal. Ketumpatan sampel ditentukan dengan Prinsip
Archimedes manakala ujian tenaga hentaman diperolehi melalui Ujian Izod.
Keliangan sampel telah ditentukan dengan kaedah analisis BET dan pekali
ketelapannya ditentukan dengan menggunakan ujian kepala ketelapan malar.
Sementara itu, perubahan fasa sampel ditentukan menggunakan kaedah pembelauan
sinar-X (XRD) yang mana turut juga dibuktikan oleh analisis penyebaran tenaga
sinar-X(EDAX). Struktur mikro dan morfologi permukaan telah ditentukan dengan
menggunakan Mikroskop Pengimbasan Elektron (SEM) dan Spektroskopi
Inframerah (IR) telah digunakan untuk menentukan kewujudan kandungan air di
dalam sampel. Ketumpatan sampel adalah di dalam julat 1.785 gcm-3
hingga 2.2817
gcm-3
manakala tenaga hentaman yang menggunakan ujian izod adalah di dalam
julat 2.183 KJ/m2 hingga 6.320 KJ/m
2 bergantung pada kandungan kulet. Pekali
ketelapan adalah diantara 5.208x10-4
cms-1
ke 1.812x10-4
cms-1
yang berada dalam
tren menurun. Kaedah analisis BET menunjukkan porositi adalah didalam julat
13.34m2g hingga 14.5m
2g dan sampel-sampel dengan jisim 30-35 peratus kaca
mempunyai keliangan yang optimum. Juga, terdapat dua fasa utama yang dinamakan
fasa kuartz dan fasa kristobalite wujud di dalam seramik manakala terdapat juga
fasa-fasa minor seperti Aluminium Oksida, “devitrite” dan natrium silikat. Morfologi
sampel mendedahkan strukturnya adalah berbentuk lamela dengan saiz plat menjadi
semakin besar dengan peningkatan kandungan kaolin. Analisis EDX digunakan
untuk mengukur komposisi dalam kawasan sampel yang dipilih. Elemen yang
banyak dikenalpasti adalah Si, Al dan O dan lain-lain atom seperti K, Ca, Na dan Pt..
Sementara itu, Spektroskopi Inframerah juga digunakan untuk menggambarkan
kesan kumpulan OH dalam sampel. Spektroskopi Inframerah menunjukkan bahawa
dengan penurunan kumpulan OH, ketelepan akan meningkat.
vii
TABLE OF CONTENTS
CHAPTER TITLE PAGE
THESIS TITLE i
DECLARATION SHEET ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF FIGURES xi
LIST OF TABLES xiii
LIST OF SYMBOLS AND ABREVIATIONS xiv
CHAPTER 1 INTRODUCTION 1
1.1 Problem Overview 1
1.2 Problem Statement 5
1.3 Aim of the Project 6
1.4 Objective of Study 6
1.5 Scope of Study 7
1.6 Significance of the Study 7
viii
CHAPTER 2 LITERATURE REVIEW 8
2.1 Ceramic 8
2.1.1 Introduction 8
2.1.2 Definitions 9
2.1.3 Ceramic Properties 11
2.1.4 Types of Ceramic 12
2.1.4.1 Crystalline Ceramics 13
2.1.4.2 Non-Crystalline Ceramics 13
2.2 Recycle Glass 14
2.2.1 Introduction 14
2.2.2 Definitions of Glass 15
2.2.3 Glass Container 16
2.2.4 Cullet 18
2.3 Kaolin 19
2.3.1 Introduction 19
2.3.2 Kaolin Forming 19
2.3.3 Kaolin Structure 20
2.3.4 Characteristics of Kaolinite 23
2.4 Forming Processes 25
2.4.1 Introduction 25
2.4.2 Slip Casting 25
2.5 Polyethylene Glycol (PEG) 27
2.6 Ceramic Sintering 28
2.7 Density 29
2.8 Izod Test 30
2.9 BET Specific Surface Area 32
2.10 Permeability Test 34
2.11 X-ray Diffraction 35
2.12 Scanning Electron Microscope (SEM) 37
2.13 Energy Dispersive X-ray Analysis (EDX) 39
2.14 Fourier Transform Infrared Spectroscopy (FTIR) 42
ix
CHAPTER 3 EXPERIMENTAL 45
3.1 Introduction 45
3.2 Sample Preparation 46
3.3 Raw Material 50
3.3.1 Kaolin 50
3.3.2 Cullet 50
3.3.3 Aluminium Oxide 51
3.3.4 Polyethylene Glycol (PEG) 52
3.4 Sample Characterization 52
3.4.1 Density Test 52
3.4.2 Izod Impact Strength Testing 53
3.4.3 Brunauer-Emmett-Teller (B.E.T) Test 54
3.4.4 Permeability Test 55
3.4.5 X-ray Diffraction 56
3.4.6 Scanning Electron Microscope (SEM) 57
3.4.7 Energy Dispersive X-ray Analysis (EDX) 58
3.4.8 FTIR 58
CHAPTER 4 RESULTS AND DISCUSSION 60
4.1 Introduction 60
4.2 Sample Preparation 60
4.3 Density 61
4.3 Impact Energy 62
4.4 Brunauer-Emnett-Teller (BET) Analysis 64
4.5 Permeability Test 66
4.6 X-ray Diffraction (XRD) 68
4.7 Scanning Electron Microscope (SEM) 72
4.7.1 Ceramic Microstructure 72
4.7.2 Surface Morphology 74
4.8 EDX Analysis 76
4.9 Fourier Transform Infra Red 79
x
CHAPTER 5 CONCLUSION 81
5.1 Introduction 81
5.2 Conclusions 81
5.2.1 Sample Preparation 82
5.2.2 Physical and Mechanical Properties 82
5.2.3 Phase Occurrence 82
5.2.4 Microstructure and Surface Morphology 83
5.2.5 Permeability of the Sample 83
5.2.6 Elemental Composition 84
5.2.7 Specific Surface Area and Particle Size 84
5.3 Suggestions for Future Work 84
5.3.1 Cullet 85
5.3.2 Firing Temperature 86
REFERENCES 86
xi
LIST OF FIGURES
NO TITLE PAGE
2.1 Atom arrangements in the unit cell of a two layer mineral
(schematic)
21
2.2 Structure of 1:1 clay minerals 22
2.3 Structure of 2:1 clay minerals 23
2.4 Morphology of kaolin 24
2.5 Izod Test drawing 31
2.6 Schematic of the Izod impact test 31
2.7 Principle of X-ray Diffraction 36
2.8 Cross section of typical Scanning Electron Microscope 39
2.9
Elements in an EDX spectrum are identified based on the energy
content of the X-rays emitted by their electrons as these electrons
transfer from a higher-energy shell to a lower-energy one
41
2.10 Example of EDX spectrum 42
2.11
Schematic sketch of the essential features of a Fourier transform
infrared (FTIR) spectrometer
43
2.12 An example scan of an FTIR spectrum 44
3.1 Flow Chart of sample preparation 47
3.2 Polyethylene Jar for a mixing purpose
48
3.3 Diagram of PoP moulding 49
3.4 Izod Test instrument 54
xii
3.5 Micromeritics ASAP 2010 instrument 55
3.6 Diagram of apparatus arrangement for permeability test 56
3.7
X-ray Diffractometer (Siemens Diffractometer D5000) at Faculty
of Mechanical Engineering, Universiti Teknologi Malaysia,
Skudai
57
3.8
SEM at Ibnu Sina Institute, Universiti Teknologi Malaysia,
Skudai
58
3.9
FTIR spectroscopy at Chemistry Department, Universiti
Teknologi Malaysia, Skudai
59
4.1 Density of glasses versus cullet level sintered at 1000C 62
4.2 Impact Energy of glasses versus cullet level sintered at 1000C 64
4.3 Specific surface area and particle size versus cullet level sintered
at 1000C
66
4.4 Permeability coefficients of sintered ceramic samples 67
4.5
X-ray Diffraction pattern after sintered at 1000C (q: quartz; C:
cristobalite; a: aluminium oxide, d: devitrite; s: sodium silicate)
70
4.6 X-ray Diffraction plane for fired samples 71
4.7 Microstructure of sintered ceramics at 1000C for 30 minutes 73
4.8 Surface morphology of sintered ceramics 75
4.9 Elemental composition of ceramic as analysed by EDX 78
4.10 The IR spectra of cullet-kaolin ceramic at different cullet level 80
xiii
LIST OF TABLES
NO TITLE PAGE
1.1 Breakdown of solid waste created by Malaysians in 2003 2
2.1 Typical Chemical Composition of Container Glass 18
2.2 The characteristics of PEG 28
3.1 Nominal composition (wt %) of the samples 48
3.2 The specification for the preparation of Plaster of Paris (PoP)
moulding
49
3.3 A typical flint cullet composition 51
4.1 Density of cullet-kaolin ceramic at different cullet level 61
4.2 Impact Energy of cullet-kaolin ceramic at different cullet level 63
4.3
Specific Surface Area and particle size of Cullet-Kaolin
ceramic at different cullet level
65
4.4 Permeability coefficient of recycle glass-kaolin ceramic 67
4.5 Atomic percentage in the sample 76
xiv
LIST OF SYMBOLS AND ABREVIATIONS
SiO2 Silicon Oxide
CaO Calcium Oxide
Na2O Sodium Oxide
Al2O3 Aluminium Oxide
MgO Magnesium Oxide
K2O Potassium Oxide
Fe2O3 Iron Oxide
H2O Water
Cr2O3 Chromium Oxide
Pt Platinum
Na Sodium
Ca Calcium
Al Aluminium
O Oxygen
Si Silicon
K Potassium
Cu Copper
OH- Hydroxyl
O2- Oxygen ion
H+ Hydrogen ion
[Si2O5]2- Silicon Pentoxide ion
Al2Si2O5(OH)4 Kaolinite
xv
Mg3(Si2O5)2(OH)2 Talc
KAl3Si3O10(OH)2 Muscovite
KBr Potassium bromide
FTIR Fourier Transform Infrared
XRF X-ray Fluorescence
EDAX Energy Dispersive Analysis of X-ray
SEM Scanning Electron Microscope
BET Brunauer-Emnett-Teller
XRD X-ray Diffraction
ASTM American Standard Testing Material
PoP Plaster of Paris
ICDD International Centre for Diffraction Data
mL Milliliter
cm Centimeter
cm2 Centimeter square
K Kelvin
nm Nanometer
α Alfa
Beta
Gamma
Density
Theta
Å Angstrom
C Degree Celsius
M Molar
m Mass
V Volume
m Micrometer
g/cm3 Gram per Centimeter cubic
ft-lb/in Pound per Inch
J/cm Joule per Centimeter
m2/kg Meter square per Kilogram
P/Po Pressure difference
CHAPTER 1
INTRODUCTION
1.1 Problem Overview
Nowadays, people have becoming more aware on the global wastes issues. It
is reported that over 15,000 tons of waste has been produced every day.
Approximately ten percent(10%) municipal refuse is glass, most of which is in the
form of discarded containers from beverages, food products and the like (Duane A.
Mosch, 1998). The quantities are very huge and urged steps need to be taken to
reduce the increasing quantity of waste. The clock is ticking and it is only a matter of
time before the space to dispose of them is run out. Much waste glass are dumped in
landfill sites but in many countries there are a limited number of suitable sites and
furthermore this disposal method is generally considered to be environmentally
unfriendly. Because of the undesirability of dumping, the direct costs to the waste
producer (handling, transport costs, etc.) are in many cases significantly increased by
government taxes. A consequence of these environmental and financial
considerations is that there is a growing demand for wastes to be re-used or recycled.
Thus re-use of cullet for the production of ceramics is a promising development.
2
Recycling had attracted a great interest as a major way to reduce wastes.
Recycling reduces pollution and as well as saves energy. In the developed countries,
a growing interest in conservation of via recycling has led to an increasing in the
recovery of solid wastes including glass, some of which is re-melted and some had
turn wastes into something useful such as ceramic.
In Malaysia itself, experts believed a landfill exist can last 10 years longer if
Malaysians do recycled their 50% of waste. As examples, the residents of Johor
Bahru itself generate 1300 tons of waste every day and it will take only 3 days to fill
the entire length of the Johor Causeway with this amount of waste. “Currently, our
country needs to spend RM400 mil just to manage these wastes. We can use
these savings on other development projects. Recycling can also reduce our
need to extract new economic resources while the industry itself can generate
business opportunities and jobs,”(Abdullah, 2003). If compared to other developed
countries, where the recycling rate is about 30% to 47%, Malaysia is falling behind.
There is not enough number of recycling centers and the practice is not widespread.
Also, despite the recycling program being implemented three years ago, it had only
managed a recycling rate of around 3% (Abdullah, 2003). Table 1.1 demonstrates
roughly solid waste generated by Malaysians.
Table 1.1 : Breakdown of solid waste created by Malaysians in 2003 (Abdullah,
2003)
Types of Waste
Materials Weight (%)
Paper 27
Steel 3.9
Glass 3.7
Plastic 16.4
Others 12.5
3
To encourage recycling and minimize waste, there are national regulations
and legislated guidelines being implemented in reinforcing environmental protection
measures. There is a great interest in finding alternative technological options
capablity, at the same time, to convert a waste product into a new marketable
material. The transformation recycle glass (cullet) by wet forming process appears a
promising solution because it is able to convert, at relatively low cost, simple
chemical compositions into useful materials with good technological properties.
Cullet waste glass (Holloway, 1973) means the broken bottle. It is a special
terminology used in glass industry. This word probably derived from the French
word, collet, as collat. In those days of hand-pressed glass, it refers to the portion of
glass cut off from the article which will be discarded or remelted later, the shape of
which looked like a collar. Cullet has been used in glass container manufacturing
industry since the earliest days of glass making for the purpose of assisting melting
and saving raw materials consumption (Owen-Broadway, 1994). It has been reported
that for every 60% of cullet used, 30% of fuel energy may be saved (Sahar et al.,
2003)
Cullet is commonly used in various manufacturing activities, (for example
glass reforming or melting additives for ceramics), mainly due to its low softening
temperature. The Italian production of cullet in the year 2005 was around 106 tons.
Great importance must be given to the colour of cullet while proposing its reuse for
the production of ceramics, in particular light colour products require colourless
cullet (Asquini et al., 2008).
Collection of cullet is much depending on the willingness of the glass
industry to collect and to process them. There are several reasons why cullet has to
be recycled. It has been known that sand is natural resources that highly contained
with up 70%-90% of silica which is the main component for glass production. If all
the glass industries are simultaneously using this material, the chance is the
tarnishing of environment in every part of the world. Every day, tonnages of bottles
4
and containers are being produce and marketed. If this glasses are not being recycle,
then the abundance of cullet are being dumped somewhere. This activity would
require some space. It has been known that for every 1 ton of glass container, it
requires about 3 meter square of space. If this happen and the space factor is very
crucial, then the space could be waste in term of profit and economics.
This product would be firing in the furnace to obtain a solid sample.
Generally all the steps, since raw material preparation, drying conditions and firing
cycle are going to have a strong influence in the product qualities. The firing cycle
influence is related to the kind of furnace, firing atmosphere, maximum temperature
and soaking time. All these parameters are related to quality and cost of the products.
Because all of these parameters, firing temperature is set to 1000oC and 30 minutes
soaking time. Although cullet-kaolin has been previously fabricated, very little
information concerning on the microstructure and permeation rate of ceramic.
Therefore this study has the significant importance and the result will be presented
and discussed with respect to cullet content.
Ceramics is well known material and has been given an increasing attention
for their successful applications in bioceramics (Engin, 1999), catalyst supports
(Ismagilov, 1997), hot gases filter (Jo, 1997), liquid food production (Bennasar,
1982), sensors (Burgraaf, 1996), and membrane reactors (Coronas, 1994). Glass
cullet (GC) is classified, in the European Waste Catalogue. In the present research a
recycle glass containing SiO2, CaO, Na2O, Al2O3 as most abundant components and
minimal amounts of MgO, K2O and Fe2O3 was used (Maschio et al., 2009).
In another study soda-lime float or container glass was introduced, in
replacement of soda feldspar in typical porcelain stoneware bodies (up to 10 wt.%)
that underwent a laboratory simulation of tile making process, with a technological
and compositional characterization of both fired and unfired tiles. Soda-lime glass
had no significant effect on semi-finished products, but it influenced remarkably the
firing behaviour, increasing shrinkage and closed porosity, decreasing open porosity
5
and bulk density, and lowering mechanical and tribological performances (Jiann-
Yang Hwang, 2006).
A new ceramic materials can be produce by adding a recycle glass(cullet) as
part in new materials as reported elsewhere (Luz, 2007; Maschio et al., 2009). For
example, the resulting ceramics with porous surfaces applicable for filter application,
tile, brick, etc can be formed. In some cases a kaolin (Al2O3.2SiO2.2H2O) powder can
be employed as a starting material. The detailed sequence of chemical reactions
during the sintering of kaolin bodies is very complicated, depending on the
compositions of raw materials, characteristics of powders, and fabrication
conditions. Commonly used kaolin powder containing a small amount of quartz, then
by adding recycle glass (cullet) which acts as fluxing agent (Bragança & Bergmann,
2004) and alumina to increase the strength (Sahar et al., 2003), a new ceramic can be
formed.
1.2 Problem Statement
This research is meant to reduce the problem of waste glass. A large amount
of waste glass has already affected the environment and an urged steps must be taken
to encounter the problem. Also, these large amounts of waste glass will require a lot
of space to store them and thus the space value would be wasted. This research will
encounter such problems by turning them into a new ceramic product. In this
research, recycle glass will be mixed with kaolin to produce ceramic with attractive
properties. By doing so, not only new ceramic will be formed but more important is
that the problems stated before can be solved.
6
1.3 Aim of the Project
The aim of this work is to study the possibility of the use of glass powder
waste (cullet), in ceramic mixtures, for manufacturing of new ceramic material
namely Cullet-Kaolin ceramic. Cullet powder when incorporated into a mixture of
kaolin and alumina has a good potential as a new fluxing agent in replacement of
traditional feldspar and open possibility to obtain a porous microstructure during
sintering. This project will stress on the effect of cullet on ceramic. Thus a suitable
combination of cullet, kaolin and alumina would be determined. The effects due to
the use of cullet powder is investigated in laboratory experiments and discussed in
terms of cullet level and physical–mechanical properties (Luz, 2007). Therefore, the
use of cullet as part of the composition would likely to reduce this effect and thus
conserve the energy resources.
1.4 Objective of Study
The main objectives of this research are ;
i. To prepare a new ceramic material samples based on mixtures of
cullet-kaolin ceramic materials.
ii. To determine the physical properties such as density and impact
energy of the sample.
iii. To determine the permeability coefficient of the sample.
iv. To investigate the sample surface morphology.
v. To study the phase changes in the sample at different cullet level.
vi. To determine the specific surface area and particle size of the sample.
vii. To analyse the composition of the sample.
7
1.5 Scope of Study
To achieve the objectives that have been listed, the scope of research is
outlined.
i. Preparations of new Cullet-Kaolin ceramic based on (X) Recycle
Glass – (70-X) Kaolin – 30 Alumina where 10≤ X ≤ 60 weight
percent.
ii. Determination of density using Archimedes Principle and Impact
energy using Izod Test.
iii. Determination of permeability coefficient using Constant Head
Permeability test.
iv. Determination of sample morphology using Scanning Electron
Microscope.
v. Determination of phase changes using X-Ray Diffraction.
vi. Determination of Specific Surface Area and particle size using
BET (Brunauer-Emmet-Teller).
vii. Determination of composition of sample using Energy dispersive X-
Ray analysis.
viii. Determination of OH-group
1.6 Significance of the Study
In the fast growing field of ceramic material, there are lots of their
applications in this modern world such as tiles, filter water, kitchenware and
toiletries. Because of this useful application, a new Cullet-Kaolin ceramic probably
could be use in one this application. Furthermore, this ceramic is one of the ways to
preserve and avoid natural resources such as silica and clay from tarnishing forever.