STRUCTURAL CHARACTERIZATION OF ASYMMETRIC YTTRIA...

STRUCTURAL CHARACTERIZATION OF ASYMMETRIC YTTRIA-

STABILIZED ZIRCONIA HOLLOW FIBRE MEMBRANE

SYAFIKAH HUDA BINTI PAIMAN

UNIVERSITI TEKNOLOGI MALAYSIA

STRUCTURAL CHARACTERIZATION OF ASYMMETRIC YTTRIA-

STABILIZED ZIRCONIA HOLLOW FIBRE MEMBRANE

SYAFIKAH HUDA BINTI PAIMAN

A thesis submitted in fulfilment of the

requirement for the awards of

the degree of Master of Engineering (Gas)

Faculty of Chemical and Energy Engineering

Universiti Teknologi Malaysia

FEBRUARY 2016

iii

ACKNOWLEDGEMENT

Alhamdulillah. Praised to Allah SWT with His blessed and guidance I got

the opportunity and successfully finished my master study. Deeply thanks to my

parents (Paiman bin Sanusi and Rozi Noriah binti Sukarno), my sister (Nurul Azwa)

and my brother for their constant encouragement, advice and du’a. I truly appreciate

their love, tolerance and understanding.

I would sincerely like to thank my supervisor Dr. Mukhlis bin A Rahman for

his guidance, endless support and du’a throughout my master study and for the

opportunities I have been given to attend conference which give a chance to develop

my presentation skill. I felt very comfortable expressing my opinion at all times and I

am grateful to have benefited from his extensive experience and knowledge not only

in membrane study but also in many other aspects of life as a researcher and as a

slave of Allah in general. I would like to thank Dr. Mohd Hafiz Dzarfan bin Othman

for his excellent advice offered as my co-supervisor.

Special thanks to my friends Miss Halimah, Miss Shuhaida, Miss Fazliana,

Mrs. Iera, Muhazri, Zureen, Azuwa, Azlan and Hilmi Mohamad for their endless

help from the very beginning of instrument installation to the experimental work and

for their kindly help and advice.. Also, thanks to AMTEC’s research officer for help

I have received and everyone in the AMTEC team. Lastly, I am grateful to Ministry

of Science, Technology and Innovation (MOSTI) and Universiti Teknologi Malaysia

(UTM) for financial supports.

iv

ABSTRACT

Ceramic membrane is proven to overcome a limitation of using polymeric

membrane for applications that requires a high temperature and pressure. In this

study, Yttria-stabilized zirconia (YSZ) was selected as a ceramic material due to its

superior mechanical strength. YSZ hollow fibre membrane was fabricated using

combined dry-wet phase inversion and sintering technique. Four parameters involved

during fabrication process have been varied systematically to study the effect on

YSZ hollow fibre membrane structure and properties. The ceramic loading was

varied from 55 wt.% to 67 wt.% and the YSZ/polyethersulfone (PESf) ratio was

varied from 7 to 10 during YSZ suspension preparations. Then, the air-gap length

was varied from 15 cm to 30 cm during spinning process. Lastly, the sintering

temperature was varied from 1250 oC to 1400

oC during sintering step. The YSZ

hollow fibre membrane produced were characterized in terms of morphology,

mechanical strength, apparent porosity, pure water flux and solute rejection. The

results successfully showed an asymmetric YSZ hollow fibre membranes consist of

finger-like voids and sponge-like voids were produced. The YSZ suspension

viscosity was increased with the increase of YSZ loading and decrease of YSZ/PESf

ratio. High suspension viscosity favored the growth of finger-like voids and limited

the formation of sponge-like region across the membrane. This result was similar to

increase of the air-gap length during spinning. Significant densification occurred at

the sponge-like region during sintering. The formation of isolated voids at 1400 oC

hindered the pure water permeation. However, the mechanical strength increased

with the sintering temperature. From the permeation test, the YSZ hollow fiber

membrane prepared with 65 wt.% loading, ceramic/polymer ratio of 10, spinning at

20 cm air-gap length and sintered at 1300 oC was the most preferable membrane.

This membrane had a pure water flux of 118.4 Lm-².hr

-¹ with a molecular weight cut

off of 50 – 60 kDa and mechanical strength of 224 MPa.

v

ABSTRAK

Membran seramik terbukti boleh mengatasi masalah penggunaan membran

polimer untuk aplikasi yang memerlukan suhu dan tekanan yang tinggi. Yttria-stabil

zirkonia (YSZ) telah dipilih sebagai bahan seramik dalam kajian ini kerana kekuatan

mekanikal yang tinggi. Membran asimetrik gentian gerongga YSZ telah dihasilkan

menggunakan gabungan teknik penyongsangan fasa kering dan pensinteran. Empat

parameter yang terlibat telah diubah semasa proses penghasilan untuk mengkaji

kesan terhadap struktur dan sifat membran gentian gerongga YSZ. Kandungan

seramik diubah dari 55 % jisim hingga 67 % jisim dan nisbah YSZ/polietersulfon

(PESf) telah diubah dari 7 hingga 10 semasa penghasilan larutan YSZ. Selain itu,

panjang sela udara semasa proses pemejaman diubah daripada 15 cm hingga 30 cm.

Akhir sekali, suhu ketika proses pembakaran dinaikkan dari 1250 oC hingga 1400

oC.

Membran gentian gerongga YSZ yang terhasil dicirikan dari segi morfologi,

kekuatan mekanikal, keliangan ketara, kebolehtelapan air tulen dan penolakan bahan

larut. Keputusan menunjukkan membran asimetrik gentian gerongga YSZ terdiri

daripada lompang seperti jari dan lompang seperti span berjaya dihasilkan. Kelikatan

larutan YSZ meningkat dengan peningkatan kandungan YSZ dan pengurangan

nisbah YSZ/PESf. Kelikatan yang tinggi, kadar pertumbuhan lompang seperti jari

adalah tinggi dan menyekat pertumbuhan lompang seperti span dalam membran.

Keputusan ini sama dengan kesan peningkatan jarak sela udara semasa proses

pemejaman. Peningkatan suhu pembakaran menyebabkan pemadatan pada bahagian

struktur-mikro dan mengurangkan keliangan. Pembentukan lompang terpencil pada

suhu 1400 oC telah menghalang penelapan air tulen. Namun, peningkatan suhu

pembakaran telah meningkatkan kekuatan mekanikal. Ujian penelapan menunjukkan,

membran gentian gerongga YSZ yang dihasilkan dengan kandungan 65 % jisim,

nisbah seramik/polimer 10, panjang sela udara 20 cm dan disinter pada suhu 1300 oC

menghasilkan fluks air tulen sebanyak 118.4 Lm-².hr

-¹ dengan berat molekul terputus

sebanyak 50 hingga 60 kDa dan kekuatan mekanikal 224 MPa.

vi

TABLE OF CONTENT

CHAPTER TITLE PAGE

TITLE PAGE i

DECLARATION ii

ACKNOWLEDGEMENT iii

ABSTRACT iv

ABSTRAK v

TABLE OF CONTENT v

LIST OF TABLES ix

LIST OF FIGURES xi

LIST OF ABBREVIATIONS xv

LIST OF SYMBOLS xvii

LIST OF APPENDICES xxvix

1 INTRODUCTION 1

1.1 Background of Study 1

1.2 Problem Statement 4

1.3 Objective 5

1.4 Scope of Study 6

1.5 Significant of Study 7

1.6 Thesis Structure 7

2 LITERATURE REVIEW 9

2.1 Introduction of Ceramic Membrane 9

2.2 The Configuration of Ceramic Membrane 13

2.3 Fabrication Method of Ceramic Membrane 15

2.3.1 Slip Casting 16

vii

2.3.2 Tape Casting 17

2.3.3 Dip Coating 18

2.3.4 Extrusion 20

2.4 Ceramic Hollow Fibre through Combined Phase Inversion

and Sintering Process 21

2.4.1 Ceramic Suspension 23

2.4.2 Spinning 27

2.4.3 Sintering 32

2.5 Applications 36

2.5.1 Membrane Filtration 36

2.5.2 Catalyst Substrate for Microreactor 40

3 RESEARCH METHODOLOGY 42

3.1 Introduction 42

3.2 Materials 44

3.2.1 Zirconia 45

3.3 Fabrication of Ceramic Hollow Fibre Membrane 47

3.3.1 Preparation of Ceramic Suspension Solution 48

3.3.2 Spinning Process 50

3.3.3 Sintering Process 52

3.4 Characterization 54

3.4.1 Scanning Electron Microscopy 54

3.4.2 Three Point Bending Test 55

3.4.3 X-Ray Diffraction 56

3.4.4 Atomic Force Microscopy 56

3.4.5 Viscosity 56

3.4.6 Apparent Porosity 57

3.4.7 Pure Water Permeation 57

3.4.8 Solute Rejection 59

4 RESULTS AND DISCUSSIONS 61

4.1 The Effect of Ceramic Loading on the YSZ Hollow Fibre

Membrane 62

4.1.1 Rheology of Ceramic Suspension 62

viii

4.1.2 Morphology 64

4.1.3 Mechanical Properties 66

4.2 The Effect of Air-gap Length on the YSZ Hollow Fibre

Membrane 68

4.2.1 Morphology 68


4.3 The Effect of Ceramic/Polymer Ratio on the YSZ Hollow

Fibre Membrane 73

4.3.1 Rheology of Ceramic Suspension 73

4.3.2 Morphology 74


4.4 The Effect of Sintering Temperature on the YSZ Hollow

Fibre Membrane 78

4.4.1 Morphology 78


4.4.3 Apparent Porosity 86

4.4.4 XRD Pattern 87

4.4.5 Pure Water Flux 88

4.4.6 PEG Rejection 90

5 CONCLUSION AND RECOMMENDATION 92

5.1 Conclusion 92

5.2 Recommendation 94

REFERENCES 96

APPENDIX A 105

APPENDIX B 106

ix

LIST OF TABLES

TABLE NO. TITLE PAGE

2.1 The general comparison of ceramic, metal and polymer 10

2.2 The applications for the porous ceramic membrane 12

2.3 The applications for the dense ceramic membrane 12

2.4 The comparison between hollow fibre, tubular and flat

sheet membrane configuration 15

2.5 The list of dip-coating method 20

2.6 The factors that affecting the suspension solution

preparation 25

2.7 The spinning condition involves during spinning process 28

2.8 Microstructural changes observed during sintering

process 35

2.9 The sintering conditions that effect the final membrane

formation 36

2.10 The type and characteristic of membrane filtration 38

3.1 Mechanical properties of stabilized zirconia 47

3.2 The composition of YSZ suspension solution with

different ceramic loading 49

3.3 The composition of YSZ suspension solution with

different ceramic: polymer ratio 50

3.4 The spinning condition for ceramic hollow fibre

membranes 52

4.1 The wall thickness of YSZ hollow fibre membrane wall

thickness prepared at different ceramic loading and

sintered at 1400 oC 67


thickness at different air-gap length and prepared at 65

wt. % ceramic loading 71

x

4.3 The wall thickness of YSZ hollow fibre membrane

prepared at different ceramic/polymer ratio and sintered

at 1400 oC 78


thickness at different sintering temperature and prepared

at 65 wt. % YSZ loading 86

xi

LIST OF FIGURES

FIGURE NO. TITLE PAGE

1.1 The simple mechanism of membrane process 2

1.2 Polymer and ceramic membrane timeline 3

2.1 The a) asymmetric and b) symmetric ceramic hollow

fibre membrane structure 11

2.2 Flat sheet membrane configuration i.e. a) flat sheet

membrane and b) the process 13

2.3 Hollow fibre membrane configuration i.e. a) different

type of tubular membrane and b) the process 14

2.4 Tubular membrane configuration i.e. a) hollow fibre

membrane and b) the process 15

2.5 The general step of fabricating ceramic membrane 16

2.6 Slip casting 17

2.7 The illustration of tape casting method 18

2.8 The illustration of dip-coating method 19

2.9 The illustration of extrusion method 21

2.10 Surface morphology of YSZ hollow fibre membrane

sintered at 1200 oC and prepared at (a) 0.1 μm and (b)

0.1 μm/20 nm 26

2.11 The illustration of tube-in-orifice spinneret from the

bottom side 27

2.12 The asymmetric structure of ceramic membrane i.e. a)

finger-like void (microstructure) and b) sponge-like

void (macrostructure) 28

2.13 The asymmetric Al2O3 hollow fibre membrane

prepared at different ceramic suspension viscosity; a)

18.5 Pa.s and b) 45 Pa.s 29

xii

2.14 The sandwich structure of ceramic hollow fibre

membrane 30

2.15 The schematic diagram of spinning process for ceramic

hollow fibre membrane 30

2.16 The sintering profile 33

2.17 Mechanism for grain growth of sintering model: (a)

two particles are in contact; (b) neck growth between

the particles by surface diffusion; (c) grain growth 34

2.18 The changes in microstructure of SCYb hollow fibre

membrane over sintering process; a) before sintering

and b) sintering at 1400 oC 36

2.19 The type of membrane filtration with the type of filtrate 37

2.20 The membrane filtration mode. (a) dead-end filtration

and (b) crossflow filtration 39

2.21 Asymmetric hollow fibre: (a) sponge-like region and

(b) finger-like region with catalyst deposition 40

2.22 Four different features of incorporated catalyst in

ceramic hollow fibre membrane 41

3.1 The flow chart of experimental work 44

3.2 Three crystalline forms in zirconia structure 46

3.3 The general procedure of fabrication of ceramic hollow

fibre membranes 47

3.4 The preparation steps of ceramic suspension solution 49

3.5 The schematic diagram of degassing system 50

3.6 The schematic diagram of spinning system for ceramic

hollow fibre fabrication 51

3.7 The spinneret used during experiment with dimension

of outer diameter/ internal diameter of 2.8 mm/0.5 mm 52

3.8 The sintering profile of sintering process 53

3.9 The schematic diagram preparation of hollow fibre

membrane for SEM characterization 54

3.10 The schematic diagram of three point bending strength

test 55

3.11 The schematic diagram of ceramic hollow fibre

membrane module 58

xiii

3.12 The schematic diagram of hollow fibre membrane

filtration system 59

4.1 The rheological behavior of YSZ/NMP/PESf/Arlacel

suspension solution prepared with different ceramic

loading 63

4.2 Photographic image of YSZ hollow fibre membrane

prepared with 55 wt. % YSZ loading and sintered at

1400 oC 64

4.3 The overall morphology (i) and cross-sectional

structure (ii) of YSZ hollow fibre membrane, extruded

at 10 ml/min, bore fluid rate at 7 ml/min, 15 cm air-gap

and sintered at 1400 oC with different ceramic loading:

(a) 62 wt. %, (b) 65 wt. % and (c) 67 wt. % 65

4.4 The mechanical strength of YSZ hollow fibre

membranes prepared with different ceramic loading; 62

wt. %, 65 wt. % and 67 wt. % and sintered at constant

sintering temperature; 1400 oC 66

4.5 The illustration of ceramic loading 67


structure (ii) of YSZ hollow fibre membrane prepared

with 65 wt. % of ceramic loading, extruded at 10

ml/min bore fluid rate, 7 ml/min extrusion and varying

air-gap length; (a) 15 cm, (b) 20 cm and (c) 30 cm and

sintered at 1400 oC 70


membrane prepared at ceramic loading 65 wt. %

ceramic loading at varying air-gap length and sintered

at 1400 oC 72

4.8 The rheological behavior of YSZ/NMP/PESf/Arlacel

suspension solution prepared with different ceramic:

polymer ratio 74


structure (ii) of 65 wt. % YSZ hollow fibre membrane,

extruded at 10 ml/min, bore fluid rate at 7 ml/min, 15

cm air-gap and sintered at 1400 oC with different

ceramic/polymer ratio; (a) 10/1, (b) 9/1, (c) 8/1 and (d)

7/1 76


membrane sintered at 1400 oC, prepared different

ceramic/polymer ratio, extruded at 10 ml/min, bore

fluid rate of 7 ml/min and air-gap length of 15 cm 77

xiv

4.11 The overall morphology structure (i) and cross-

sectional structure (ii) of YSZ hollow fibre membranes

sintered at different sintering temperature; (a) 1250 oC,

(b) 1300 oC, (c) 1350

oC and (d) 1400

oC 80

4.12 The sponge-like region structure (microstructure) of

YSZ hollow fibre membranes sintered at different

sintering temperature; (a) 1250 oC, (b) 1300

oC, (c)

1350 oC and (d) 1400

oC 82

4.13 The SEM images (i) and AFM images (ii) of surface

morphology structure of YSZ hollow fibre membranes

sintered at different sintering temperature; a) 1250 oC,

b) 1300 oC, c) 1350

oC and d) 1400

oC 84


membrane prepared using 65 wt. % ceramic loading

with 20 cm air-gap length and sintered at different

sintering temperature 85

4.15 The apparent porosities of YSZ hollow fibre membrane

prepared using 65 wt. % ceramic loading with 20 cm

air-gap length and sintered at different sintering

temperature 87

4.16 The XRD patterns of YSZ powder and YSZ hollow

fibre membrane sintered at different sintering

temperature 88

4.17 The pure water flux and apparent porosity of YSZ

hollow fibre membrane at different sintering

temperature; 1250 oC, 1300

oC, 1350

oC and 1400

oC 89

4.18 The morphology of YSZ hollow fibre membranes

sintered at 1400 oC; a) microstructure region and b)

surface 89

4.19 The 3P strength and pure water flux of YSZ hollow

fibre membrane at different sintering temperature 90

4.20 The solute rejection of YSZ hollow fibre membrane

using PEG with different molecular weight at different

sintering temperature 91

xv

LIST OF ABBREVIATIONS

YSZ - Yttria-stabilized zirconia

SEM - Scanning electron microscopy

AFM - Atomic force microscopy

XRD - X-ray diffraction

Al2O3 - Aluminum oxide

ZrO2 - Zirconia

TiO2 - Titanium dioxide

UF - Ultrafiltration

Pd - Palladium

HFMR - Hollow fibre micro reactor

CHFMR - Ceramic hollow fibre micro reactor

CHFMMR - Ceramic hollow fibre membrane micro reactor

WGS - Water gas shift

DRM - Dry reforming of methanol

MSR - Methanol steam reforming

LSCF - Lanthanum-strontium-cobalt-ferric

SOFC - Solid oxide fuel cell

NiO2 - Nickel oxide

TIPS - Thermally induced phase separation

DIPS - Diffusion induced phase separation

xvi

NMP - N-Methylpyrrolidone

NaOH - Sodium hydroxide

Na2ZrO3 - Sodium zirconate

Na2SiO3 - Sodium silicate

Zr(OH)4 - Zirconium hydroxide

ZrSiO4 - Zirconium silicate

Y2O3 - Yttria

MgO - Magnesium oxide

CaO - Calcium oxide

CuO - Copper oxide

MF - Microfiltration

NF - Nanofiltration

RO - Reverse osmosis

H2 - Hydrogen

ESR - Ethanol steam reforming

CeO2 - Cerium oxide

PESf - Polyethersulfone

xvii

LIST OF SYMBOLS

A - Area of hollow fibre

BF - Bending strength

cm - Centimeter

D - Dry weight

d - Thickness

Di - Inner diameter

DO - Outer diameter

g - Gram

L - Length

L - Length of hollow fibre

m - Meter

min - Minute

N - Load

M - Saturated weight

S - Suspended weight

T - Temperature

t - Time

W - Watt

wt - Weight

°C - Degree Celsius

xviii

% - Percent

µm - Micrometer

xix

LIST OF APPENDICES

APPENDIX TITLE PAGE

A Publication and presentation 105

B Calculation for the percentage distribution length of

finger-like voids and sponge-like region 106

CHAPTER 1

INTRODUCTION

1.1 Background of Study

Membrane can be defined as a semipermeable barrier between two phases

that selectively separate some components from others. In detail, membrane will only

allow a selective component to permeate through it and reject the permeation of other

components. Figure 1.1 illustrates the membrane process. The basic principles of

membrane which is simple in concept and operation, low energy consumption,

environmental friendly and more flexible as it is easy to scale-up made it well suited

for large-scale operations in various applications. The key pillar in membrane

technology is producing a membrane with a structure that have a high selectivity and

permeability. The desired membrane structure may be different based on the

applications. In addition to the selectivity and permeability, the membrane life time

and the durability are another important character which should be taken into

consideration to ensure the feasibility of the membrane in particular application and

economically viable.

Back in the 18th

century, the emergence development of membrane

technology has been started from the phenomenon of water permeation through a pig

bladder used to store alcohol which has been noticed by Jean-Antoine Nollet, a

physicist. He was probably the first to recognize the relation between a

semipermeable membrane and the osmotic pressure. Later, more studies on

semipermeable membrane and osmotic pressure were conducted by Thomas Graham

on the diffusion of gasses through different media [1]. Then, a rapid advancement of

2

membrane technology in following decades is also aided by Fick and van t’Hoff who

explained the diffusion of solutes in liquid media. It can be seen, the early stage of

membrane technology is focusing more on theoretical explanation of membrane

process. Besides, most of the early studies on membrane permeation were carried out

with natural material such as animal bladder.

Figure 1.1 The simple mechanism of membrane process

Early twentieth century, membrane science and technology entered a new

phase of producing an artificial membrane. A fabrication method that is popularly

known as phase inversion and invented by Loeb and Sourirajan [2] gives a new

phenomenon in producing artificial membrane. The flat sheet membrane produced is

in asymmetric structure with a dense skin at the surface which determined the

membrane selectivity and permeation flux while the porous structure provided the

mechanical strength. Then, progress in polymer science contributed to the fabrication

of polymeric membrane using this method. It is seen in dominating the membrane

markets as being used in spanning number of applications includes; filtration [3,4]

and gas separation [5]. Subjected to the medical applications, polymeric membrane

also found to be used for hemodialysis.

3

The nature of ceramic materials which were mechanically, thermally and

chemically resistance had gather an interest to use it for ceramic membrane

fabrication. The ceramic membrane was successfully widening the membranes

applications range to membrane reactor [6–8] and fuel cell application [9,10].

Besides, ceramic membrane may even replace the polymeric membrane application

in microfiltration [11–13], ultrafiltration [14], nanofiltration [15], reverse osmosis

[16] and gas separation [17,18]. Here, the development of membrane technology

keep expanding as it moves from the natural material to polymer membrane and then

towards ceramic membrane. Figure 1.2 shows the timeline of the development in

membrane technology.

Figure 1.2 Polymer and ceramic membrane timeline [19]

Concerning on the issue of water related problem, treating and/or purifying

the contaminated water before channeled for usage is vitality important. Even though

water is the most abundance natural resources, only less than 1 % of it is available

for human consumption. As man uses water as one of the main resources for daily

4

activities together with the rapid developments of industrial, agricultural and

domestic activities, it brings about to the broadening of water related problems. The

conventional treating method for water and wastewater includes one or more of the

processes; chemical addition, coagulation, flocculation, sedimentation, filtration,

adsorption and disinfection. However, the rising technology in membrane area has

gathered an interest to replace the conventional process with membrane process. The

ability to remove a wide range of components, ranging from suspended solids to

small organic compounds and ions have made membrane such a promising technique

for water and wastewater treatment. Yet, the renowned ceramic membrane over

polymeric membrane encourages of using ceramic membrane for filtration

applications.

1.2 Problem Statement

Phase inversion method introduced by Loeb and Sourirajan in fabricating

cellulose acetate membrane (polymeric membrane) have become the most common

method used in membrane fabrication. However, due to the differences between

polymeric and ceramic systems, particularly in dope solution preparation limits the

use of the phase inversion information in polymeric systems for ceramic membrane

fabrication. In polymeric system, the phase inversion process involved the interaction

between polymer, solvent and non-solvent. The solvent was diffused out from the

polymer solution while non-solvent was diffused into the dope solution. The solvent

and non-solvent exchanged results in solidification of polymer solution and

formation of polymeric membrane. Different in ceramic system; the solidification of

ceramic suspension solution involves in the movement of ceramic particles during

the solvent and non-solvent exchanged. Moreover, low polymer content and high

ceramic content in ceramic suspension solution influenced the phase inversion

process for ceramic membrane.

Ceramic membranes have been reported to have a number of advantages in

various applications. However, ceramic membranes have their own respective

desired morphology depending on the ceramic membranes’ applications. From the

5

aforementioned literature, it can be deduced that different ceramic materials used for

membrane fabrication produced a hollow fibre membrane with different structures

and properties. In this study, yttria-stabalized zirconia (YSZ) was selected as a

ceramic membrane material. However, limited research have been focused on the

structural study of YSZ hollow fibre membrane through phase inversion method

drives an interest to study the process conditions effects towards the structure and

properties.

The fabrication of ceramic membrane through this phase inversion method

composed of three main steps and in every step, the process conditions were

contributed to the structure formation. Aforementioned study reported that the

ceramic loading and the ceramic/polymer ratio influenced the structure formation for

alumina oxide (Al2O3) membrane. However, no study was reported on these

parameters for YSZ hollow fibre membrane structure formation. Besides, the air-gap

lengths during spinning process were reported to give a significant effect for Al2O3

hollow fibre membrane structure formation. This gathers an attention to study the

effect air-gap length on the YSZ hollow fibre membrane prior to the selection of

membrane for certain applications. Lastly, the sintering process gave impact

particularly in term of the surface morphology, microstructure, grain growth and pore

evaluation or elimination. Thus, this stage played an important role to determine the

final properties of ceramic membrane. The sintering temperature must be controlled

subjected to the feasibility of YSZ membrane for water purification application as

using YSZ membrane for this application is still new.

1.3 Objective

Referring to the problems stated in 1.2, the aim of this research study is to

fabricate a ceramic hollow fibre membrane made from Yttria-stabilized zirconia by

using combined phase inversion method and sintering process. This study involves

the preparation of ceramic suspension solution, spinning and sintering process. In

each process, there having parameters that gives influenced on the structure of

ceramic hollow fibre membrane. Thus, a morphological study of YSZ hollow fibre

6

membrane is important as it may be a guideline for the fabrication of YSZ hollow

fibre membrane for a specific application. In order to achieve this aim, the following

objectives were carried out:

1) To study the effect of ceramic loading and ceramic/polymer ratio

during suspension preparation on the morphology structure and the

properties of YSZ hollow fibre membrane

2) To study the effect of air-gap length during spinning process on the

morphology structure and the properties of YSZ hollow fibre

membrane

3) To study the effect of sintering temperature on the microstructure and

the properties of YSZ hollow fibre membrane for water purification

application

1.4 Scope of Study

The following scope of work is carried out to achieve objectives stated in

1.3:

1) Preparing the ceramic suspensions for spinning process using

planetary ball mill at different ceramic loadings and ceramic/polymer

ratios

2) Measuring the viscosities of ceramic suspensions using viscometer

3) Fabricating the ceramic hollow fibre precursor by dry-wet phase

inversion at different air-gap length

7

4) Sintering the ceramic hollow fibre precursors at different sintering

temperature using high temperature furnace

5) Characterizing the effect of ceramic loading, ceramic/polymer ratio,

air-gap length and sintering temperature on the morphology structure

and properties of ceramic hollow fibre membrane by using scanning

electron microscopy (SEM), atomic force microscopy (AFM), three

point bending test, X-ray diffraction (XRD), apparent porosity, pure

water permeation tests and solute rejection tests

1.5 Significant of Study

A structural study related to YSZ hollow fibre membrane was not well

studied yet. This research will give an overview on the effect of the process

conditions during membrane fabrication on the morphology of YSZ hollow fibre

membrane produced. Besides, it gives a guideline for the future study to prepare YSZ

membrane with a desired structure base on the application. Moreover, the

development of ceramic hollow fibre membrane through combined phase inversion

and sintering process are promising in reducing the production cost together with the

simple technology concept that can reduce the time consumed. Other than that, this

study discovers the feasibility of YSZ hollow fibre membrane to be used in water

separation applications.

1.6 Thesis Structure

This report consists of five chapters. In the first chapter, a brief description

on the research backgrounds, research problems, research objectives and scopes were

presented. In Chapter 2, the literature review discussed on the development of

ceramic membrane, the advantages of ceramic membrane over polymeric membrane,

the fabrication method of ceramic membrane and the application of ceramic

membrane were presented. In Chapter 3, the research methodology included the

8

materials, the analytical procedures and the characterization involves during study is

presented. Chapter 4 presents the results and discussions to answer the objectives

stated above. It discusses the changes occur over varying the parameters during YSZ

hollow fibre membrane fabrication onto the structure and the properties. Lastly, the

conclusion of whole study was presented in Chapter 5. Besides, few

recommendations are also listed for future study and enhancement.

96

REFERENCES

[1] Marcel Mulder, Basic Principles of Membrane Technology, vol. 72. Kluwer

Academic Publishers (1998)

[2] Sidney Loeb and Srinivasa Sourirajan. Sea Water Demineralization by Means

of an Osmotic Membrane. Advances in Chemistry American Chemical

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