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

xvi

J/m2 Joule per Meter square

g/mol Gram per Mol

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.