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i
DEVELOPING NEW CHEMICAL-RHEOLOGICAL
MODELS AND CHEMICAL-DURABILITY INDICES OF
BITUMEN
MADI HERMADIHF-080011
A thesis submitted infulfilment of the requirement for the award of the
Doctor of Philosophy
Faculty of Civil and Environmental Engineering
Universiti Tun Hussein Onn Malaysia
NOVEMBER, 2013
v
ABSTRACT
Significant correlation among chemical properties, rheological characteristics and
durability of bitumen is very important in evaluating and modifying bitumen.
However, a number of previous studies found inconsistent correlation. Therefore, a
study on developing new chemical-rheological models and chemical-durability
indices was carried out. Two bitumen fractionation method, Rostler and Corbett
methods were used to extract each chemical fraction of bitumen. A number of
experiments were conducted to evaluate the effect of each chemical fraction on
bitumen rheology such as the effect of asphaltenes, polar aromatics, naphthene
aromatics, nitrogen bases, first acidaffins, second acidaffins and paraffins on elastic
modulus (G’), viscous modulus (G”) or fatigue factor (G*sin[δ]), and rutting fator
(G*/sin[δ]). Two bitumen from different sources, namely Petronas petroleum
bitumen and Buton rock asphalt (BRA) bitumen, were used. New chemical-
rheological models were formulated to estimate the bitumen rheology in corporating
parameters which are G’, G” or (G*sin[δ]), and (G*/sin[δ]) based on the chemical
properties. Furthermore, new chemical durability indices that may indicate the
ageing rate of bitumen during short-term and long-term ageing were also formulated.
Based on statistical analyses, the models and the indices, which were developed by
using chemical properties according to Rostler method were found to be invalid
because the real and the predicted rheology were significantly different. While
according to Corbett method the models and the indices were valid because the
differences is not significant since t-score of the models and the indices were
maximum 2.679 and 2.119 or less than t-critical 2.797 and 2.861 respectively). The
novelties of this study are the new models and the new indices can be used to predict
the bitumen rheology and ageing rate based on the chemical composition.
Furthermore, they are very important as guides in modifying a bitumen chemical
composition to produce a bitumen mixture with the desired rheology and short-term
or long-term ageing rate.
vi
ABSTRAK
Korelasi yang signifikan antara sifat kimia, ciri reologi dan ketahanan bitumen adalah
sangat penting dalam menilai dan mengubahsuai bitumen. Walau bagaimanapun,
beberapa kajian sebelum ini mendapati bahawa korelasi ini adalah tidak konsisten. Oleh
itu, satu kajian mengenai pembangunan model baru reologi-kimia dan indeks
ketahanan-kimia bitumen telah dijalankan. Dua kaedah pemeringkatan bitumen, iaitu
kaedah Rostler dan Corbett telah digunakan untuk mengekstrak setiap bahagian kimia
bitumen. Beberapa percubaan telah dijalankan untuk menilai kesan setiap bahagian
kimia terhadap reologi bitumen seperti kesan asphaltenes, polar aromatics, naphtene
aromatics, nitrogen bases, first acidaffins, second acidaffins dan paraffins kepada
modulus elastik (G’), modulus kelikatan (G"), factor ubah bentuk (G*sin[δ]) dan factor
aluran (G*/sin[δ]). Dua bitumen dari sumber yang berbeza, iaitu bitumen petroleum
Petronas dan asphalt batu Buton (BRA), telah digunakan. Model baru reologi-kimia
telah dirangka untuk menganggar ciri-ciri reologi bitumen, seperti G', G" atau G*sin[δ],
dan G*/sin[δ] berdasarkan sifat kimia. Di samping itu, indeks ketahanan kimia baru
yang menunjukkan kadar penuaan bitumen semasa jangka pendek dan jangka panjang
penuaan juga telah dirangka. Berdasarkan analisis statistik, model dan indeks yang
dibangunkan dengan menggunakan sifat-sifat kimia mengikut Rostler tidak sah kerana
reologi sebenar dan yang diramalkan berbeza secara ketara. Manakala menurut kaedah
Corbett, model dan indeks tersebut adalah sah kerana perbezaan sebenar dan yang
diramalkan tidak ketara atau t-skor model dan indeks adalah maksimum 2,679 dan
2,119 atau kurang dari pada masing-masing t-kritikal 2,797 dan 2,861. Penemuan ini
merangkumi model dan indeks baru yang boleh digunakan untuk meramalreologi dan
indeks ketahanan bitumen berdasarkan ciri-ciri kimia. Tambahan pula, penemuan ini
juga adalah sebagai panduan dalam mengubahsuai bitumen untuk menghasilkan
campuran dengan ciri-ciri reologi dan kadar penuaan jangka pendek atau jangka
panjang yang dikehendaki..
vii
TABLE OF CONTENTS
TITLE
DECLARATION
i
ii
DEDICATION iii
ACKNOWLEDGEMENTS iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF TABLES xiii
LIST OF FIGURES
LIST OF SYMBOLS AND ABBREVIATIONS
xviii
xxiii
LIST OF APPENDICES xxvii
CHAPTER 1 INTRODUCTION 1
1.1 Background of study 1
1.2 Problem statement 6
1.3 Research aim and objectives 7
1.4 Research scopes 8
1.5 Thesis organization 9
CHAPTER 2 LITERATURE REVIEW 11
2.1 Introduction 11
2.2 Bitumen chemistry 13
2.2.1 Bitumen chemical properties according
to Rostler precipitation method 17
2.2.2 Bitumen chemical properties according
to Corbett chromatography method 19
viii
2.2.3 Bitumen chemical properties according
to other methods 21
2.3 Rheological characteristics of bitumen 26
2.3.1 Viscosity of bitumen 31
2.3.2 Rheological characteristics of bitumen to
address rutting and fatigue cracking 33
2.3.3 Rheological characteristics of bitumen to
address low temperature cracking 37
2.3.4 Short term ageing of bitumen 40
2.3.5 Long term ageing of bitumen 41
2.3.6 Performance grade bitumen specification 42
2.4 Relationship of Rostler bitumen component
fractions to bitumen durability 47
2.5
2.6
2.7
2.8
29
Relationship of Corbett bitumen component
fractions to bitumen durability
Asphalt mixture performance
2.6.1 Superpave mix design method of HMA
2.6.2 Mixture performance tests of HMA
Buton Rock Asphalt
2.7.1 History of Buton Rock Asphalt
2.7.2 Deposit of Buton Rock Asphalt
2.7.3 BRA Utilization as an asphalt
pavement binder
2.7.4 The utilization technology of Lawele
BRA as an asphalt pavement binder
Method in previous studies
Chapter summary
51
56
56
58
63
64
64
68
69
71
72
CHAPTER 3 RESEARCH METHODOLOGY 76
3.1 Introduction 76
3.2 Experimental approach
3.2.1 Extracting the chemical fraction
component of bitumen according to
76
ix
Rostler method (ASTM D 2006)
3.2.2 Extracting the chemical fraction
component of bitumen according to
Corbett method (ASTM D 4124)
3.2.3 Rheological characteristics tests of
bitumen by dynamic shear rheometer
3.2.4 Ageing conditioning of bitumen
3.2.5 Formulation of new chemical-
rheological models and chemical
durability indices of bitumen
3.2.6 Validation of chemical-rheological
models and chemical durability indices
77
78
80
80
81
82
3.3 Materials selection
3.3.1 Description of BRA bitumen
3.3.2 Description of petroleum bitumen
3.3.3 Description of aggregates
87
87
89
90
3.4 Selection of the experimental variables and
data analysis method 91
3.5
3.6
The differences of assessing technique
between previous and this study
Chapter summary
94
95
CHAPTER 4 EFFECT OF BITUMEN CHEMICAL
FRACTIONS BASED ON ROSTLER ON
RHEOLOGICAL CHARACTERISTICS OF
BITUMEN AND ITS CHEMICAL DURABILITY
INDICES 96
4.1 Introduction 96
4.2 Factorial analysis of the effect of chemical
fractions according to Rostler method on
bitumen rheological characteristics 97
4.3 Regression analysis of the effect of chemical
fractions according to Rostler method on
x
bitumen rheological characteristics 100
4.4 Effect of asphaltenes (based on Rostler) on
bitumen rheological characteristics 104
4.5 Effect of nitrogen bases on bitumen
rheological characteristics 106
4.6 Effect of first acidaffins on bitumen
rheological characteristics 108
4.7 Effect of second acidaffins on bitumen
rheological characteristics 109
4.8 Effect of paraffins on bitumen rheological
characteristics 110
4.9 Effect of test temperature on bitumen
rheological characteristics in the regression
equation (based on Rostler) 111
4.10 Effect of un-treatment constant on bitumen
rheological characteristics in the regression
equation (based on Rostler) 112
4.11 Proposed chemical-rheological models of
bitumen based on Rostler chemical properties 113
4.12
4.13
Proposed chemical durability indices of
bitumen based on Rostler chemical properties
Chapter summary
117
120
CHAPTER 5 EFFECT OF BITUMEN CHEMICAL
FRACTIONS BASED ON CORBETT ON
RHEOLOGICAL CHARACTERISTICS OF
BITUMEN AND ITS CHEMICAL DURABILITY
INDICES 122
5.1 Introduction 122
5.2 Factorial analysis of the effect of Corbett
chemical properties on bitumen rheological
characteristics 123
5.3 Regression analysis of the effect of Corbett
xi
chemical properties on bitumen rheological
characteristics 125
5.4 Effect of Corbett asphaltenes on rheological
characteristics of bitumen 129
5.5 Effect of polar aromatics on rheological
characteristics of bitumen 130
5.6 Effect of naphthene aromatics on rheological
characteristics of bitumen 130
5.7 Effect of saturates on rheological
characteristics of bitumen 131
5.8 Comparison of the effect of test temperature on
bitumen rheological characteristics based on
Rostler and Corbett 133
5.9 Comparison of the effect of non-treatment
constant on bitumen rheological characteristics
based on Rostler and Corbett 134
5.10 Proposed chemical-rheological models of
bitumen based on Corbett chemical properties 135
5.11
5.12
Proposed chemical durability indices of
bitumen based on Corbett chemical properties
Chapter summary
138
142
CHAPTER 6 VALIDATION OF THE NEW CHEMICAL-
RHEOLOGICAL MODELS AND CHEMICAL
DURABILITY INDICES OF BITUMEN 143
6.1 Introduction 143
6.2 Chemical properties of the blended bitumen 144
6.3 Rheological characteristics of the blended
bitumen 146
6.4 Validation of the new chemical-rheological
models of bitumen
6.4.1 The new chemical-rheological models
based on Rostler chemical properties
155
155
xii
6.4.2 The new chemical-rheological models
based on Corbett chemical properties 160
6.5 Validation of the new chemical durability
indices of bitumen
6.5.1 The new chemical durability indices
based on Rostler chemical properties
6.5.2 The new chemical durability indices
based on Corbett chemical properties
165
166
167
6.6 Chapter summary 169
CHAPTER 7 PERFORMANCE OF BITUMEN AND ITS
MIXTURE 171
7.1 Introduction 171
7.2 The optimum composition and volumetric of
the mixtures 172
7.3 Indirect tensile stiffness modulus 174
7.4 Dynamic creep stiffness 176
7.5 Fatigue test of long term aged mixture 178
7.6 Chapter summary 183
CHAPTER 8 CONCLUSION AND RECOMMENDATION 184
8.1 Conclusion 184
8.2 Recommendations 187
PUBLICATIONS DURING STUDY 189
REFERENCES 191
xiii
LIST OF TABLES
2.1 Structures and dipole moment values of some organic
molecules 16
2.2 Viscosity of bitumen fractions at same average
molecular weight (Petersen, 1982) 24
2.3 Performance Grade (PG) Specification of bitumen
(ASTM D6373 - 2007) 45
2.4 RDR value criteria for bitumen binder (Rostler, 1985) 48
2.5 Fractional composition of the original and aged Cold
Lake and Ural Bitumen in % (Michalica et al., 2008b) 53
2.6 Estimation of natural asphalt deposit in the world
(Deputy Minister of Energy and Mineral Resources,
1999) 65
2.7 Estimation of Lawele B.R.A. deposit (Ministry of Public
Work, 2006) 66
2.8 Requirement of Processed Lawele BRA (Directorate
General of Highway, 2009) 70
2.9 Requirement of Lawele BRA bitumen (Directorate
General of Highway, 2009) 70
3.1 Gradation limits for asphaltic concrete 83
3.2 Characteristics of BRA raw material 88
3.3 Characteristics of pre-processed BRA 89
3.4 Characteristics of BRA bitumen 89
3.5 Characteristics of the petroleum bitumen penetration
grade 80-100 (Petronas, Malaysia) 90
3.6 Characteristics of the fine and coarse aggregates 90
3.7 Factor and level of factor based on Rostler chemical
fractions 92
3.8 Factor and level of factor based on Corbett chemical
xiv
fractions 93
3.9 Variants 93
3.10 The differences of assessment technique between
previous and this study 94
4.1 Factor and level factor in the factorial strip plot design
analysis of the effect of Rostler chemical properties on
bitumen rheology 98
4.2 The factorial analysis results of the effect of the bitumen
chemical fraction based on Rostler method on complex
modulus (G*) 99
4.3 The factorial analysis results of the effect of the bitumen
chemical fraction based on Rostler on phase angle (δ) 99
4.4 Linearity analysis of the relationship between bitumen
chemical fractions based on Rostler with rheology
characteristics of non-aged bitumen 101
4.5 Linearity analysis of the relationship between bitumen
chemical fractions based on Rostler with rheology
characteristics of RTFOT-aged bitumen 101
4.6 Linearity analysis of the relationship between bitumen
chemical fractions based on Rostler with rheology
characteristics of PAV-aged bitumen 102
4.7 The coefficients in regression of the effect of bitumen
chemical fractions based on Rostler on rheological
characteristics of the non-aged bitumen 102
4.8 The coefficients in regression of the effect of bitumen
chemical fractions based on Rostler on rheological
characteristics of the RTFOT-aged bitumen 103
4.9 The coefficients in regression of the effect of bitumen
chemical fractions based on Rostler on rheological
characteristics of the PAV-aged bitumen 103
4.10 The average molecular weight number (Mn) of Cold
Lake bitumen and Ural bitumen using a vapour pressure
osmometer (VPO) (Michalica et al., 2008b) 105
xv
4.11 Carbonyl and sulfoxide index of the asphaltenes of Cold
Lake and Ural bitumen (Michalica et al., 2008b) 106
4.12 Elemental composition of the original and aged Cold
Lake and Ural bitumen (Michalica et al., 2008b) 111
4.13 The contribution of the Rostler chemical fractions of the
bitumen RTFOT Ageing Indices 118
4.14 The contribution of the Rostler chemical fractions of the
bitumen PAV Ageing Indexes
119
5.1 Factor and level factor in the factorial strip plot design
analysis of the effect of Corbett chemical properties on
bitumen rheology 123
5.2 The Analysis of variants results of the effect of the
Corbett chemical fractions on natural logarithmic of
complex modulus (ln G*) 124
5.3 The Analysis of variants results of the effect of the
Corbett chemical fraction on phase angle (δ) 124
5.4 Linearity of relationship between Corbett chemicals
with rheology of non-aged bitumen 126
5.5 Linearity of regression between Corbett chemicals with
rheology of RTFOT aged bitumen 126
5.6 Linearity of regression between Corbett chemicals with
rheology of PAV bitumen 127
5.7 The coefficients in regression of the effect of Corbett
chemicals on rheological characteristics of the non-aged
bitumen 127
5.8 The coefficients in regression of the effect of Corbett
chemicals on rheological characteristics the bitumen
after RTFOT 128
5.9 The coefficients in regression of the effect of Corbett
chemicals on rheological characteristics the bitumen
after PAV 128
5.10 The contribution of the Corbett chemical fractions on
Chemical Durability Indices of RTFOT-aged bitumen 140
xvi
5.11 The contribution of the Corbett chemical fractions of the
bitumen PAV Ageing Indices 140
6.1 Percentage of Rostler chemical fractions of the blended
bitumen 144
6.2 Percentage of Corbett chemical fractions of the blended
bitumen 145
6.3 Elastic modulus of the blended bitumen at non-aged
condition 146
6.4 Viscous modulus of the blended bitumen at non-aged
condition 147
6.5 Rutting factor of the blended bitumen at non-aged
condition 148
6.6 Elastic modulus of the blended bitumen at RTFOT-aged
condition 149
6.7 Viscous modulus of the blended bitumen at RTFOT-
aged condition 150
6.8 Rutting factor of the blended bitumen at RTFOT-aged
condition 151
6.9 Elastic modulus of the blended bitumen at PAV-aged
condition 153
6.10 Viscous modulus or fatigue factor of the blended
bitumen at PAV-aged condition
154
6.11 Comparison of rheological characteristics of the blended
bitumen at non-aged condition between actual and
predicted based on Rostler chemical properties 156
6.12 Comparison of rheological characteristics of the blended
bitumen at RTFOT-aged condition between actual and
predicted based on Rostler chemical properties 157
6.13 Comparison of rheological characteristics of the blended
bitumen at PAV-aged condition between actual and
predicted based on Rostler chemical properties 158
6.14 Rheological characteristics of the blended bitumen
based on actual tests and predicted using Rostler
xvii
chemical properties 159
6.15 Comparison of rheological characteristics of the blended
bitumen at non-aged condition between actual and
predicted based on Corbett chemical properties 161
6.16 Comparison of rheological characteristics of the blended
bitumen at RTFOT-aged condition between actual and
predicted based on Corbett chemical properties 162
6.17 Comparison of rheological characteristics of the blended
bitumen at PAV-aged condition between actual and
predicted based on Corbett chemical properties 163
6.18 Rheological characteristics of the blended bitumen
based on actual tests and predicted using Corbett
chemical properties 164
6.19 Durability indices of the blended bitumen based on
actual tests and predicted by using Rostler chemical
properties
166
6.20 Durability indices of the blended bitumen based on
actual tests and predicted by using Corbett chemical
properties
168
7.1 The mixture volumetric at optimum compensations and
the requirement 174
7.2 Dynamic creep stiffness and bitumen rutting factor
estimated at 400C 177
7.3 Ageing and fatigue characteristics of bitumen and
mixture 179
xviii
LIST OF FIGURES
2.1 The broad structures of aliphatics hydrocarbon in
bitumen 13
2.2 The broad structures of cyclics hydrocarbon in bitumen 14
2.3 The broad structures of aromatics hydrocarbon in
bitumen 14
2.4 The combining structures of hydrocarbon in bitumen 14
2.5 Heteroatom structure of hydrocarbon in bitumen 15
2.6 Bitumen chemical precipitation test according to Rostler
method (ASTM D2006-1965) 18
2.7 Bitumen chemical sparation test according to Corbett
method (ASTM D4124-2001)
20
2.8 Glassy, elastic and viscous behaviour of bitumen (Breen
& Stephens, 1967)
27
2.9 Viscous, elastic and viscoelastic behaviour 28
2.10 Stress-strain response between the two extremes
bitumen (U.S. National Highway Institute, 2009) 29
2.11 Stress-strain response of viscoelastic bitumen (U.S.
National Highway Institute, 2009) 30
2.12 Viscous and elastic behaviour comparison of two typical
bitumen samples 30
2.13 Rheological characteristic tests at each ageing bitumen
condition (U.S. National Highway Institute, 2009) 31
2.14 Rotational Viscometer (U.S. National Highway
Institute, 2009) 32
2.15 Temperature – viscosity relationship (The Asphalt
Institute, 1996) 33
2.16 Oscillation at dynamic shear rheometer (U.S. National
xix
Highway Institute, 2009) 35
2.17 Used dimension in stress and strain calculations (U.S.
National Highway Institute, 2009) 35
2.18 Vertical and Horizontal Components of Complex
Modulus, (Hrdlicka, 2007) 36
2.19 Loading and Unloading of Asphalt Binder for the First
Three Cycles (Hrdlicka, 2007) 37
2.20 Schematic of bending beam rheometer (BBR) (National
Highway Institute, 2009) 38
2.21 The two evaluated parameters in BBR (U.S. National
Highway Institute, 2009) 39
2.22 DTT measurement principle (U.S. National Highway
Institute, 2009) 40
2.23 Typical changes in chemical composition of bitumen
(Brownridge, 2010) 50
2.24 The effect of ageing on chemical composition of binder
recovered from porous asphalt (Isacsso & Zeng, 1997) 54
2.25 Change composition of Ural and Cold lake bitumen
during ageing (Michalica et al., 2008) 54
2.26 SARA fractions for Ras Tanura and Riyadh bitumens
before and after 85 min and 340 min RTFOT ageing
(Lesueur, 2009)
55
2.27 SARA fractions for Kuwait and Bahrain bitumens
before and after 85 min and 340 min RTFOT ageing
(Lesueur, 2009)
55
2.28 Location and map of Buton Island (Ministry of Public
Work, 2006) 65
2.29 Kabungka BRA deposit of Sarana Karya 66
2.30 Lawele BRA deposit of Sarana Karya 67
2.31 Lawele BRA deposit of Buton Asphalt Indonesia 67
2.32 The effect of BRA percent on stiffness modulus of hot
mix asphalt mixture (Directorate General of Highway,
2006) 68
xx
3.1 Flow Chart of Research Activity 77
3.2 Chemical precipitation method according to Rostler 78
3.3 Chemical chromatography method according to Corbett 79
3.4 Chromatographic column for separation of bitumen by
elution-absorption 79
3.5 Correlation between loss on heating of BRA with
penetration of BRA-bitumen 88
4.1 The treatment-effect-coefficient of asphaltenes in the
regression equations based on Rostler composition 104
4.2 The treatment-effect-coefficient of nitrogen bases in the
regression equations based on Rostler composition 107
4.3 The treatment-effect-coefficient of first acidaffins in the
regression equations based on Rostler composition 108
4.4 The treatment-effect-coefficient of second acidaffins in
the regression equations based on Rostler composition 109
4.5 The treatment-effect-coefficient of paraffins in the
regression equations based on Rostler composition 110
4.6 The treatment-effect-coefficient of temperatures in the
regression equations based on Rostler composition 112
4.7 The non-treatment-effect-coefficient in the regression
equations based on Rostler composition 113
5.1 Comparison of the treatment effect coefficient between
Rostler and Corbett asphaltenes in the regression
equations 129
5.2 The treatment effect coefficient of polar aromatics in the
regression equations based on Corbett composition 130
5.3 The treatment effect coefficient of naphthene aromatics
in the regression equations based on Corbett
composition
131
5.4 The treatment-effect-coefficient of saturates in the
regression equations based on Corbett composition 132
5.5 Comparison of the treatment-effect-coefficient of
temperatures on the bitumen rheological characteristics
xxi
in the Rostler and Corbet regression equations 133
5.6 Comparison of the non-treatment effect coefficient in
the Rostler and Corbett regression equations 134
6.1 The effect of percentage of BRA bitumen on Rostler
chemical properties of the blended bitumen
144
6.2 The effect of percentage of BRA bitumen on Corbett
chemical properties of the blended bitumen
145
6.3 Elastic modulus of the blended bitumen at non-aged
condition 146
6.4 Viscous modulus of the blended bitumen at non-aged
condition 147
6.5 Rutting factor of the blended bitumen at non-aged
condition 148
6.6 Elastic modulus of the blended bitumen at RTFOT-aged
condition 149
6.7 Viscous modulus of the blended bitumen at RTFOT-
aged condition 150
6.8 Rutting factor of the blended bitumen at RTFOT-aged
condition 151
6.9 The effect of percentage of BRA bitumen ontemperature at which the Superpave requirement forG*/sin[δ] is fulfilled
152
6.10 Elastic modulus of the blended bitumen at PAV-aged
condition 153
6.11 Viscous modulus of the blended bitumen at PAV-aged
condition 154
6.12 Actual and predicted (based on Rostler chemical
composition) of the blended bitumen temperature at
G*/sin[] is fulfilled requirement 160
6.13 Actual and predicted (based on Corbett chemical
composition) of the blended bitumen temperature at
G*/sin[] is fulfilled requirement 165
7.1 The aggregate gradation of the mixtures 172
xxii
7.2 Mixing and compaction temperatures of petroleum and
BRA bitumen 173
7.3 Indirect tensile stiffness modulus of the mixtures with
different binders 175
7.4 Creep strain slope of the mixtures at 40 0C 177
7.5 Creep strain slope of the mixtures and G*/sin[] of the
bitumen at 40 0C 178
7.6 The correlation between G*sin[] of bitumen and
fatigue life of mixture at 400C 180
7.7 The correlation between percentage of BRA bitumen
and chemical durability indices of short-term age at
400C 180
7.8 The correlation between percentage of BRA bitumen
and chemical durability indices of long-term age at 400C 181
7.9 The effect of percentage of BRA bitumen on fatigue life
(Nf) at 400C of the asphalt mixture 181
7.10 The effect of the chemical durability index of short-term
ageing bitumen on fatigue life (Nf) of the asphalt
mixture at 400C 182
7.11 The effect of the chemical durability index of long-term
ageing bitumen on fatigue life (Nf) of the asphalt
mixture at 400C 182
xxiii
LIST OF SYMBOLS AND ABBREVIATIONS
A Asphaltenes
A1 First acidaffins
A2 Second acidaffins
AI Ageing Index
BBR Bending Beam Rheometer
BRA Buton Rock Asphalt, that natural rock asphalt from Buton
Island
CDI Chemical Durability Index
CDI-I Chemical Durability Index based on Rostler fractionation
method
CDI-II Chemical Durability Index based on Corbett fractionation
method
cP Centi Poises
CSS Creep Strain Slope
DSR Dynamic Shear Rheometer
DTT Direct Tension TestESALs Equivalent single axle loads
δ phase angle
FID Fame Ionization Detection
FTIR Fourier Transforms Infrared Spectroscopy
G’ Elastic modulus
G” Viscous modulus
G* Complex shear modulus
G*/sin[δ] Rutting factor to indicate rutting susceptibility
G*sin[δ] Fatigue factor to indicate fatigue susceptibility
Gmm Maximum specific gravity
GR Gotolski Ratio
xxiv
H2SO4 Sulfuric acid
85% H2SO4 Glover sulfuric acid
98% H2SO4 Concentrated sulfuric acid
H2SO4+SO3 Fuming sulfuric acid
H2S2O7 Fuming sulfuric acid
HP-GPC High Performance Gel Permeation Chromato-graphy
HMA Hot mix asphalt
HMAC Hot mix asphalt concrete
Hz Hertz
I.E.C. Ion Exchange Chromatography
IA Asphalten Index
IG Gastel Index
IC Colloidal Index
IDT Indirect tension
ITFT Indirect Tensile Fatigue Test
ITSM Indirect tensile stiffness modulus
Kabungka BRA Buton Rock Asphalt from Kabungka region
kPa Kilo Pascals
Lawele BRA Buton Rock Asphalt from Lawele region
Long-term ageing Ageing of bitumen during asphalt pavement construction
and in service
MP Melting point
N Nitrogen bases
Ni Gyration numbers at initial compaction
Nd Gyration numbers at design compaction
Nmax Gyration numbers at maximum compaction
OBC Optimum bitumen content
P Paraffins
Pa.S Pascal Second
PAV Pressure Ageing Vessel that used to simulate long-term
ageing condition of bitumen
PAV-aged After long-term ageing that simulated by PAV
PG Performance Grade
xxv
POBC Predicted optimum bitumen content
RDR Rostler Durability Ratio
RTFOT Rolling Thin Film Oven Test that used to simulate short-
term ageing condition of bitumen
RTFOT-aged After short-term ageing that simulated by RTFOT
RV Rotational Viscometer
SARA Saturates, Aromatics, Resin and Asphaltene
SGC Superpave Gyratory Compactor
Short-term ageing Ageing of bitumen during construction of asphalt
pavement
SHRP Strategic Highway Research Program
T Maximum applied torque,
TFOT Thin Film Oven Test that used to simulate short-term
ageing condition of bitumen
Tg Glass transition temperature
TLC Thin Layer Chromatography
TSR Tensile strength ratio
UTM Universal Testing Machine
UV Ultraviolet rays or electromagnetic radiation with a
wavelength shorter than that of visible light, but longer
than X-raysVMA Voids in Mineral Aggregate
Wc Work dissipated per load cycle,
shear stress
shear strain response
max Maximum applied shear stress
γmax Maximum response shear strain
σo Applied stress
0 Strain
R Radius of specimen
Deflection (rotation) angle
H Height of specimen
S(t) Creep stiffness at the time
xxvi
L Applied constant load or peak value of the applied vertical
load
B beam width
l Distance or length between beam supports
∆(t) Deflection at time
f Failure stress
Sm Indirect tensile stiffness modulus (MPa)
D Amplitude of the horizontal deformation
H Thickness of the test specimen
Poisson's ratio which for bituminous mixtures is normally
assumed to be 0.35
D(t) the creep compliance at time t (1/kPa),
GL Gage length (meters),
H Horizontal deformation (meters),
D Diameter of specimen (meters,),
Ccmpl nondimensional creep compiliance factor that is
calculated as 0.6354(X/Y)-1-0.332,
X/Y the ratio of horizontal to vertical deformation.
εx max Maximum tensile horizontal strain at the centre of the
specimen in micro-strain (µε)
σx max Maximum tensile stress at the centre of the specimen in
kPa,
Nf Fatigue life (number of cycles to failure)
0 Initial tensile (microstrain),
Stress (Newtons per square meter)
3600 strain at 3600th cycle
1200 strain at 1200th cycle
xxvii
LIST OF APPENDICES
APPENDIX TITLE PAGE
A The data of the effect of chemical properties basedon reactivity to sulfuric acid (Rostler method) onrheological characteristics of bitumen
201
B Regression analysis of the effect of chemical
properties based on reactivity to sulfuric acid
(Rostler method) on rheological characteristics of
bitumen
256
C The data of the effect of chemical properties based
on polarity (Corbett method) on rheological
characteristics of bitumen
266
D Regression analysis of the effect of chemical
properties based on polarity (Corbett method) on
rheological characteristics of bitumen
292
E Rostler chemical composition, predicted and actual
rheological characteristics of the blended bitumen
302
F Corbett chemical composition, predicted and actual
rheological characteristics of the blended bitumen
318
G Statistical analysis of validation of chemicals-
rheological models and chemical-durability indices
based on Rostler and Corbett methods
334
1
CHAPTER 1
INTRODUCTION
1.1 Background of study
The worldwide need of petroleum bitumen is continuously increasing but the supply
is limited and the price tends to increase continuously. On the other hand, there is a
potential deposit of natural rock asphalt in Buton Island, Indonesia. It is called
Buton Rock Asphalt (BRA) that consists of around 30% bitumen (Affandi, 2012).
Currently, BRA is not fully utilized because the bitumen should first be modified to
ensure that its characteristics could meet the current bitumen specification. A proper
modification method requires knowledge about the chemical composition and its
relation with the rheological characteristics of bitumen.
A significant relationship among chemicals, rheology and durability of
bitumen can be used as guidance in modifying bitumen, including BRA bitumen;
however, previous studies have indicated that they were not significantly related (Lu,
2002; Hermadi & Sjahdanulirwan, 2005; Michalica, Daucik & Zanzotto, 2008b)
thus, there is a need to study and find a new approach, as claimed in this study.
1.1.1 The needs and sources of bitumen
Bituminous mixture or asphalt is a commonly used pavement material around the
world. It plays a vital role in global transportation infrastructure, drives economic
growth and social well-being in developed as well as developing countries
(Mangum, 2006). In addition to the construction and maintenance of roads and
2
highways, bitumen is also used extensively for airport runways and taxiways, private
roads, parking areas, bridge decks, footways, cycle paths, and sports and play areas.
Asphalt covered more than 90 % of the four million kilometres of roads and
highways and about 85% of airport runways in North America. A similar percentage
of 5.2 million kilometres of roads and highways in Europe are also covered with
asphalt whilst in Asia, about four million kilometres of roads are surfaced with
asphalt (EAPA and NAPA, 2011).
About 1,600 million metric tonnes of asphalt were produced during the year
of 2007 alone (EAPA & NAPA, 2011). With bitumen content within the range of
five to six % of total weight of asphalt mix and bitumen for other applications such
as chip seal, prime and tack coats, it is estimated that the current world use of
bitumen is approximately 102 million metrical tonnes per annum. The vast majority
of bitumen (85%) is used in asphalt pavement. Around 10% are used in roofing
application and the remainder for a variety of other purposes (The Asphalt Institute
& Eurobitum, 2011). Global consumption of bitumen is forecasted to advance 4.1 %
annually from a very weak 2010 base to 119.5 million metric tons in 2015, which is
equivalent to 725 million barrels of primary bitumen (The Freedonia Group, 2012).
The main source of bitumen that the world relies on is petroleum where the
availability and price of bitumen are depending on the reserve, production and price
of crude oil. It is well recognised that, for crude oil supply, the world depended very
much on the Middle East and the North African region. Proven crude oil reserve of
this region is about 727.5 billion barrel which accounted for almost 70 % of the
global oil reserve and contributed about 30% of the world crude oil production
(Okogu, 2003). However, instability of geopolitical conditions in the Middle East
constantly provokes the crude oil price escalation and world anxiety of supply
shortage of petroleum.
In the last decade, the increase of crude oil price has significantly increased
the price of bitumen. The bitumen price increment as high as 250% during the
period of 2005 to 2008 were reported (Portland Cement Association, 2009). It is
estimated that the bitumen supplies will likely become more expensive and
unreliable in future.
Besides the political situation in the middle-east and economic distress in
many countries, there are two other reasons for the price increment. Firstly, as non-
3
renewable material, crude oil prices increased continuously and as a result, the
bitumen prices also increased. Secondly, the changes in oil refining practices have
led to a reduction in heavy crude production. This production shift was made
possible by supplementing existing refining processes with equipment called cokers.
Refineries with installed cokers produce fewer lower-margin residual products such
as bitumen (Portland Cement Association, 2009). Therefore, it is realistic to look for
other alternatives of refined bitumen such as Portland cement, recycling asphalt
mixture, and exploring natural bitumen reserve. Natural bitumen is reported in 586
deposits in 22 countries. It occurs in clastic and carbonate reservoir rocks and
commonly in small deposits at, or near, the earth’s surface. One of them is Buton
Island deposit in Indonesia (Attanasi & Meyer, 2007). The current production levels
of natural extra-heavy oil and natural bitumen in the world is just under 2% of world
crude oil production (Attanasi & Meyer, 2007).
1.1.2 Potential of Buton Rock Asphalt
The use of Buton Rock Asphalt (BRA) as an alternative to petroleum bitumen has
been explored with total estimated deposit of above 700 million tons (Ministry of
Public Work, 2006). It is probably the largest source of rock asphalt in the world.
However, the utilization of BRA in the past was limited mainly because, as a
naturally occurring material, BRA has a number of disadvantages compared to
conventional bitumen such as:
(i) Bitumen of BRA is impregnated inside the rock;
(ii) Bitumen content of BRA is low and widely varies (in range 10% to 30%);
(iii) Wide variation of bitumen consistency (i.e. from very hard to very soft);
(iv) High water content,
The disadvantages of BRA are expected to cause difficulties during the
construction process as well as low quality of the final product (asphalt mixes). The
low bitumen content makes the transportation cost of BRA high because only a small
proportion of the transported material is bitumen while the rest is rock which, in case
of conventional bitumen, should be available locally at project sites.
In order to overcome the above problems, ideally, bitumen of BRA should be
4
extracted to produce bitumen identical to conventional petroleum bitumen.
According to Affandi (2012), especially for BRA from Lawele region, pure BRA
bitumen can be categorized as PG 70 or better than petroleum bitumen penetration
grade 60/70 that is mostly categorized as PG 58.
Refinery of rock asphalt would be expensive because unlike refinery of crude
oil; it required a large quantity of additional solvent, which may not be 100%
recoverable, and it only produces a single end product which is bitumen. In the past,
this option would not be economically competitive enough; however, as the source
of petroleum bitumen has declined and the price of crude oil increased, it is believed
that the refinery of BRA is becoming profitably feasible thus; the extracted bitumen
can be utilized as ordinary bitumen.
1.1.3 The importance of chemical properties of bitumen
As a binder, bitumen should have the physical properties desired to produce stable
asphalt in terms of its ability to carry the traffic and its durability or ability to
maintain its performance during the expected service life. The performance of
bitumen includes all phases of its life from spraying, mixing, laying, compaction,
and its service life. In the latter, resistance to plastic deformation and fatigue
cracking is especially important.
As thermoplastic and viscoelastic material, bitumen characteristic is affected
by temperature, loading and duration of loading, its behaviour under applied force or
stress can better describeits rheological properties.
Superpave uses dynamic shear rheometer (DSR) to characterize the elastic
(G’) and viscous (G”) behaviour of bitumen (ASTM D7175) at the high and
intermediate pavement service temperature. The DSR measures the complex shear
modulus (G*) and phase angle (δ). Superpave uses G*/sin[δ] to address rutting
susceptibility, and G*sin[δ] to indicate fatigue cracking resistance.
It is widely known that characteristic and performance of bitumen are
strongly affected by its chemical properties. Theoretically, it should be possible to
correlate the change of bitumen behaviour under different temperature and duration
5
of loading with its chemical composition. The knowledge on this matter can be
utilized to evaluate and modify or improve conventional bitumen.
However, bitumen consists of thousands of different hydrocarbon molecules
with different and complex chemical structure. As a result, the effect of chemical
properties on performance of bitumen is complicated and difficult to identify.
Moreover, publications related to this subject were also quite limited.
Lu &Isakson (2002) found that chemical and rheological changes were
generally inconsistent. Michalica et. al. (2008a) concluded that there is definite
relationship between the chemical and rheological (physical) properties of bitumen
however it is very complex due to the concurrent actions of various material
properties. Chiu & Chiu (2008) stated that the composition test based in fractional
separation is not consistent with field performance.
Most of the research used advanced instrumentation to analyse and determine
the chemical composition of bitumen. The work involved a number of bitumen from
different sources with different chemical composition. Rheology of each bitumen
was then determined, and the correlation between thechemical composition and
rheology of bitumen was developed. It is postulated that the inclusiveness of the
reported results appeared because of the effect of each fraction cannot be
distinguished or identified. To address this problem, a new technique to identify the
contribution of each chemical fraction on rheology is necessary.
The current practice to identify durability of bitumen is either by (i)
comparing the amount of the more reactive to the less reactive to the environment
with hydrocarbon molecules of the bitumen, or (ii) comparing the physical or
rheology of bitumen before and after short-term and long-term ageing (Demirebs,
2002; Kumar et al., 2009; Michalica et al., 2008b,). The earlier is known as the
durability ratios while the latter is the ageing indices.
Two durability ratios have been introduced in the past. They are Rostler
Durability Ratios (RDR) and Gotolski Ratios (GR). Both are based on the ratio of
the reaction amount of hydrocarbon molecules to sulphuric acid. Both ratios can be
illustrated as Equation (1.1) and Equation (1.2).
(1.1)
5
of loading with its chemical composition. The knowledge on this matter can be
utilized to evaluate and modify or improve conventional bitumen.
However, bitumen consists of thousands of different hydrocarbon molecules
with different and complex chemical structure. As a result, the effect of chemical
properties on performance of bitumen is complicated and difficult to identify.
Moreover, publications related to this subject were also quite limited.
Lu &Isakson (2002) found that chemical and rheological changes were
generally inconsistent. Michalica et. al. (2008a) concluded that there is definite
relationship between the chemical and rheological (physical) properties of bitumen
however it is very complex due to the concurrent actions of various material
properties. Chiu & Chiu (2008) stated that the composition test based in fractional
separation is not consistent with field performance.
Most of the research used advanced instrumentation to analyse and determine
the chemical composition of bitumen. The work involved a number of bitumen from
different sources with different chemical composition. Rheology of each bitumen
was then determined, and the correlation between thechemical composition and
rheology of bitumen was developed. It is postulated that the inclusiveness of the
reported results appeared because of the effect of each fraction cannot be
distinguished or identified. To address this problem, a new technique to identify the
contribution of each chemical fraction on rheology is necessary.
The current practice to identify durability of bitumen is either by (i)
comparing the amount of the more reactive to the less reactive to the environment
with hydrocarbon molecules of the bitumen, or (ii) comparing the physical or
rheology of bitumen before and after short-term and long-term ageing (Demirebs,
2002; Kumar et al., 2009; Michalica et al., 2008b,). The earlier is known as the
durability ratios while the latter is the ageing indices.
Two durability ratios have been introduced in the past. They are Rostler
Durability Ratios (RDR) and Gotolski Ratios (GR). Both are based on the ratio of
the reaction amount of hydrocarbon molecules to sulphuric acid. Both ratios can be
illustrated as Equation (1.1) and Equation (1.2).
(1.1)
5
of loading with its chemical composition. The knowledge on this matter can be
utilized to evaluate and modify or improve conventional bitumen.
However, bitumen consists of thousands of different hydrocarbon molecules
with different and complex chemical structure. As a result, the effect of chemical
properties on performance of bitumen is complicated and difficult to identify.
Moreover, publications related to this subject were also quite limited.
Lu &Isakson (2002) found that chemical and rheological changes were
generally inconsistent. Michalica et. al. (2008a) concluded that there is definite
relationship between the chemical and rheological (physical) properties of bitumen
however it is very complex due to the concurrent actions of various material
properties. Chiu & Chiu (2008) stated that the composition test based in fractional
separation is not consistent with field performance.
Most of the research used advanced instrumentation to analyse and determine
the chemical composition of bitumen. The work involved a number of bitumen from
different sources with different chemical composition. Rheology of each bitumen
was then determined, and the correlation between thechemical composition and
rheology of bitumen was developed. It is postulated that the inclusiveness of the
reported results appeared because of the effect of each fraction cannot be
distinguished or identified. To address this problem, a new technique to identify the
contribution of each chemical fraction on rheology is necessary.
The current practice to identify durability of bitumen is either by (i)
comparing the amount of the more reactive to the less reactive to the environment
with hydrocarbon molecules of the bitumen, or (ii) comparing the physical or
rheology of bitumen before and after short-term and long-term ageing (Demirebs,
2002; Kumar et al., 2009; Michalica et al., 2008b,). The earlier is known as the
durability ratios while the latter is the ageing indices.
Two durability ratios have been introduced in the past. They are Rostler
Durability Ratios (RDR) and Gotolski Ratios (GR). Both are based on the ratio of
the reaction amount of hydrocarbon molecules to sulphuric acid. Both ratios can be
illustrated as Equation (1.1) and Equation (1.2).
(1.1)
6
(1.2)
where:
Nb = nitrogen bases
A1 = first acidaffins
A2 = second acidaffins
P = paraffins
A = asphaltenes
It can be seen from the above formulations that Rostler and Gotolski have
different opinion regarding the reactivity of the second acidaffins and asphaltenes.
These two formulas had been subjected to a number of critics and being rejected by
scientists and practitioners thus both indices were never being used in any bitumen
specification.
Expression of the durability of bitumen by comparing the physical or
rheology of bitumen before and after ageing has been adopted worldwide. For
examples, penetration before and after Thin Film Oven Test(TFOT) was adopted in
ASTM D946 Standard Specification for Penetration-Graded Asphalt Cement for
Use in Pavement Construction. Viscosity before and after TFOT was adopted in
ASTM D3381 Standard Specification for Viscosity-Graded Asphalt Cement for Use
in Pavement Construction. Rheology before and after short-term ageing by Rolling
Thin Film Oven Test (RTFOT) and long-term ageing by Pressure Ageing Vessel
(PAV) aged was adopted by Strategic Highway Research Program (SHRP)
specification, which later also adopted by ASTM D 6373 Standard Specification for
Performance Graded Asphalt Binder. Nevertheless, the usefulness of these indices
are limited because they do not provide any information on why and how the ageing
of bitumen different from each other.
1.2 Problem statement
From the preceding discussion, it may be concluded that the need for petroleum
bitumen worldwide is increasing but the supply is limited and the price tends to
6
(1.2)
where:
Nb = nitrogen bases
A1 = first acidaffins
A2 = second acidaffins
P = paraffins
A = asphaltenes
It can be seen from the above formulations that Rostler and Gotolski have
different opinion regarding the reactivity of the second acidaffins and asphaltenes.
These two formulas had been subjected to a number of critics and being rejected by
scientists and practitioners thus both indices were never being used in any bitumen
specification.
Expression of the durability of bitumen by comparing the physical or
rheology of bitumen before and after ageing has been adopted worldwide. For
examples, penetration before and after Thin Film Oven Test(TFOT) was adopted in
ASTM D946 Standard Specification for Penetration-Graded Asphalt Cement for
Use in Pavement Construction. Viscosity before and after TFOT was adopted in
ASTM D3381 Standard Specification for Viscosity-Graded Asphalt Cement for Use
in Pavement Construction. Rheology before and after short-term ageing by Rolling
Thin Film Oven Test (RTFOT) and long-term ageing by Pressure Ageing Vessel
(PAV) aged was adopted by Strategic Highway Research Program (SHRP)
specification, which later also adopted by ASTM D 6373 Standard Specification for
Performance Graded Asphalt Binder. Nevertheless, the usefulness of these indices
are limited because they do not provide any information on why and how the ageing
of bitumen different from each other.
1.2 Problem statement
From the preceding discussion, it may be concluded that the need for petroleum
bitumen worldwide is increasing but the supply is limited and the price tends to
6
(1.2)
where:
Nb = nitrogen bases
A1 = first acidaffins
A2 = second acidaffins
P = paraffins
A = asphaltenes
It can be seen from the above formulations that Rostler and Gotolski have
different opinion regarding the reactivity of the second acidaffins and asphaltenes.
These two formulas had been subjected to a number of critics and being rejected by
scientists and practitioners thus both indices were never being used in any bitumen
specification.
Expression of the durability of bitumen by comparing the physical or
rheology of bitumen before and after ageing has been adopted worldwide. For
examples, penetration before and after Thin Film Oven Test(TFOT) was adopted in
ASTM D946 Standard Specification for Penetration-Graded Asphalt Cement for
Use in Pavement Construction. Viscosity before and after TFOT was adopted in
ASTM D3381 Standard Specification for Viscosity-Graded Asphalt Cement for Use
in Pavement Construction. Rheology before and after short-term ageing by Rolling
Thin Film Oven Test (RTFOT) and long-term ageing by Pressure Ageing Vessel
(PAV) aged was adopted by Strategic Highway Research Program (SHRP)
specification, which later also adopted by ASTM D 6373 Standard Specification for
Performance Graded Asphalt Binder. Nevertheless, the usefulness of these indices
are limited because they do not provide any information on why and how the ageing
of bitumen different from each other.
1.2 Problem statement
From the preceding discussion, it may be concluded that the need for petroleum
bitumen worldwide is increasing but the supply is limited and the price tends to
7
increase continuously due to political instability of the Middle East and world
anxiety of petroleum supply shortage. In another hand, there is a large deposit of
BRA in Buton Island that is a potential to substitute petroleum bitumen but currently
has not been fully explored. Some BRA consists of bitumen that does not meet the
requirement of asphalt binder. Improvement of the quality of bitumen (either
petroleum or natural bitumen) can be implemented effectively if a solid knowledge
on chemical-rheological relationship of bitumen was available however; previous
study found that the correlation is not significant (Lu, 2002; Hermadi &
Sjahdanulirwan, 2005; Michalica, Daucik & Zanzotto, 2008b) hence, in order to
develop the knowledge of the correlation between chemical properties and
rheological characteristics of bitumen to use in improving the performance of
bitumen, some problems were identified and stated as follows:
(i) Chemical properties of bitumen and how they affect the performance of
bitumen, in terms of rheology and durability is not fully understood.
(ii) Although it is acknowledged that a strong relationship between the chemical
properties and performance of bitumen exist, most researchers tried to
develop a structured relationship which leads to inconclusive results.
(iii) Guidance on how to utilize the knowledge of chemical-rheological bitumen
to improve the performance of bitumen is presently not available.
1.3 Research aim and objectives
The above stated problem provided a justification for the aim of the experiment
described in this thesis, which directed toward the development of new chemical-
rheological models and chemical durability indices of bitumen. A different approach
in assessing the effect of chemical fractions on the rheology of bitumen is required.
The approach should be simple yet able to distinguish the effect of individual
chemical fractions.
From the arguments presented above, the specific objectives of the study are
as follows:
8
(i) To develop a new technique for the assessment on the effect of chemical
fractions on rheology and durability of bitumen.
(ii) To develop new models of chemical-rheological characteristics and chemical
durability indices of bitumen.
(iii) To verify the models and indices by experimentally studying the relationship
between chemical and rheological characteristics of bitumen of different
sources.
1.4 Research scopes
The scopes of this research are as follows:
(i) The two sources of bitumen were used in this study that is the BRA bitumen
from Lawele region in Indonesia and petroleum bitumen penetration grade
80-100 dmm from Kemaman Malaysia.
(ii) The coarse and fine aggregates used in this experiment were from Hanson
quarry in Batu Pahat, Malaysia.
(iii) In reviewing the physical characteristics of the bitumen, the specifications
used were penetration grade specification (ASTM D 946) and performance
grade specification (ASTM D 6373).
(iv) Ageing bitumen was conducted artificially in the laboratory. The standard
test methods used were RTFOT (ASTM D2872) for short-term ageing and
PAV (ASTM D 6521) for long-term ageing.
(v) In this study, two standard test methods to evaluate the chemical properties of
the bitumen were used. These were ASTM D 2006 “Method of Test for
Characteristic groups in Rubber Extender and Processing Oils by the
Precipitation Method” and ASTM D 4124 “Standard Test Methods for
Separation of Asphalt into Four Fractions”. ASTM D 2006 separated the
9
bitumen into five fractions based on their reactivity to sulphuric acid and
ASTM D 4124 separated the bitumen into four fractions based on their
polarity. The other test methods, such as Thin Layer Chromatography (TLC),
Size Exclusion High Performance Gel Permeation Chromatography (HP-
GPC), Ion Exchange Chromatography (IEC), and Fourier transforms infrared
spectroscopy (FTIR) were not used because those methods cannot physically
isolate and extract the chemical fractions of bitumen. The extracted fractions
were very important in the experiment to evaluate each fraction’s effect on
the bitumen rheological characteristics.
(vi) The test method that was used to evaluate the bitumen rheological
characteristic was ASTM D 7175 Determining the Rheological Properties of
Asphalt Binder Using a Dynamic Shear Rheometer. By this method, the
viscous modulus, the elastic modulus, deformation susceptibility at high
temperature and crack susceptibility at medium range temperatures (which
addressed fatigue cracking) could be evaluated. The other test methods, such
as Bending Beam Rheometer (BBR) and Direct Tension Test (DTT) which
addressed cracking at a low temperature were not covered in this study.
(vii) Mixture performance test on the bituminous mixture of BRA and petroleum
bitumen were based on Superpave guide line. The tests covered testing and
evaluated the mechanistic properties of bituminous mixtures using Universal
Test Machine to test Creep stiffness, Indirect Tensile Stiffness Modulus, and
Indirect Tensile Fatigue.
1.5 Thesis organization
This thesis is organized into eight chapters. The background and purposes of the
research program are presented in this first chapter. The scope of the research
program along with the objectives is discussed.
Chapter Two provides a review on chemical and rheological of bitumen,
asphalt mixture performance and Buton Rock Asphalt including chemical and
rheological of bitumen, characterizations and correlation of both. Asphalt mixture
10
performance was discussed covering Superpave volumetric mix design, permanent
deformation, fatigue cracking, low temperature cracking, moisture damage, and
ravelling effort. Furthermore, Chapter Two also describes location, deposit and
current utilization technology of BRA as asphalt binder.
Methodology of this study is described in Chapter Three which includes
experimental design, preparation of samples, chemical properties tests, rheological
characteristics tests, and ageing conditioning of bitumen. Performance tests of
asphalt mixture and data analysis are also covered within this chapter.
Chapter Four and Five present the results and discussion on the effect of
chemical properties on rheological characteristics of bitumen. Chapter Four based
on Rostler chemical properties, while Chapter Five based on Corbett's chemical
properties. Development of new chemical-rheological models and chemical
durability indices are discussed in both chapters. Furthermore, validation of the
models and the durability indices are described in Chapter Six and Seven. The
validation based on bitumen rheological characteristics is in Chapter Six and based
on mixture performance is in Chapter Seven.
Finally, the conclusion and recommendation that made through the study are
presented in Chapter Eight.
11
CHAPTER 2
LITERATURE REVIEW
2.1 Introduction
This chapter elaborates the chemical properties and rheological characteristics of
bitumen, their methods of measurement, relationship with asphalt mixture
performance, and Superpave performance grade (PG) specification of bitumen that
was developed through the Strategic Highway Research Programme (SHRP).
Furthermore, this chapter also discusses about Buton Rock Asphalt (BRA), covering
its history, potential deposit, and current utilization technology as a binder of asphalt
pavement.
Theoretically, bitumen characteristics are formed by each chemical
component characteristic. Therefore, the chemical composition of bitumen is useful
for evaluating and modifying a bitumen composition to produce bitumen with better
physical and rheological characteristics however; bitumen consists of thousand types
of hydrocarbon molecules, which make it practically impossible to analyse the
bitumen based on its individual molecule type thus the chemical composition of
bitumen is usually analysed by chemical fractionation.
In fractionation, the molecules which have the same characteristics were
grouped in one fraction. According to Rostler method (ASTM D2006), bitumen is
fractionated to five fractions according to their reactivity to sulphuric acid. The
fractions are asphaltenes, nitrogen bases, first acidaffins, second acidaffins, and
paraffins. Corbett (1969) suggested a method to analyse bitumen chemical
composition based on their polarity. The fractions are asphaltenes, polar aromatics,
naphthene aromatics, and saturates. This method was standardized as ASTM D4126.
12
The other methods of fractionation are based on similarity of molecule
weight, acidity-alkalinity and functional groups. These methods are also discussed
throughout this chapter.
Rheological characteristic of bitumen is important because it influences the
performance of asphalt mixtures from the construction stage up to the in-service
lifetime.
Bitumen is a viscoelastic material which exhibits both viscous and elastic
characteristics when undergoing deformation (Kamboozia & Arabani, 2012; Meyer
& Chawla, 2009). The rheological characteristics depend on temperature and the
level of ageing. At high temperatures, such as during mixing and compaction of
asphalt, bitumen dominantly exhibits viscous behaviour, while at very low-in-service
temperature bitumen exhibits more as elastic material. In between these two
extremes, it exhibits as viscoelastic material.
Bitumen of hot mix asphalt is subjected to non-ageing or fresh, short-term
ageing, and long-term ageing conditions. These conditions are related with before
construction, after construction or early in-service and after long-term in-service
condition stages of asphalt respectively. Performance of asphalt in terms of its
resistance to permanent deformation and fatigue can be explained based on the
rheological characteristics of its bitumen at relevant age condition.
Understanding the relationship of chemical properties with rheological
characteristic of the bitumen is very useful in investigating and modifying the
bitumen. Most chemical separation is based on the reactivity or polarity of the
various molecular types thus bitumen molecules can be conveniently separated or
grouped into molecular types or fractions with a narrower range of properties based
on their chemical functionality. The separation and classification of molecular types
have been useful in providing chemically definitive component fractions for further
characterization, thus aiding in determining how different molecular types affect the
physical or rheological and chemical properties of the whole bitumen and how the
bitumen mixer differs chemically from one another (Petersen, 2009).
13
2.2 Bitumen chemistry
Bitumen is a complex mixture of organic molecules which varies widely in its
composition, molecular weight, and compound types with hydrocarbon as dominant
molecules (Petersen, 2009). It also consists of heterocyclic and functional groups
containing oxygen, sulphur and nitrogen, even in a minor amount. Metals, such as
iron, nickel, magnesium calcium, vanadium, etc., may also be found in bitumen in
traced quantities (Airey, 1997; Meyer & Witt, 1990). All chemical molecules have a
contribution on bitumen characteristics such as chemical, physical, rheological and
ageing. However, the composition of bitumen is very complex. The number of
molecules with different chemical structure is extremely large hence it is impossible
to separate and identify every different molecule. Currently, the chemical
composition of bitumen is characterized by separating different groups or fractions
based on chemical reactivity, precipitation or solubility, chromatography, molecular
size and spectroscopic (Bell, 1989; Youtcheff & Jones, 1994).
There are three broad group structures of hydrocarbon molecules in bitumen,
namely aliphatic, cyclics and aromatics (Robertson, 1991; Berkers, 2005; Polacco et
al., 2008; Jones, 1992; Lesueur, 2009). The structures are shown in Figures 2.1, 2.2
and 2.3. The other molecules are a combination of them as shown in Figure 2.4.
While the major mass of bitumen is hydrocarbons, large proportion of molecules
also contained one or more heteroatoms such as nitrogen, sulphur, oxygen and
metals as shown in Figure 2.5. As a single structure, the molecules are non-polar but
if the structure is combined with each other or contained heteroatoms, the molecules
became polar. The polarity of molecules that indicated by Dipole moment value at
various molecule structures are shown in Table 2.1.
Saturate un-saturate
Figure 2.1: The broad structures of aliphatic hydrocarbon in bitumen
13
2.2 Bitumen chemistry
Bitumen is a complex mixture of organic molecules which varies widely in its
composition, molecular weight, and compound types with hydrocarbon as dominant
molecules (Petersen, 2009). It also consists of heterocyclic and functional groups
containing oxygen, sulphur and nitrogen, even in a minor amount. Metals, such as
iron, nickel, magnesium calcium, vanadium, etc., may also be found in bitumen in
traced quantities (Airey, 1997; Meyer & Witt, 1990). All chemical molecules have a
contribution on bitumen characteristics such as chemical, physical, rheological and
ageing. However, the composition of bitumen is very complex. The number of
molecules with different chemical structure is extremely large hence it is impossible
to separate and identify every different molecule. Currently, the chemical
composition of bitumen is characterized by separating different groups or fractions
based on chemical reactivity, precipitation or solubility, chromatography, molecular
size and spectroscopic (Bell, 1989; Youtcheff & Jones, 1994).
There are three broad group structures of hydrocarbon molecules in bitumen,
namely aliphatic, cyclics and aromatics (Robertson, 1991; Berkers, 2005; Polacco et
al., 2008; Jones, 1992; Lesueur, 2009). The structures are shown in Figures 2.1, 2.2
and 2.3. The other molecules are a combination of them as shown in Figure 2.4.
While the major mass of bitumen is hydrocarbons, large proportion of molecules
also contained one or more heteroatoms such as nitrogen, sulphur, oxygen and
metals as shown in Figure 2.5. As a single structure, the molecules are non-polar but
if the structure is combined with each other or contained heteroatoms, the molecules
became polar. The polarity of molecules that indicated by Dipole moment value at
various molecule structures are shown in Table 2.1.
Saturate un-saturate
Figure 2.1: The broad structures of aliphatic hydrocarbon in bitumen
13
2.2 Bitumen chemistry
Bitumen is a complex mixture of organic molecules which varies widely in its
composition, molecular weight, and compound types with hydrocarbon as dominant
molecules (Petersen, 2009). It also consists of heterocyclic and functional groups
containing oxygen, sulphur and nitrogen, even in a minor amount. Metals, such as
iron, nickel, magnesium calcium, vanadium, etc., may also be found in bitumen in
traced quantities (Airey, 1997; Meyer & Witt, 1990). All chemical molecules have a
contribution on bitumen characteristics such as chemical, physical, rheological and
ageing. However, the composition of bitumen is very complex. The number of
molecules with different chemical structure is extremely large hence it is impossible
to separate and identify every different molecule. Currently, the chemical
composition of bitumen is characterized by separating different groups or fractions
based on chemical reactivity, precipitation or solubility, chromatography, molecular
size and spectroscopic (Bell, 1989; Youtcheff & Jones, 1994).
There are three broad group structures of hydrocarbon molecules in bitumen,
namely aliphatic, cyclics and aromatics (Robertson, 1991; Berkers, 2005; Polacco et
al., 2008; Jones, 1992; Lesueur, 2009). The structures are shown in Figures 2.1, 2.2
and 2.3. The other molecules are a combination of them as shown in Figure 2.4.
While the major mass of bitumen is hydrocarbons, large proportion of molecules
also contained one or more heteroatoms such as nitrogen, sulphur, oxygen and
metals as shown in Figure 2.5. As a single structure, the molecules are non-polar but
if the structure is combined with each other or contained heteroatoms, the molecules
became polar. The polarity of molecules that indicated by Dipole moment value at
various molecule structures are shown in Table 2.1.
Saturate un-saturate
Figure 2.1: The broad structures of aliphatic hydrocarbon in bitumen
14
Figure 2.2: The broad structures of cyclics hydrocarbon in bitumen
Figure 2.3: The broad structures of aromatics hydrocarbon in bitumen
Figure 2.4: The combining structures of hydrocarbon in bitumen
14
Figure 2.2: The broad structures of cyclics hydrocarbon in bitumen
Figure 2.3: The broad structures of aromatics hydrocarbon in bitumen
Figure 2.4: The combining structures of hydrocarbon in bitumen
14
Figure 2.2: The broad structures of cyclics hydrocarbon in bitumen
Figure 2.3: The broad structures of aromatics hydrocarbon in bitumen
Figure 2.4: The combining structures of hydrocarbon in bitumen
15
Sulfoxide Ketone
Carboxylic Amine
Organo-metalic of vanadium
Figure 2.5: Heteroatom structures of hydrocarbon in bitumen
15
Sulfoxide Ketone
Carboxylic Amine
Organo-metalic of vanadium
Figure 2.5: Heteroatom structures of hydrocarbon in bitumen
15
Sulfoxide Ketone
Carboxylic Amine
Organo-metalic of vanadium
Figure 2.5: Heteroatom structures of hydrocarbon in bitumen
16
Table 2.1: Structures and dipole moment values of some organic molecules
Names Structures Dipole Moment Polarity
Hexane 0.00 D
Cyclohexane 0.00 D
Less-Polar
Benzene 0.00 D
Toluene 0.36 D
0-xylene 0.45 D
Chlorobenzen 1.57 D
Water H2O 1.87 D
Pyridine 2.37 D
More Polar
16
Table 2.1: Structures and dipole moment values of some organic molecules
Names Structures Dipole Moment Polarity
Hexane 0.00 D
Cyclohexane 0.00 D
Less-Polar
Benzene 0.00 D
Toluene 0.36 D
0-xylene 0.45 D
Chlorobenzen 1.57 D
Water H2O 1.87 D
Pyridine 2.37 D
More Polar
16
Table 2.1: Structures and dipole moment values of some organic molecules
Names Structures Dipole Moment Polarity
Hexane 0.00 D
Cyclohexane 0.00 D
Less-Polar
Benzene 0.00 D
Toluene 0.36 D
0-xylene 0.45 D
Chlorobenzen 1.57 D
Water H2O 1.87 D
Pyridine 2.37 D
More Polar
17
2.2.1 Bitumen chemical properties according to Rostler precipitation method
The test method based on solubility and chemical reactivity was developed by
Rostler-Stenberg and had been standardized in ASTM D2006-1965 Method of Test
for Characteristic Groups in Rubber Extender and Processing Oils by the
Precipitation Method which was discontinued in 1976. Nevertheless, the standard is
still being used in evaluating, modifying or rejuvenating bitumen. Boyer (2000),
Siswosoebrotho et al., (2005), Houston et al., (2005), Shen et al., (2007), and
Brownridge, (2010) used the test standard in evaluating bitumen.
Basically, the test separates bitumen into five fractions, namely asphaltenes
(A), nitrogen bases (N), first acidaffins (A1), second acidaffins (A2) and paraffins
(P). The percentage of asphaltenes is the amount of bitumen that is insoluble in low
molecular weight of normal paraffins such as n-pentane, n-hexane and n-heptane.
Nitrogen base percentage is the amount of bitumen parts that is soluble in low
molecular weight of normal paraffins but become insoluble after being treated by
glover sulphuric acid (85% sulphuric acid, H2SO4). The percentage of the first
acidaffins is determined by calculating the amount of the bitumen fractions that is
soluble in low molecular weight of normal paraffins and still soluble after being
treated with glover sulphuric acid, however, the fraction becomes insoluble after
being treated by concentrated sulphuric acid (98% sulphuric acid). The percentage
of second acidaffins is the amount of the bitumen fractions that is soluble in low
molecular weight of normal paraffins and still soluble after being treated with glover
and concentrated sulphuric acid. The second acidaffins becomes insoluble after
being treated by fuming sulphuric acid (H2SO4+30%SO3 or H2S2O7). The last
fraction is paraffins percentage of bitumen fractions that is soluble in low molecular
weight of normal paraffins and after being treated by glover, concentrated and
fuming sulphuric acids. The test method is showed in Figure 2.6.
Asphaltenes are large, discrete solid inclusions of bitumen. They are
responsible for the presence of structure in asphalts and for their non-Newtonian
rheological behaviour. They are the most highly polar molecules, insoluble in non-
polar solvent such as low molecular weight normal paraffins. The function of
asphaltenes in bitumen is as the thickening, structuring or bodying agent and impart
strength, stiffness and colloidal structure (Boyer, 2000; Oyekunle, 2005).
18
Asphaltenes are most complex molecules presented in bitumen containing aliphatic
hydrocarbon side chines, aromatics core system, heteroatoms and metals (Siddiqui,
2003). Oyekunle (2006) described asphaltenes as a black or brown coloured, hard,
non-plastic, non-malleable high molecular weight compound ranging between 1,200
and 200,000 g/mol. They contain predominantly carbon and hydrogen with sulphur,
oxygen, nitrogen and other heteroatoms. Hardee (2005) found asphaltenes as a
brittle amorphous solid, which are highly condensed aromatic compounds with
molecular weight 2,000-5,000 g/mol and constitute to 5-25% of the total weight of
asphalts.
Figure 2.6: Bitumen chemical precipitation test according to Rostler method (ASTMD2006-1965)
Deasphaltene bitumen or parts of bitumen which is soluble in low molecular
weight of normal paraffins, such as n-pentane, n-hexane and n-heptane are called
petrolenes or maltenes (Lesueur, 2009). According to Rostler method (ASTM D
2006), maltenes is defined as parts of bitumen, which is soluble in n-pentane. It
consists of nitrogen bases, first acidaffins, second acidaffins and paraffins.
Nitrogen bases are polar compounds. It is a bitumen fraction of highly
reactive resins, which acts as a peptizer for the asphaltenes (Boyer, 2000; Petersen,
2009). Nitrogen bases mostly consist of hydrocarbon containing nitrogen molecules,
19
however, it also contains all molecule bases and heteroatoms that can react and
precipitated with glover sulphuric acid.
First acidaffins are resinous hydrocarbon components, which functions as a
solvent for the peptized asphaltenes (Boyer, 2000). The molecules are mostly
consisted of aromatics.
Second acidaffins are components of slightly unsaturated hydrocarbon that
also serve as a solvent for the peptized asphaltenes (Boyer, 2000).
Paraffins are saturated hydrocarbon, functioning as bonding agent for the
asphalt components (Boyer, 2000). The molecules consist of saturated, aliphatic and
cyclic which cannot react with fuming sulphuric acid.
2.2.2 Bitumen chemical properties according to Corbett chromatography
method
The test method was introduced by Corbett & Swarbrick (1969) based on
absorption-desorption chromatography and has been standardized in ASTM D 4124-
2001 Standard Test Methods for Separation of Asphalt into Four Fractions. As
shown in Figure 2.7, the test separates the bitumen based on solubility and polarity
grade into four components which are asphaltenes, saturates, naphthene aromatics,
and polar aromatics. Asphaltenes is the insoluble part of bitumen in n-heptane
solvent. Saturates or saturated oil components is the soluble part of bitumen in n-
heptane solvent and cannot be absorbed by alumina absorbent. Naphthen aromatics
or aromatics oil component is the soluble part of bitumen that can be absorbed by
alumina absorbent and can be eluted by toluene solvent. Polar aromatics or resin
component is the soluble part of bitumen that can be absorbed by alumina absorbent
and can be eluted by trichloroethylene solvent or mix of methanol and toluene in 1:1
proportion.
Asphaltenes based on Corbett method and Rostler test is basically identical as
an insoluble part of bitumen in low molecular weight normal paraffins.
Saturates fraction of bitumen is a mixture of pure aliphatics, aliphatics with
side chains, cycloaliphatics, and cycloaliphatics with side chains. The average
molecular weight of the oil is in the C40-C50 range, and it is colourless liquid. The
20
average molecular weight is around 600 g/mol with very few polar atoms or
aromatic ring content (Lesueur, 2009). Saturates are viscous liquids or solids
ranging from straw to clear in colour, consisting mainly of a long chain saturated
hydrocarbons with some branched chain compounds, alkyl aromatics with long side
chains and cyclic paraffins (naphthenes), with molecular weights of 500-1,000
g/mol. It constitutes 5-20% of the total weight of the asphalt (Hardee, 2005).
Figure 2.7: Bitumen chemical separation test according to Corbett method (ASTM D4124-2001)
Naphthene aromatics or aromatics are the most abundant constituents of
bitumen binder together with polar aromatics or resins, since they contain about 30 -
45% of the total bitumen. They consist of several aryl groups connected by aliphatic
chains and appear as yellowish to red liquid at room temperature. They are
somewhat more viscous than saturates at the same temperature because of a higher
glass transition temperature around -20oC. The average number of molecular weight
is around 800 g/mol (Lesueur, 2009). According to Hardee (2004), naphthen
aromatics are viscous dark-brown liquids containing mainly carbon, hydrogen and
sulphur with minor amount of oxygen and nitrogen, with a molecular weight of 500-
900 g/mol, which constitutes to 45-60% of the total weight of bitumen.
Polar aromatics that are also called resins consist of aliphatics, naphthenes
21
and aromatics in multi ring structure along with sulphur, oxygen and nitrogen
compounds. It is black semi-solid materials with average number of molecular
weight around 11,800 g/mol. It is polar and sometimes can be more polar than
asphaltenes and functions as a stabilizer for the asphaltenes (Lesueur, 2009). Polar
aromatics are brown-black, adhesive, shiny solids or semi-solid which comprised
heterogeneous polar aromatics compounds with a small amount of oxygen, nitrogen
and sulphur with molecular weights of 800-2,000 g/mol and constitutes to 15-25% of
the total weight of bitumen (Hardee, 2005).
2.2.3 Bitumen chemical properties according to other methods
Separation and other characterization methods in analysing chemical properties of
bitumen may also be performed using other methods such as:
(i) Thin layer chromatography (TLC-FID),
(ii) Size exclusion (High Performance Gel Permeation Chromatography/HP-
GPC),
(iii) Ion Exchange Chromatography (IEC),
(iv) Characterization of Bitumen Chemical Properties According to Fourier
transforms infrared (FTIR) spectroscopy.
Comparing with Rostler and Corbett methods, these methods are faster and
more accurate however; the methods were not designed to extract the chemical
components of bitumen.
Even though Rostler and Corbett methods are classical, the two methods are
able to isolate and extract the chemical components. This feature enables the
investigation of the effect of individual chemical fraction on the characteristics of
bitumen.
2.2.3.1 Characterization of bitumen chemical properties based on thin-layer
chromatography with flame ionization detection (TLC-FID)
The TLC-FID is a method to analyse and separate bitumen into four fractions:
saturates, aromatics, resins, and asphaltenes. In the TLC-FID, 2% (w/v) solutions of
22
bitumen were prepared in dichloromethane, and 1 µl sample solution spotted on
Chromatography rods using a spotter. Bitumen is then separated into four generic
fractions (saturates, aromatics, resins and asphaltenes) by a three-stage development
using n-heptane, toluene and dichloromethane/methanol (95/5 by volume),
respectively. The fractions were determined by an Iatroscan MK-5 analyser (Lu &
Isacsson, 2002; Guern et. al., 2010).
TLC-FID test are faster and more accurate than the conventional tests
(Corbett and Rostler tests) in determining a chemical fraction composition of
bitumen however; the procedure cannot be used to extract and recover the chemical
fractions hence the chemical fraction cannot be analysed individually in identifying
its effect on the bitumen rheological characteristics. A research on the effect of
chemical properties on rheological characteristics can only be done by correlating or
regressing chemical composition or its change with rheological characteristics.
Percentage ratio of each chemical fraction in bitumen has strong correlation with
percentage ratio of another chemical fraction. It causes one or more chemical
fraction to become excluded variables. If percentage of one chemical fraction
decreased or increased, then percentage of the other fractions will increased or
decreased accordingly. As a consequence, it is not clear which fraction will affect
the rheological characteristics of the bitumen.
Lu & Issacsson (2002) conducted a chemical characteristic study on bitumen
and compared test results from TCL-FID and rheology. According to their study,
ageing of bitumen decreases aromatics and increases the content of resins and
asphaltenes at the same time. The content of saturates changes slightly due to their
inert nature to oxygen. However, as a result of the chemical changes, the
mechanical properties of aged bitumen become more solid-like, as indicated by
increased complex modulus and decreased phase angle. They also found the
chemical and rheological changes generally inconsistent.
Montepara & Giulani (2001) evaluated the chemical properties of bitumen
using TLC-FID of fresh, short-term ageing process by RTFOT and after long-term
ageing by PAV. They concluded that saturates remain substantially unchanged in
bitumen during short-term and long-term ageing process. On the other hand, the
reactivity of aromatics and resins to air induced the formation of polar groups, and
increased their concentration in bitumen significantly.
23
The other study was reported by Guern et.al. (2010). They used TLC–FID
Iatroscan to determine the colloidal instability index or Gaestel index (Ic). The index
is a ratio of asphaltenes and saturates percentage to aromatics and resin percentage.
It is typically used to characterize the colloidal stability of bitumen. It was
compared to the agglomerate content value determined by HS-SEC. The result
showed a significant evolution in agglomerate content hence the concept of stability
provided by the colloidal index did not appear to be systemically correlated with
agglomerate content.
2.2.3.2 Characterization of bitumen chemical properties based on high
performance gel permeation chromatography (HP-GPC)
HP-GPC involves the separation of bituminous materials into their components
according to molecular size. Size exclusion chromatography (HP-GPC) separates
components of the bitumen based on the apparent size (hydrodynamic volume) of
molecules and molecular aggregations or associations in dilute solution. The
chromatogram describes the molecular size profile of bitumen. For the purpose of
HP-GPC determination, the bitumen sample is introduced into a solvent (typically
tetrahydrofuran or toluene) flowing at high pressure through a column packed with a
highly porous, solid material. The liquid transports the asphalt through and around
the porous packing material in the column and as a result smaller size molecules in
the asphalt can enter freely into all the pores of the column packing while larger
molecules can enter none of those pores (Yapp et al., 1991).
Molecules of intermediate size have access to varying amounts of available
pore volume thus the larger molecules move through the column faster than the
smaller ones. The Large Molecular Size portion of the bitumen leaves the column
first, followed by the medium-size and then the small size components. A detector
measures the amount of each component. The resultant chromatogram represents
the relative amount of material appearing at a given elution time (Yapp et al., 1991).
Furthermore, Yapp et al. (1991) investigated the relationship between HP-
GPC parameters and performance of bituminous concrete pavements however; the
relationships are inconsistent and likely to be confounded by test method, methods
24
of interpretation of the HP-GPC test data, and relationship to different types of
pavement distress (i.e., transverse cracking, fatigue cracking, rutting or tender
mixes).
Even though the molecule size generally can affect the bitumen consistency,
it could be fuzzy if the molecule polarity or molecule structure is different. Polarity
and molecule structure that cannot be detected by HP-GPC can also affect the
bitumen consistency as shown in Table 2.2. Since the relationships between HP-
GPC parameters and bituminous consistency were not consistent, as a consequence,
the relationships of the parameters on rutting of bituminous pavement become
inconsistent as well.
On the other hand, molecules size of bitumen fractions cannot indicate
bitumen elasticity, brittleness and ageing reactivity hence it cannot indicate cracking
performance of the bituminous pavement.
Table 2.2: Viscosity of bitumen fractions at same average molecular weight(Petersen, 1982)
Fraction Polarity Apparent molecularwt.
ViscosityPa.S
Saturates Less polar 500 10Aromatics 500 1,000Resins More polar 500 100,00
2.2.3.3 Characterization of bitumen chemical properties based on Ion Exchange
Chromatography (IEC)
Ion exchange chromatography (IEC) is a technique used to separate bitumen into
distinct chemical fractions based on chemical functionality without the need for
initial asphaltene precipitation. IEC accomplishes this fractionation by pumping
solution of bitumen, dissolved in selected solvents, into columns filled with activated
cation or anion resins. Bitumen components containing acidic functional group
absorbed on anion resins, from which they can be desorbed. Bitumen component
having basic functional groups are absorbed in cation resins. Component containing
191
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