PRODUCTION AND CHARACTERIZATION OF BITUMEN-

WASTE RUBBER BLENDS SUITABLE FOR CONSTRUCTION

OF ROAD PAVEMENTS

BY

IGBINWOLE KEHINDE SOLOMON

CHE/2016/1017

A PROJECT REPORT SUMBITTED TO THE DEPARTMENT

OF INDUSTRIAL CHEMISTRY, FACULTY OF SCIENCE,
FEDERAL UNIVERSITY OYE-EKITI, OYE-EKITI IN PARTIAL
FULFILLMENT OF THE REQUIREMENT FOR THE AWARD
OF BACHELOR OF SCIENCE (B.Sc.) DEGREE IN INDUSTRIAL
CHEMISTRY

SUPERVISOR: Prof. DOSU MALOMO

AUGUST, 2021.
 CERTIFICATION

This is to certify that this report was written and carried out by IGBINWOLE KEHINDE
SOLOMON student of the department of Industrial chemistry, having met the standard as
required by the institution and approved as to contents and style by:

_________________________ ___________________
Supervisor Date
Prof. Dosu Malomo

_________________________ ___________________
Head of department Date
Dr. Ayanda

ii
 DEDICATION

This project report is dedicated to God almighty, the maker and giver of life and also to my
family for their love, support, encouragement and everyone else that contributed towards
making this a success.

iii
 ACKNOWLEGEMENT

I give thanks to God almighty for His love, care and blessings. I want to appreciate my
supervisor, Prof. D. Malomo for his fatherly and financial support on this research work, also for
his technical input in this research work, I really appreciate.

I also want to appreciate the Head of Department Dr. Ayanda, all my lecturers as well as the
entire staff of the Department of Industrial Chemistry for their training and mentorship.

I will forever appreciate my parents; Mr. and Mrs. Igbinwole, My siblings; Seyi, Sunday and
Taiwo for their love and care during the course of this research. I acknowledge my project mates
Toyin and Joshua for their supports. I also acknowledge my entire course mates and friends,
showed me the meaning of love and family most especially Ayomikun, Goodness, Dare, Lola,
Gloria, Jaiye, Abimbola, Toyosi, Lekan, good friends who are more like brothers and sisters.

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 Table of Content
Title page………………………………………………………………………………….. i

Certification………………………………………………………………………………. ii

Dedication ………………………………………………………………………………... iii

Acknowledgement ………………………………………………………………………… iv

Table of content …………………………………………………………………………… v

List of Tables ……………………………………………………………………………… viii

List of Figures ……………………………………………………………………………. ix

Abstract ……………………………………………………………………………………. x

CHAPTER ONE
INTRODUCTION
1.1 Background of study………………………………………………………………….. 1

1.2 Bitumen ……………………………………………………………………………….. 3

1.3 Historical perspective ………………………………………………………………… 4

1.4 Waste inner tune……………………………………………………………………….. 6

1.4.1 Materials for waste inner tube…………………………………………………........ 7

1.5 Aim and objectives……………………………………………………………………. 7

1.5.1 Aim………………………………………………………………………………… 7

1.5.2 Objectives…………………………………………………………………………... 7

1.6 Significance…………………………………………………………………………… 8

CHAPTER TWO
LITERATURE REVIEW
2.1 modifier………………………………………………………………………………… 9

2.2 Rubber…………………………………………………………………………………. 10

2.3 Polymer………………………………………………………………………………... 10

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2.3.1 Types of polymer…………………………………………………………………….. 11

2.3.2 Other method of classification of polymer………………………………………….. 12

2.4 polymer modification………………………………………………………………….. 13

2.4.1 Popular polymers for bitumen modifications……………………………………….. 14

2.4.2 Developments for removing drawbacks ……………………………………………. 15

2.5 Historical Development of crumb rubber……………………………………………. 17

2.6 Benefits of polymer modified bitumen………………………………………………. 18

2.7 Limitations of polymer modified bitumen…………………………………………… 20

2.8 Method of blending…………………………………………………………………… 21

2.8.1 Dry process………………………………………………………………………….. 21

2.8.2 Terminal blend process……………………………………………………………… 21

2.8.3 Wet process………………………………………………………………………….. 21

2.8.4 Factors affecting blending…………………………………………………………… .22

2.8.4.1 Blending mechanism…………………………………………………………….… 23

2.8.4.2 Blending time……………………………………………………………………… 23

2.8.4.3 Blending Temperature…………………………………..…………….………….. 23

2.9 Interaction between bitumen and rubber……………………………………………… 23

2.9.1 Rubber swelling…………………………………………………………………….. 24

2.10 Future development………………………………………………………………….. 25

CHAPTER THREE
MATERIALS AND METHODS

3.1 Equipment and Apparatus…………………………………………………………….. 27

3.1.1 Reagent……………………………………………………………………………… 27

3.1.2 Solvent ……………………………………………………………………………… 27

3.1.3 Sample Collection ………………………………………………………………….. 28

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3.2 Method………………………………………………………………………………… 28

3.2.1 Step one……………………………………………………………………………… 28

3.2.2 Ductility test………………………………………………………………………… 29

3.2.3 Moisture content……………………………………………………………………. 29

3.2.4 Viscosity test………………………………………………………………………… 30

3.2.5 Softening point test ………………………………………………………………….. 31

3.2.6 Penetration Test……………………………………………………………………… 31

3.2.7 Specific gravity……………………………………………………………………… 31

3.2.8 FTIR…………………………………………………………………………………. 32

CHAPTER FOUR
RESULTS AND DISCUSSION
4.1 Results………………………………………………………………………………… 33

4.2 Discussion……………………………………………………………………………. 34

4.3 FTIR Analysis………………………………………………………………………… 42

CHAPTER FIVE
SUMMARY, CONCLUSION AND RECOMMENDATION
5.1 Conclusion……………………………………………………………………………. 45

5.2 Recommendation…………………………………………………………………….. 45

REFERENCES…………………………………………………………………………… 46

APPENDIX ………………………………………………………………………………. 51

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 List of Tables
Table 2.1: Categories, example and advantage of bitumen ……………………………… 15

Table 2.2: Attempted measurement or removing PMB drawback ………………………. 17

Table 2.3 Properties of Bitumen …………………………………………………………. 26

Table 4.1: Physico-mechanical properties of Bitumen …………………………………. 33

Table 4.2: Result of FTIR for sample A ………………………………………………. 43

Table 4.3: Result of FTIR for sample B ……………………………………………… 43

Table 4.4: Result of FTIR for sample C ……………………………………………… 44

Table 4.5: Result of FTIR for sample D ……………………………………………… 44

Table 4.6: Result of FTIR for sample E ………………………………………………. 44

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 List of Figures
Figure 1.1: Image of Bitumen ………………………………………………… 2

Figure 1.2: Image of an inner tube ………………………………………………… 7

Figure 3.1: Image of orifice viscometer ……………………………………………… 30

Figure 4.1: Specific gravity (60oc) …………………………………………………… 35

Figure 4.2: Specific gravity (90OC) ………………………………………………….. 36

Figure 4.3: Viscosity …………………………………………………………………. 37

Figure 4.4: Water content …………………………………………………………….. 38

Figure 4.5: Loss on heating …………………………………………………………… 39

Figure 4.6: Ductility ………………………………………………………………….. 40

Figure 4.7: Softening point …………………………………………………………... 41

Figure 4.8: Penetration test ………………………………………………………….. 42

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 ABSTRACT
In this research work, bitumen and ground inner tube was blended together in different
ratio and all the samples was subjected to different physico-mechanical testand FTIR
characterization using standard method. The results of the physico-mechanical test carried out on
the samples showed that the specific gravity in the ranged of 0.9938 to 0.8753 from pure bitumen
sample to modified bitumen composition, viscosity in ranged of 10.484 to 11.521 (cp) from pure
bitumen sample to modified bitumen composition, water content in ranged of 11.638 to 7.096
from pure bitumen to modified bitumen composition, loss on heating ranged of 1.841 to 1.050
from pure bitumen to modified bitumen, ductility in the ranged of 19.200 to 9.100 from pure
bitumen to modified bitumen, softening point in ranged of 57.900 to 65.210 from pure bitumen
to modified bitussmen and penetration in ranged of 46.220 to 49.120 from pure bitumen to
modified bitumen.

The FTIR shows the presence of the following functional groups C-C bend, C-H bend, C-H
stretch, O-H stretch, N-H bend, and the result of all the samples showed that the blends with
higher waste rubber content show better resistance to water compared to blends with lower
crumb rubber content.

x
 CHAPTER ONE
INTRODUCTION

1.1 Background of study

Bitumen is not a polymeric material but a complex mixture consisting of hydrocarbons of

different size, polarity and aromaticity. It may also contain small amounts of hetero atoms, such

as sulphur (0–9 wt.%), nitrogen (0–2 wt.%), oxygen (0–2 wt.%) and traces of metals (e.g.

vanadium and nickel). The number-average molecular weight of bitumen generally ranges from

600 to 1500 Da and therefore, bitumen molecules cannot be considered as macromolecules in the

polymeric sense. Given the highly complex molecular structure of bitumen, it is almost

Impossible to conduct detailed chemical analysis (Lesueur 2009).

Over the years, the damage in roadway pavement in Nigeria has been kept on the

increase. Lots of maintenance work need to be repaired to reduce defect or damage on the

roadway, this is because of heavy traffic load or increasing road users in Nigeria. When the road

users increase, the loading on the road will be increased and the pavement will have problem if

the pavement cannot support the high loading or volume (Sulyman, 2014).Moreover, asphalt

cannot withstand drastic weather changes because Asphalt is hard in cold environment and soft

in hot environment. Previous studies showed that number of failures represented by the low

temperature cracking, fatigue cracking, and the rutting (or permanent deformation) at high

temperature, causing its quality and pavement performance to decrease. Besides, asphalt also has

a thickness problem, bleeding, flushing and drain-down. Therefore to overcome this problem,

crumb rubber is suggested as one of the methods that might be able to solve the environmental

problem and roadway pavement. Crumb rubber will increase the strength and will give elastic

property to the roadway pavement. Besides, waste inner tubes contributes to one of the

1
environmental problems in Nigeria and this problem needs to be urgently addressed because

waste tubes are not easily disposed that is, they are non-biodegradable. This leads to various

environmental problems which include increase in landfill space, air pollution associated with

open burning of tyres (particulates, odor, and other harmful contaminants such as polycyclic

aromatic hydrocarbon and oxides of nitrogen) and aesthetic pollution (Niraj D. Baraiya, 2013).

It is thought that the application of recycled automobile tires and plastics will not only solve

environmental problem but also act as very promising modifiers for the improvement of asphalt

pavement material (M. Sienkiewicz et al., 2012).

Therefore, the potential of crumb rubber as additive in asphalt pavement will be utilized in this

research. A crumb rubber will prevent the pavement to crack in the cold or melt in the heat. It

can also increases film thickness in the aggregate that can prevent bleeding, flushing and reduce

noises. Crumb rubber also has higher durability than asphalt. Therefore, crumb rubber will be

used as additives in asphalt pavement.

Figure 1.1 Image of Bitumen

2
1.2 Bitumen

Bitumen is one of the oldest known engineering materials (Morgan. 1995) and it has been

used for thousands of years in various ways, e.g. as adhesive, sealant, preservative,

waterproofing agent and pavement binder. Ancient inhabitants directly used the natural bitumen

which is usually in the earth‟s surface (Polacco. 2006). In the early 1900s, refined bitumen was

first produced by refining crude oil in the USA. Since then, the world consumption of bitumen

has increased rapidly, most of which was used in road construction. According to a joint

publication of Asphalt Institute and Euro bitumen in 2011, the current world consumption of

bitumen is approximately 102 million tonnes per year, 85% of which is used in various kinds of

pavements. In fact, the chemical composition of bitumen is very complex and variable; and the

properties are closely related to the crude oil sources and the refinery processes. By selecting

good crude oil or proper refinery processes, some good bitumen properties can be obtained.

However, the limited oil resources for producing good-quality bitumen and the lack of effective

control during refinery, as well as the driving force of earning the maximum economic benefits,

made industries pay more attention to bitumen modification [Becker. 2001]. Additionally,

pavement industry has developed rapidly all over the world during the last few decades,

especially in developing countries. Following the rapid development, increased traffic load,

higher traffic volume, and insufficient maintenance led to many severe distresses (e.g. rutting

and cracking) of road surfaces. The harsh reality was demanding more on bitumen quality. In

order to obtain bitumen with enhanced quality, an increasing number of investigations also began

to focus on bitumen modification. Among all attempted or investigated modification methods of

bitumen, polymer modification has been one of the most popular approaches.

3
1.3 Historical Perspective

Bitumen polymer modification has a long history. Even before refined bitumen was

produced, people began to modify natural bitumen and some patents were granted for natural

rubber modification (Morgan. 1995). Synthetic polymers, however, were not widely used until

after the end of World War II. One well-known early example is neoprene (polychloroprene)

latex, which began to be increasingly used for bitumen modification in North America from the

1950s (Yildirim. 2007.).

Plastomers have a longer history of artificial synthesis than thermoplastic elastomers.

Most of the currently popular plastomers began to be produced commercially before 1960.

Regarding thermoplastic elastomers, the first commercially acceptable SBS product was

developed in the USA in 1965 and the first hydrogenated (or saturated) product, SEBS, was

announced in 1972 (Legge. 1972) In the early years, these commercial polymers were mainly

used in packaging, rubber, footwear or adhesive industries.

Bitumen polymer modification was firstly used in the roofing industry, and then the

paving industry. In 1965, atactic polypropylene (APP), which is a by-product of isotactic

polypropylene (IPP) manufacturing, was firstly used to modify bitumen for roofing in Italy and

the first commercial product was marketed in 1967 (Legge. 1972). SBS, however, was not

widely used until the early 1970s in Europe. As for the USA, it was in 1978 that Americans

began to widely use modified bitumen in roofing. Around 1980, the first American PMB

manufacturer started (Legge. 1972).

Bitumen polymer modification for road construction is a field extensively covered by

intellectual property. A patent, relating a bituminous composition with base bitumen and

4
polyisobutylene, was granted as early as 1940. After that, SBS was introduced to bitumen

modification, a large number of patents were applied all over the world. Due to the oil crises of

1973 and 1979, attempts for use of bitumen polymer modification for road construction began to

increase (Rostler 2002). During the 1970s, researchers proved that the addition of polymers,

including plastomers and thermoplastic elastomers, could improve some properties of paving

bitumen, such as reducing temperature sensitivity or increasing the resistance to permanent

deformation (Chaffin. 1978). In 1978, Chaffin et al. reported the potential storage stability

problems of bitumen modified with elastomers, but they also wrote that their field test sections

constructed in Texas in 1976 were performing well.

During the 1980s, the demand of thin layer for pavement drove more systematic

investigations (Piazza. 1980) to focus on bitumen polymer modification. For example, in 1980,

the research carried out by Piazza et al., revealed the features of bitumen modified by plastomers

and thermoplastic elastomers. In 1982, Kraus studied the morphology of modified bitumen by

elastomers and reported the swelling of polymers in bitumen. In 1983, a binder for pavement

wearing courses, which comprises PE modified bitumen, was reported by Denning et al.,

although it led to phase separation problems and higher manufacturing and compacting

temperatures. During the following several years, more investigations (Miłkowski. 1985) on PE

modified bitumen were being published. Bowering reviewed the necessity of modifying bitumen

with polymers in 1984 and claimed that the relatively high cost of PMB might be outweighed by

the effects of reduced layer thickness and extended life of PMB pavements. In 1987, the US

Congress established the Strategic Highway Research Program (SHRP) which promoted the

popularity of PMB by developing a performance-based specification for both conventional and

modified bitumen with emphasis on rheology. In 1989, Reese et al. reported the good resistance

5
to ageing and cracking of PMB after a two-year field test in California, although they pointed out

that further evaluations needed to be performed for conclusive success of the modification.

By the early 1990s, increased interest in research of bitumen polymer modification was

observed in many countries (Isacsson. 1995). Researchers systematically investigated the

mechanical properties, rheology, temperature sensitivity, morphology, thermal behavior, storage

stability and ageing of different PMBs (Wardlaw et al., 1992). The advantages and disadvantages

of widely used PMBs were gradually found out. On the one hand, it was concluded that polymer

modification resulted in some improved properties of bitumen, such as better elastic recovery,

higher cracking resistance at low temperatures and higher rutting resistance at high temperatures

of SBS modified bitumen. On the other hand, some drawbacks were proven, such as the thermal

instability of some polymer modifiers and phase separation problems of some PMBs. In June

1998, a World Road Association (PIARC) International Symposium on polymer modification of

bitumen was held in Rome, which gave an overview of the situation at that time and encouraged

the publication of a report in 1999. Furthermore, attempts to remove PMB‟s drawbacks began

from the 1990s. In 1996, Giavarini et al. claimed that PP modified bitumen could be stabilized

by adding polyphosphoric acid (PPA) and they believed PPA could help to improve storage

stability of PMB by changing the bitumen structure from sol to gel.

1.4 Waste Inner Tube

An inner tube is an inflatable ring that forms the interior of some pneumatic tires. The tube is

inflated with a valve stem, and fits inside of the casing of the tire. The inflated inner tube

provides structural support and suspension, while the outer tire provides grip and protects the

more fragile tube. They are widely used in bicycles and are also used in many motorcycles and

6
heavy road vehicles such as trucks and buses. They are now less common in other wheeled

vehicles because of the benefits of having no tube, such as the ability to operate at low pressure

and at high pressure (unlike a tube tire, which would pinch at low pressure and burst at high

pressure), without going flat. Large inner rings also make effective flotation devices and are

widely used in the leisure activity of tubing.

1.4.1 Materials for Inner Tube

The tube is made out of a mix of natural and synthetic rubber. Natural rubber is less prone to

punctures and is often more pliable, while synthetic rubber is cheaper. Often racing bikes will

have a higher percentage of natural rubber than regular run-of-the-mill bikes.

Figure 1.2: Image of an inner tube.

1.5 Aim and Objectives

1.5.1 Aim:

To produce and characterize polymer modified bitumen suitable for making road pavement.

1.5.2 Objectives:

I. To pick, clean and

II. Producing bitumen-waste rubber blends for road construction pavement

7
III. To determine the properties of polymer modified bitumen when added with crumb

rubber

IV. To determine the physical and rheological properties of waste rubber modified

bitumen.

V. To investigate the potential of crumb rubber as additives in asphalt pavement

It is expected that the research would help to explore the potential use of waste inner rubber tube

in flexible pavement construction and minimizing of the environmental pollution.

1.6 Significance of Study

This research is intend to solve the problem of pavement strength and environmental

problem which comes from waste tube. The two issues will be addressed by reuse the scrap tubes

and produces crumb rubber before using it in the road construction by adding as sub base or

surface coarse pavement layer when crumb rubber is added to bitumen it increases the bitumen's

viscosity, lowering penetration while increasing the softening point. The addition of rubber gives

the additional binding strength, increasing elasticity and softening point of the asphalt and

Carbon present in rubber acts as an anti-oxidant and prevents bitumen from ageing and

oxidization.

Furthermore, the used of crumb rubber in the road pavement will reduce noises, prevent

bleeding, flushing and drain down, increase the performance life, economical and increase

safety. The rubber aggregate solves the problem of permanent deformation and thermal cracking

when used for road construction and can stand higher temperature, hence it is suitable for

tropical regions. It can also resist the effect of water.

8
 CHAPTER TWO
LITERATURE REVIEW

The use of polymer as a modifier of bitumen is not very new as Polymer modified

bitumen (PMB) is becoming an increasingly important material for building and maintaining

roads. Many countries have been using polymer with bitumen for the last few decades. Scientific

research is going on the modification of bitumen with different types of polymer and

purposefully new types of polymers are being invented. Besides, some countries are trying to use

scarp tyre, waste polythene bag, pet bottle and other waste plastic materials for the economic and

environmental considerations.

2.1 Modifier

Additives, which are used to modify or improve the quality of virgin materials is simply called

the modifier of it. Modifiers are blended directly with the binder or added to the asphalt concrete

mix during production to improve the properties and or performance of the pavement. It should

be mentioned here that a huge quantity of bituminous binder is required every year for pavement

construction. Hence the researchers have been thinking of quality improvement of bitumen and

trying to extend the life span of bituminous pavement since long ago. The recent trend in

pavement industry is to use polymer as a modifier of bitumen since polymer is to some extent

similar in nature to some constituents of bitumen. Due to the similarities in nature of polymer

and copolymer of different category and grade are being used as the modifier of bitumen for its

overall quality improvement. Polymer increases the viscosity of bitumen (Murphy et al., 2001).

9
2.2 Rubber

Rubbers are materials that display elastomeric properties, this means they can be stretched and

will spring back when the stress is removed. Rubber is produced from the juice of a tropical plant

or manufactured artificially, natural rubber is found as a milky liquid in the bark of the rubber

tree, Hevea brasiliensis. Natural rubber is vulcanized with sulphur and other materials to make it

less susceptible to temperature, the tyres of vehicles and automobiles are made of vulcanized

rubber. Rubber is more elastic than polymer. Natural rubber and the crumb rubber from the used

tyres of vehicles can be used for the modification of bituminous binder. Scrap rubber have be

used in aggregate during pavement construction to improve riding quality (Infratech Polymers

Inc.; Rubberized Asphalt Concrete Technology Centre, 2000) and reduce noise of vehicular

movement.

2.3 Polymer

Polymer comes from the two Greek words "poly", which means many, and "meros",

which means unit. A polymer may have one type of repeating unit of many different types of

repeating units. A polymer is indeed made by covalently linking small simple molecules

together. Polymeric molecules are gigantic in comparison to the hydrocarbon molecules.

Therefore, they are often referred to as macromolecules. Within each molecule, the atoms are

bound together by covalent bonds. For most polymers, these molecules are in the form of long

and flexible chains in which a string of carbon atoms constitutes the backbone. Furthermore,

these long molecules are composed of structural entities called mer units, which are repeated

along the chain. A single mer is called a monomer, and the term polymer means many mer units.

10
Molecular structures of polymer can be classified into four different categories: (i) linear, (ii)

branched, (iii) cross linked and (iv) network (Hossain, 2006).

When polymers are added to bitumen, the properties of the modified bitumen depend on the

polymer systems used (Peterson, 1998). The molecules of polymers are very much larger than

that of bitumen. So, when combined with bitumen, polymer creates drastic changes in the

physical properties of the final binder.

2.3.1 Types of Polymers

Polymer is a chemical compound and it is manufactured artificially in chemical industry

for use in various ways. Polymers can be classified according to their origin, structure chain,

molecular weight, density, thermal and deformation properties etc. However, in asphalt research

the focus falls on thermal and deformation properties. A simple classification (Hossain, 2006) of

polymer based on their properties can be as follows:

a) Thermoplastic Polymer (plastic like): Thermoplastics are the most common type of polymer

used. These polymers deform in a plastic or viscous manner at melting temperatures and become

hard and stiff at low temperatures, i.e. the structure is reversibly broken down with the

application of heat. These types of polymer are linear or slightly branched. These polymers can

be melted and reshaped, they are recyclable.

Thermoplastic polymers are used for pavement application. Examples of this type of polymers

are polyvinyl chloride (PVC), poly ethylene (PE), ethylene vinyl acetate (EVA), poly propylene

(PP), polyethylene terapthalate (PET), linear low-density polyethylene (LLDPE), high-density

polyethylene (HDPE), acronitrile butadiene styrene (ABS), polyethylene methacrylate (Acrylic).

b) Elastomer (rubber like): An elastomer is a polymer that has a flexible 'rubber' backbone and

large side-chains in its structure. The molecular structure of this type of polymer is usually

11
linear. The copolymers of this group have radial form of molecular chain. The most potential

modifiers are available in this family. Examples of these types of polymers are styrene butadiene

styrene (SBS), synthetic rubber, neoprene latex, natural rubber latex etc.

c) Thermo-harden Polymers: Thermo-harden or thermosetting polymers are heavily cross-

linked polymers, which are normally rigid and intractable. They consist of dense three-

dimensional molecular networks and degrade rather than melt on the application of heat. They

are not recyclable. They cannot be remolded or reshaped once manufactured to final product.

The most common thermo-harden polymers are celluloid, bakelite, epoxy resins, polyurethanes

etc.

2.3.2 Other methods of Classification of Polymers:

a) Based on Structure

Linear: The molecular chain of this type polymer is un-branched. It has low melting point and

high flow index compared to others; such as linear low-density polyethylene (LLDPE), linear

high-density polyethylene (LHDPE) and linear polypropylene (LPP)

Non-linear: The chain of this polymer is branched. This type of polymer has high melting point.

b) Based on Density

Low Density Polymer: The molecular weight of this polymer is less compared to others.

Example of low-density polymer is LLDPE.

High Density Polymer: The molecular weight of this type of polymer is high compared to other

polymers. Example of high-density polymer is HDPE (high-density polyethylene).

c) Based on Physical Form

Pellets: Most of the polymers available in the market are in pellet form.

12
Powder: Polymer are also available in powdered form.

Latex: colloidal deposition of polymer in aqeous medium.

Recycled: These are reclaimed polymer materials after service life or when discarded after use.

d) Based on Deformation Properties:

Elastomer: Elastomer exhibits high extensibility (up to 1000%) from which they recover rapidly

upon removal of the stress.

Plastomer: Plastomer, which exhibit plastic behavior at service temperature, will deform, but

will not return to original dimension when load is released.

2.4 Polymer Modification

Polymer modification of bitumen is the incorporation of polymers in bitumen by

mechanical mixing or chemical reaction (X. Lu. On polymer modified road bitumens [doctoral

dissertation]. Stockholm: KTH Royal Institute of Technology; 1997). During the last 40 years,

more and more researchers began to concentrate on polymer modification of bitumen and a

rapidly increasing number of research articles have been published since then. The polymers

investigated included plastomers (e.g. polyethylene (PE), polypropylene (PP), ethylene-vinyl

acetate (EVA), ethylene-butyl acrylate (EBA)) and thermoplastic elastomers (e.g. styrene-

butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), and styrene- ethylene/butylene-styrene

(SEBS) (Polacco et al.,2005), although none of these were initially designed for bitumen

modification. These polymers were reported to have improved properties of bitumen, such as

higher stiffness at high temperatures, higher cracking resistance at low temperatures, better

moisture resistance or longer fatigue life (Tayfur et al., 2007.). In (Polacco. 2006), an extensive

summary was given that an effective polymer modification results in a thermodynamically

unstable but kinetically stable system in which the polymer is partially swollen by the light

13
components of bitumen. Some important factors, including the characteristics of the bitumen and

the polymer themselves, the content of polymer and the manufacturing processes, determine the

final properties of polymer modified bitumen (PMB). As polymer content increases, phase

inversion may occur in some PMBs: from bitumen being the dominant phase to polymer

becoming the dominant phase (Sengoz, et al., 2008.). However, an ideal microstructure for PMB

contains two interlocked continuous phases, which determines the optimum polymer content for

bitumen modification. With these two interlocked continuous phases, PMB usually shows better

overall performance with respect to mechanical properties, storage stability and cost-

effectiveness.

2.4.1 Popular polymers for bitumen modification

Synthetic polymers began to be used to modify bitumen. Over the years, researchers

developed various polymer modifiers. Today, widely used polymers for bitumen modification

can be classified into two categories: plastomers and thermoplastic elastomers. As Stroup-

Gardiner et al., (stroup. 1995) reported, plastomers have little or no elastic component, usually

resulting in their quick early strength under load and the following permanent deformation or

brittle failure. As for thermoplastic elastomers, they soften on heating, harden on cooling

(Isacsson. 1994) and are able to resist permanent deformation by stretching under load and

elastically recovering once the load is removed, which leads to their greater success than

plastomers as bitumen modifiers. Some popular polymers for bitumen modification are listed in

Table below with their advantages and disadvantages. Among them, SBS attracted the most

attention due to its relatively good dispersibility (or appropriate solubility) in bitumen as well as

the relatively excellent properties and acceptable cost of SBS modified bitumen. Of course,

besides these listed polymers, some others like styrene-butadiene rubber (SBR, random

14
copolymers), styrene-butadiene diblock copolymers (SB) and ethylene-propylene-diene

monomer rubber (EPDM) were also popular for bitumen modification (Zhang et al., 2010). In

addition, some small- molecule organic materials, such as PPA and paraffin wax, were also

widely used as modifiers for bitumen.

Table 2.1: The Categories, Examples, Advantages and Disadvantages of Bitumen

CATEGORIES EXAMPLES ADVANTAGES DISADVANTAGES

PLASTOMERS Polyethylene(PE) High temperature Limited improvement in

properties. elasticity

PLASTOMERS polypropylene Relatively low cost Phase separation problem

PLASTOMERS Ethylene-vinyl Relatively good Limited improvement in

acetate (EVA storage stability elastics recovery

THERMOPLASTICS Styrene-butadiene- Increased stiffness. Compatibility problems in

ELASTOMERS styrene (SBS) Reduced temperature some bitumen.
sensitivity.
Relatively high cost

THERMOPLASTICS Styrene- High resistance to Storage instability problems.

ELASTOMERS ethylene/butylene- heat, oxidation and Relatively reduced elasticity
styrene (SEBS). ultraviolet

2.4.2 Developments for removing drawbacks

Great advances have been achieved in the field of bitumen polymer modification, there are still

various drawbacks which are limiting its future developments, such as higher costs, some PMBs‟

low ageing resistance and poor storage stability. Researchers have attempted different ways to

remove these drawbacks, including sulfur vulcanization (Wen. 2001.), adding antioxidants

(Ouyang 2006.), using hydrophobic clay minerals [90-98] and functionalization (including

application of reactive polymers) (Becker. 2003). Including saturation (Palaco. 2006). some

15
attempted measurements for removing PMB‟s drawbacks are listed in Table below with their

advantages and disadvantages.

 Sulfur vulcanization

Sulfur vulcanization, a chemical process widely used in the rubber industry, was found to be able

to improve the storage stability of some PMBs with unsaturated polymer modifiers (e.g. SBS

modified bitumen) (Wen. 2001). It is believed that sulfur works in two ways: chemically

crosslinking the polymer molecules and chemically coupling polymer and bitumen through

sulfide and/or polysulfide bonds. The crosslinking of polymer molecules leads to the formation

of a stable polymer network in bitumen; while the coupling between polymer and bitumen

directly reduces the possibility of separation. Sulfur vulcanization led to some improved

properties of some PMBs. Besides enhanced storage stability, some researchers (Wen 2002)

claimed that sulfur vulcanization could also improve the elasticity, deformation resistance and

some rheological properties of the PMB, but other ones (Zhang. 2010) found that sulfur

vulcanization made the PMB more susceptible to oxidative ageing and dynamic shear and

concluded that it is not a good idea to use sulfur as a sole additional modifier in PMB.

 Antioxidants

Some PMBs are sensitive to oxidation, e.g. SBS modified bitumen. In these cases, using

antioxidants could be helpful to retard oxidation of the PMB. Various antioxidants, including

hindered phenols, phosphites and organic zinc compounds, have been introduced in PMB in the

laboratory. They work by scavenging the free radicals and/or decomposing the hydroperoxides

that are generated in the process of oxidation (Ouyang. 2006.). These intermediates are very

reactive and contribute a lot to the oxidation. By controlling them, those antioxidants were

16
proven to retard oxidation of the PMB to some extent in the laboratory, but the real service

conditions of a road are quite different with the laboratory conditions.

 Hydrophobic clay minerals

Hydrophobic clay minerals have been used in both base bitumen and PMB. It is claimed that

their use in PMB is mainly for two aims: (1) improving the ageing resistance of PMB with

barrier properties of the dispersed clay platelets and (2) enhancing the storage stability of PMB

by decreasing the density difference between polymer modifiers and bitumen (Galooyak. 2010.).

Table 2.2: Attempted measurement for removing PMB’s drawback.

ATTEMPTED ADVANTAGES DISADVANTAGES
MEASUREMENT
Sulfur vulcanization Improved storage stability. Hydrogen sulfide released. Poor
recyclability.
Antioxidants Reduced oxidation High cost.
Hydrophobic clay minerals Increased ageing resistance Limited improvement in low-
temperature properties ductility and
elastic recovery.
Saturation Increased resistance to heat, High cost.
oxidation and ultraviolet.

2.5 Historical Development of Crumb Rubber In Pavement

In 1840s, the earliest experiments had involved incorporating natural rubber into asphalt

binder to increase its engineering performance properties. The process of asphalt modification

involving natural and synthetic rubber was introduced as early as 1843 (Thompson and A. J.

Hoiberg. 1979). In 1923, natural and synthetic rubber modifications in asphalt were further

improved (Yildirim, 2007).

The first attempt to modify bitumen or asphalt binders by adding rubber was made in 1898 by

Gauedmberg, who patented a process for manufacturing asphalt rubber, France was then given

credit for installing the first road with a crumb rubber modified asphalt surfacing material

(Mahrez, 1999). In 1950, the use of scrap tyre in asphalt was reported (Hanson et al., 1994).

17
 In the early 1960s, Charles Donald working as head of Material Engineer for the city of

Phoenix, Arizona, found that, after completing the mixing of crumb rubber with the virgin

asphalt cement and allowing it to blend for mix duration of 45–60minutes, there were new

material properties produced. There was swelling in the size of the rubber particles at higher

temperatures allowing for higher concentrations of liquid asphalt contents in pavement mixes

(Huffman, 1980). The application of rubber-modified asphalt pavement started in Alaska in 1979

and it involved placement of seven rubberized pavements totaling 4 lane km using the Plus Ride

dry process between 1979 and 1981 was reported. The performance of these sections in relation

to mixing, compaction, durability, fatigue, stability and flow and tyre traction and skid resistance

were described. Asphalt rubber using the wet process was first applied in Alaska in 1988 (Raad

and Saboundjian, 1998)

In Malaysia, the use of rubber as an additive for road pavement construction supposedly

started in the 1940s, but there has not been any official record of such practices. The first

recorded trial using rubberized bitumen technology was reported in 1988, when the wet mix

process was used with the mix of rubber additives in the form of latex into bitumen binder

(Sufian and Mustafa, 1997)

2.6 Benefits of Polymer Modified Bitumen (PMB)

The purpose of polymer modification of bitumen is to construct durable pavement with greater

stiffness and stability in order to minimize maintenance cost. Use of polymer some time may

increase cost of construction. In this case the benefit is evaluated by quality improvement of

pavement. The use of RPE (recycled polyethylene) and CR (crumb rubber) give benefits in

quality improvement and cost effectiveness as well as environmental hazards. The benefits of

PMB are assessed in three ways (Hossain,2006).

18
  Quality improvement of binder.

 A significant improvement in pavement.

 Environmental pollution control.

Other benefits of binders in bitumen includes the following:

• Polymer Increases binders viscosity that allows greater film thickness in paving mixes without

excessive drain down or bleeding

• It increases the binder's qualities to better cope with cracking and dynamic deformation of the

pavement internal layers.

• It improves the binder's behaviour to fatigue by increasing its mechanical resistance particularly

to tractive force.

• It raises the softening point of binder which helps in reducing bleeding.

• It increases elasticity and resilience at high temperatures

• It increases the cohesion of binder.

• It reduces thermal susceptibility to both low and high temperature.

• To rejuvenate aged asphalt binders.

A significant improvement in pavement is possible as-

• It increases flexibility of pavement.

• It reduces deformation in pavement.

• Improved aging and oxidation resistance due to higher binder contents, thicker binder films,

and anti- oxidants in the tire rubber.

19
• It provides greater fatigue resistance.

• It provides greater resistance to stripping.

• It provides greater durability.

Environmental improvement

Use of waste plastic in road construction could lead to a significant consumption of waste

plastic daily generated, which would be helpful in keeping the environment clean, reducing

clogging of drains. This reduces various hazards including health hazard, reducing dumping of

plastic materials wastes going into land fill.

2.7 Limitations of Polymer Modified Bitumen (PMB)

Polymer modified binder are not the solution to all pavement problems. It must be

properly selected, designed, produced, and constructed to provide the desired improvements to

pavement performance. Pavement structure and drainage must also be adequate. Limitations on

use of PMB include:

• Mobilization costs for polymer modified bitumen production equipment. For large projects, this

cost can be spread over enough tonnage so that increased unit price may be offset by increased

service life, lower maintenance costs, and reduced lift thickness. For small projects, however,

mobilization cost is the same, resulting in greater increase in unit price that may not be

economically viable.

• If work is delayed more than 48 hours after blending the asphalt rubber, some binders may not

be usable.

• Potential odour and air quality problems

• Polymer modified binders are often difficult to hand work because of stiffer binder and coarser

mixture.

20
2.8 Method of Blending

There are generally considered to be three basic processes which may utilize recycled plastic

(Polymer)/Tyre Rubbers or Crumb Rubber modifier (CRM) in the production of different types

of asphalt concrete pavements. These processes are known as the Dry Process, the Terminal

Blend Process, and the Wet Process.

2.8.1 Dry Process

The dry process is suitable for blending the crumb rubber with aggregate and asphalt without

using any special equipment required by other processes. Recycled rubber tyre is sized in a

particular form. Generally a cubical, uniformly shaped cut crumb rubber particle with low

surface area in size from 1/2-1/8 inches is normally used and is blended dry into the asphalt mix.

The aggregate grading is gap graded to allow for space for the 3% of rubber that is added. The

time at "reaction" temperature is limited by limiting mixing time and the rubber retains its

integrity. The surface only interacts with the asphalt creating a durable bond.

2.8.2 Terminal Blend Process

Terminal blend asphalt rubber is produced at a refinery or central blend plants and trucked to the

job site. Such materials are relatively new and use synthetic polymers with lower percentages of

crumb rubber than AR and significantly less rubber crumb than the wet process. The University

of Calgary has reported some success with terminal blend trials and the U.S. Turner Fairbanks

site reports chemically modified (stabilized) crumb rubber blends, which would fall into this

category.

2.8.3 Wet process: Wet process is the most common method of polymer modification of

bitumen. It is also called the McDonald process. This process requires special equipment to

blend polymer. The polymer/waste plastic is mixed and digested in the asphalt by either low or

21
high shear mixing in the wet process. The rubber undergoes a specific interaction with the

asphalt which often referred to as a reaction. It is rather a physiochemical reaction rather than

simply a chemical one. The polymer/rubber swells in components of the asphalt to produce a

composite. The wet process is used mostly in Australia, South Africa and USA. There are three

wet process (Hossain, 2006).They are (a) Chemical reaction process, (b) Gelatin process and (c)

Blending process.

Chemical Reaction Process: The polymer chemically reacts with bitumen and produces a

blend. The process is performed at the refinery. The blend from this method has higher storage

stability.

Gelatin Process: Here polymers do not react with bitumen. Polymer is dispersed into the

bitumen to form a two-phase homogeneous mixer.

Blending Process: This process may be called cooking process and suitable for scrap polymer

and rubber. Polymer/rubber is cooked in the bitumen in this process. This method requires a

blending/cooking system. Major parts of the blending equipment are a container, a mechanical

stirrer with shear blade and controlled heating facilities. Bitumen is heated in the container to

make it liquid. Then the polymer in particular form (powder, shredded, pellet, latex) is added to

the bitumen and stirring is continued up to completion of blending. Required blending time and

temperature and speed of stirrer depend on the type of polymer used.

The drawback with these systems is that mixing uniformly is difficult and often leads to

segregation of waste plastics.

2.8.4 Factors Affecting Blending

The process of blending compatible polymer with bitumen is affected by the

Following factors.

22
2.8.4.1 Blending Mechanism: The possible problems with modified bitumen are mainly in the

storage of the bitumen, mixing temperatures, and the length of time the material is held at

elevated temperatures before laying. The blending of bitumen and polymer is not an easy process

because two complex materials are forced together to form a two-phase system. The polymer

must disperse uniformly into bitumen. Hence it is required to provide high shear force during

blending. The configuration of shear blade of the stirrer of blender and the speed of the stirrer

determine the shear rate. The speed of the stirrer should not be less than 2500 rpm (Ibrahim. et

al., 1998). However some polymer does not require high shear force such as EVA and LLDPE.

2.8.4.2 Blending Time: The duration of blending time depends on the blending temperature and

applied shear rate and on the complexity of polymer system. Blending time should be kept

minimum by adjusting blending temperature and applied shear rate. Too long blending time may

cause the change of rheological properties of PMB.

2.8.4.3 Blending Temperature: Blending of polymer should be performed within a specified

temperature range. It is an important factor. Without controlling the temperature it is not possible

to prepare blend properly. The blending temperature mainly depends on the molecular weight of

the polymer. Polymer of higher molecular weight requires higher blending temperature (Baker,

1998). Blending temperature of particular polymer is above its melting point. From the economic

point of view and to diminish some change in asphalt or polymers, a temperature of the order of

the 170-190 °C is generally satisfactory.

2.9 Interaction between Bitumen and Rubber

Typically, CRMB is produced by mixing bitumen and rubber at elevated temperature for a

certain period. The bitumen–rubber interaction controls the property development of CRMB and

has a great influence on the binder transport and storage. There are two main stages which occur

23
during the interaction process: rubber swelling and degradation (Abdelrahman and Carpenter

1999, Wang et al., 2017). Rubber swelling is a physical diffusion process while the degradation

of rubber is a chemical process in which new substances are created. It is often seen in the

literature that researchers use the terminology of rubber dissolution to describe the status of

rubber particles in bitumen during the interaction. Rubber dissolution is measured by extracting

the rubber particles from the binder matrix. The portion of rubber particles in CRMB that passes

through a certain fine mesh (usually 75 μm), which is usually difficult for recognition by eyes, is

considered as the dissolved portion (Ghavibazoo et al. 2013b). From the definition, it can be seen

that dissolution here is a vague engineering term which cannot distinguish if chemical

degradation of rubber occurs or not. The dissolved portion may contain extremely fine rubber

particles that are disassociated/split from coarse rubber particles. The percentage of rubber

dissolution is often used to differentiate different types of CRMB, e.g. AR and TB. Swelling and

complete dissolution of rubber are two opposite ends of the interaction of bitumen and rubber

depending on the interaction conditions (Ghavibazoo et al., 2013).

2.9.1 Rubber Swelling

Swelling of polymers is a volume expansion process of the polymer network due to

absorption of solvents. For uncross linked polymers when exposed to suitable solvents, they can

be easily swollen up and eventually dissolve into the solvent. This process is called polymer

dissolution. The dissolution of an uncross linked polymer into a solvent involves two

phenomena, i.e. solvent diffusion-induced swelling and chain disentanglement (Tu and Ouano

1977). It should be pointed out that the definition of polymer dissolution here is different from

the term „dissolution‟ used for rubber dissolution previously in an engineering context. For cross

linked polymer systems in which links between chains or segments are established, because of

24
the constraints of the network structure, the network might be swollen by absorbing solvents but

the dissolution will hardly occur. Limited swelling is a characteristic property of polymers with

network structures (Flory and Rehner 1943). As clarified in the previous section, tire rubber

contains a large portion of vulcanized/cross linked polymer and a small portion uncross linked

polymer. Therefore, swelling of tire rubber in organic solvents is a partial dissolution process

(Stroup-Gardiner et al. 1993, Artamendi and Khalid 2006). Depending on the compatibility

between rubber and solvents, the swelling extent and dissolution rate may vary. When mixing

rubber with bitumen at high temperatures, the light fractions of bitumen will diffuse into the

rubber network and cause its swelling. The volume change of rubber particles and the formation

of the gel layer adjacent to the rubber–bitumen interface reduces the inter-particle distance and

changes the component proportions of the remaining bitumen and, therefore, stiffens the

composite material.

2.10 Future Developments

Ideally speaking, the properties of polymer modifiers should be very closely designed

with the needed PMB characteristics, seen in Table below. After mixed with bitumen, polymer

modifiers are supposed to physically or chemically interact with bitumen at a proper degree to

form a stable biphasic structure with two interlocked continuous phases (Brûl. 1996). A low

degree of interaction between polymer and bitumen could cause a separation problem; while a

high degree may lead to the gelation problem and high costs. The interaction between two

polymer molecules also should be neither too low nor too high. The polymers with a biphasic

structure of a dispersed rigid phase in a flexible continuous phase may be helpful to obtain better

PMB properties. With the modification of these ideal polymers, the bitumen properties will be

improved to a large extent.

25
Table 2.3: Properties of polymer modifiers with needed PMB modifiers
NEEDED PMB CHARACTERISTICS PROPERTIES OF POLYMER MODIFIER
To be stiff at high temperatures and soft Low temperature sensitivity
at low temperatures
To be adhesive to aggregates Outstanding contributions to adhesion of the resulting PMB
with aggregates
To be workable Excellent dispersibility (or appropriate solubility) in bitumen
To be storage-stable Appropriate compatibility with bitumen
To be durable (ageing- and fatigue-) High thermal stability and stable in-time response
To be recyclable Strong responsibility for recyclability of the final products
To be cost-effective Low cost
To be environment-friendly Low environmental impact during production and application
To be practical, compromises will always have to be made and it is therefore important to decide
on the dominant characteristics that are most needed, when designing PMB.

26
 CHAPTER THREE
MATERIALS AND METHOD

3.1 Equipment and Apparatus

 0rifice viscosity bottle

 Water bath (hh-2, pec medical use)

 Thermostat oven (model dhg-9101.sa. made in England)

 Sample plates

 Electronics weighing balance (s180709495, model ls-ej-220a. made in China)

 Spatula

 Specific gravity bottles

 Petri dish

 Mechanical stirrer(model a901d for blending made in China)

 Penetrometer

 Ring and ball

 Retort stand

3.1.1 Reagents;

 Bitumen

 Waste inner tube

3.1.2 Solvent

 Kerosene

 Petrol

 N hexane

27
3.1.3 Sample Collection; Bitumen of about 12Litres was collected at IFAKI, EKITI STATE

NIGERIA while the waste inner tube were collected from OYE EKITI and was ground at OYE.

3.2 Method;

About 500g 0f the bitumen was weighed and heated to a fluid condition in a sample plate

container for the blending of crumb rubber with bitumen, it was heated to a temperature of 160oc

and then the crumb rubber (inner tube) was added. For each mixture sample 0%, 6%, 8% , 10%

and 12% of crumb rubber was added to different sample plates labelled SAMPLE A, B, C, D

and E with bitumen by weight. The blend is mixed for about 3-4 minutes. The mixtures is then

heated to 160oc and then the whole mass was stirred with a mechanical stirrer for about

50minutes. Care was taken to maintain the temp between 1600c to 1700c. The content was

gradually stirred for about 50minutes then the modified bitumen was cooled at room

temperature and suitably stored for various tests such as penetration test, ductility test softening

point test, viscosity test, specific gravity test, water content test and loss on heating test. FTIR

test was also carried out.

3.2.1 Step 1:

SAMPLE A: A pure bitumen is used for sample i.e no crumb rubber was added.

SAMPLE B: 30g of crumb rubber was weighed and bitumen was added to make it up to

500g. (6%)

SAMPLE C: 40g of crumb rubber was weighed and bitumen was added to make it up to

500g. (8%)

SAMPLE D: 50g of crumb rubber was weighed and bitumen was added to make it up to

500g. (10%)

28
 SAMPLE E: 60g of crumb rubber was weighed and bitumen was added to make it up to

500g. (12%)

Step 2: Each samples was heated in an electrochemical oven at 1600c for about

50minutes and their whole mass was stirred using mechanical stirrer for about 50minutes.

3.2.2 Ductility Test

The bitumen sample was heated and poured in the mould assemble placed on a plate.

These samples with moulds are cooled in the air and then in water bath at 270c temperature. The

excess bitumen is cut and the surface is leveled using a hot knife. Then the mould with the

assembly containing sample was kept in the water of the ductility machine for about 90minute.

The sides of the moulds are removed, the clips are hooked on the machine and the machine was

operated. The distance up to the breaking of thread is the ductility value which is reported in cm.

3.2.3 Moisture Content

Dry petri dish was weighed and certain requirement of modified bitumen was poured into

the petri dish after which it was taken to the oven to dry at temperature of about 1050c for 24hrs.

after drying it is then weighed again to get the moisture content loss. PURE and odified bitumen

constant weight is 2.004g.

Petri dish= W1

Petri dish + bitumen = W2

Petri dish+ bitumen(after oven dry)= W3

Moisture content =

29
3.2.4 Viscosity Test

Orifice type viscometers are used to indirectly find the viscosity of liquid binders like

cutbacks and emulsions. The viscosity expressed in seconds is the time taken by 50ml bitumen

materials to pass through the orifice of a cup under standard test condition and specified

temperature.10mm orifice was cleaned with chromic acid solution, rinsed very well with water

and drained. The modified bitumen sample was placed inside clean 10mm orifice cup and placed

inside a thermosetting water bath at 90oc. It was removed and allowed to drain into 50ml flask.

The stopwatch was reading in seconds immediately the orifice opened. It was stopped when the

50ml flask filled to the mark with sample and time recorded. The same method was used for the

remaining sample at the same temperature.

Viscosity =

Figure 3.1: image of orifice viscometer

30
3.2.5 Softening Point Test

The test is conducted by using ring and ball apparatus. The brass ring containing test

sample of bitumen is suspended in liquid like water like glycerin at a given temperature. A steel

ball is placed upon the bitumen sample and the liquid medium is heated at rate of 50oc per

minutes. Temperature is noted when the softened bitumen touches the metal plate which is at a

specific distance below. Generally higher softening point indicates lower temperature

susceptibility and is preferred in hot climates. Softening point denotes the temperature at which

the bitumen attains a particular degree of softening under the specification of test.

3.2.6 Penetration Test

It measures the hardness or softness of bitumen by measuring the depth in the tenth of a

millimeter to which a standard loaded needle will penetrate vertically in 5secs. The penetrometer

consists of a needle assembly with total weight of 100g and a device for releasing and locking in

any position. The bitumen is softened to a pouring consistency, stirred thoroughly and poured

into containers at depth at least 15mm in excess of the expected penetration test. The test should

be conducted at a specified temperature of 25oc. it may be noted that penetration value is largely

influenced by any inaccuracy with regards to pouring temperature, the size of needle, weight

placed on the needle and the test temperature. A grade 40/50 bitumen means the penetration

value is in the Range 40 to 50 at standard test condition. In hot climates, a lower penetration

grade is preferred.

3.2.7 Specific Gravity

25ml specific gravity bottle with the lid was washed thoroughly with detergent, rinsed

with distilled water, oven dried at 105oC in an oven and cooled. It was weighed with the lid in

31
analytical weighing balance and recorded W1. Distilled water was poured into 60oC and the lid

inserted so that the water comes out from the narrow opening in the lid. The outer part of the

bottle and the lid were wiped with clean cloth and weighed W2. At the same temperature, this

was repeated for the remaining samples. Modified bitumen sample and weighed.

Specific Gravity =

3.2.8 FTIR

Fourier Transform Infrared[FTIR] spectroscopy Procedures infrared intensity in

opposition to wavelength of light, it is used to regulate the nature of related functional groups

and structural features of biological extracts with nanoparticles. (Amudha Murugan et al., 2014)

32
 CHAPTER FOUR

RESULT AND DISCUSSION

4.1 Results

The results for the Physico-mehanical properties (i.e. Specific gravity at 600C, Viscosity at both

900C and 1800C, Water content, Stability, Ductility 200C Softening point and Penetration of

different samples of bitumen-tube blends which are Pure bitumen-S125, bitumen with 6% of

inner-tube, bitumen with 8% of inner-tube, bitumen with 10% of inner-tube, and bitumen with

12% of inner-tube are shown in the table 4.1 below.

Table 4.1: Physico-mechanical Properties of bitumen-tube blends

PARAMETERS A (Pure ITB ITC ITD ITE

bitumen- (6%) (8%) (10%) (12%)
S125)
Specific gravity(600C) 0.9938 1.0094 0.9732 0.9649 0.8753

Viscosity (900C) (cp) 207.366 634.495 1020.2 1158.73 1209.95

Viscosity (1800C) (cp) 10.484 10.635 10.921 11.137 11.521
Water content(g/100g) 11.638 8.000 8.973 8.732 7.096
Loss on 1.841 1.530 1.310 1.152 1.050
heating/Stability(g/100g)
Ductility(200C) 19.2 11.500 11.100 9.700 9.100
0
Softening point ( C) 57.9 60.112 62.02 63.3 65.21
0
Penetration (25 C) 46.22 46.51 46.55 47.1 49.12
KEY: 1cp = 0.001Pas/sec
Recommended viscosity temperatures for various types of bitumen: 60/70 or 80/100 (Hard) =
2400C, S125 (Soft) =1800C, MCI (Softer) = 1200C, MCO (Softest) = 80-1000C.
Bitumen was confirmed to be S125.

33
4.2 Discussion of Results

Specific Gravity

This study determined the production and characterization of bitumen-tyre tube blends for

construction of road pavement. The result of the analysis from table 4.1 above and figure 4.1

below indicated that specific gravity at 600C temperature ranged from 0.8753 to 1.0094 (600C)

with Sample B (ITB (6%) having the highest specific gravity followed by sample A (Pure

bitumen-S125) and sample C (ITC (8%) with 8% inner tube with the value of 1.0094, 0.9938

and 0.9732 respectively. Meanwhile, samples with 10% and 12% tube-bitumen blend had the

least specific gravity with the value of 0.9649 and 0.8753 respectively. It was observed that

increase in substitution of tyre tube rubber bring about decrease in specific gravity of the

bitumen-tyre tube blends across the table. Specific gravity is the ratio of the density (mass of a

unit volume) of a substance to the density of a given reference material. Bitumen binder has

specific gravity in the range of 0.97 to 1.02. The presence of impurities affect the specific

gravity.

The results obtained in the table 4.1 was similar to specific gravity of bitumen-crumb rubber

blend with the value of 1.015 reported by Deshmukh &. Kshirsagar, (2017).

34
 0
Figure 4.1: Specific Gravity (60 C) of Bitumen-Inner Tube Samples

Viscosity (900C)
Table 4.1 above and figure 4.2 below shows the viscosity at (900C), the viscosity of the bitumen-

tyre tube rubber which was found to ranged from 207.366 to 1209.952 in which sample A (pure

bitumen) having the least viscosity and sample E (12% inner tube rubber) have the highest

viscosity value. As the level of substitution of tyre tube increases, decrease in viscosity was

noticed in all the samples.

35
 0
Figure 4.2: Specific Gravity (90 C) of Bitumen-Inner Tube Samples

Viscosity (1800C)
Also from table 4.1 and figure 4.3, viscosity of bitumen-tyre tube rubber was recorded (1800C)

(cp), increase inner tube rubber substitution brings a slight increase in viscosity of the samples.

Pure bitumen sample had the least viscosity at 900C and 1800C. Sample ITE with (12%) inner

tube-rubber composition have the highest viscosity with the value of 1209.952 and 11.521

respectively. Viscosity measures fluid resistance to flow and it described the internal friction of a

moving fluid. Fluid with large viscosity resists motion because its molecular makeup gives it a

lot of internal friction. Increase in viscosity with the addition rubber obtained in this study was in

tandem with the result of Kakar et al (2021) revealed that addition waste polyethylene and its by-

products increases the viscosity of in asphalt binder.

36
 0
Figure 4.3: Viscosity (180 C) (Cp) of Bitumen-Inner Tube Samples

Water Content
The water content (g/100g) of the sample is indicated in table 4.1 and figure 4.4,where it was

revealed that the value for the water content of the samples ranged from 7.096 to 11.638. The

pure bitumen sample had the highest moisture content while sample with 12% inner tube had the

least water content with the value of 7.1 and 11.6% respectively. Increase in composition of tyre

tube rubber was found to cause decrease in water content in the samples. Moisture content

obtained in this study was in similar with 10.2% water content reported by Ghabchi, Zaman and

Arshadi, (2016) in their study which examined ground tire rubber (GTR) in asphalt pavements:

literature review and dot survey.

37
Figure 4.4: water content (g/100g) of Bitumen-Inner Tube Samples

Loss of Heating/Stability
Loss on heating or stability (g/100g) of bitumen-inner tube was determined in the sample and

analysis evident from table 4.1 and figure 4.5 analysis of this study shows that higher stability

value was recorded in pure bitumen sample with the value of 1.841 followed by sample B (ITB

6%), sample C and D with an increase in composition of 6%, 8% and 10% inner tube rubber.

Whereas, the least stability value was obtained in sample E (12%) inner tube rubber. Increase in

composition of inner tyre tube rubber resulted into reduction in loss on heating or stability of the

samples. These Damage to highways typically take place at the top layer of the pavements of the

binder and erosion layers as opposed to the foundation and lower layers. Damage to the binder

and erosion layers generally comprises surface cracks, deformations, wheel ruts and potholes.

Temperature effect is the main cause of the damages to highway pavements and performance.

Low stability in bitumen-inner tube rubber of sample C, D and E with 8%, 10% and 12% inner

38
tube rubber composition may lead to various types of distress in road pavements (Ozgan, 007).

According to Tigdemir, Kalyoncuoglu and Kalyoncuoglu, (2004), the stability of bitumen-inner

tube samples pavements depends on the stiffness of the mix, bitumen content, softening point of

bitumen, viscosity of bitumen, grading of aggregate, construction practice, traffic and climate.

Figure 4.5: Loss on heating/stability (g/100g) of Bitumen-Inner Tube Samples

Ductility
Also from table 4.1 and figure 4.6, the ductility of the of the bitumen-inner rubber samples

evaluated indicated that pure bitumen sample had the highest ductility followed by sample with

6% and 8% inner tube-rubber with the value of 19.200, 11.500 and 11.100 respectively.

Meanwhile, sample E with 12% inner tube rubber had the lowest ductility. These findings

buttressed the ductility test results on bitumen-crumb rubber reported by (Deshmukh &

Kshirsagar, 2017). Ductility is the property of bitumen that permits it to undergo great

deformation or elongation. Ductility is defined as the distance in cm, to which a standard sample

39
or briquette of the material will be elongated without breaking. From the ductility test, the result

established that the inner tube rubber added will harden the bitumen. Therefore, the bitumen

becomes more viscous and harden, which would be useful to obtain stiffer bitumen asphalt for

pavement.

0
Figure 4.6: Ductility (20 C) of Bitumen-Inner Tube Samples

Softening Point

However, softening point (0C) as shown in table 4.1 and figure 4.7 show that the least softening

point was obtained from pure bitumen sample, followed by samples with 6%, 8% and 10% inner

tube rubber with the value of 57.900, 60.112 and 62.020 0C.The highest softening point was

recorded for sample E with 12% composition. Softening point indicates the temperature at which

the bitumen attains a particular degree of softening under the specifications of test. From the

result of the test, the softening point for normal pure bitumen in this study was relatively higher

than that of 42.75˚C reported by (Tigdemir et al., (2004). Softening point increases with the

40
increase amount of the inner tube added. This is an indication that the bitumen becomes less

prone to temperature changes as the content of the rubber increases

0
Figure 4.7: Softening point ( C) of Bitumen-Inner Tube Samples

Penetration

Lastly, the penetration of bitumen-inner tube rubber samples examined as indicated in table 4.1,

it was shown that as the inner tube rubber composition increases, increase in penetration value

were observed. The penetration value ranged from 46.220 to 49.1200C in which pure bitumen

sample had the least value and samples with 12% inner tube rubber sample had the highest

penetration value. Results of the penetration value obtained agrees with the penetration range

value recorded in rubber waste in the construction of flexible pavement reported by Deshmukh &

Kshirsagar (2017), where 14.33 to 690C range was recorded. Lower value makes harder grade of

asphalt, giving additional strength to the road and reduces water damage. Penetration value is a

41
measures of hardness or softness of bitumen by measuring the depth in tenths of a millimeter to

which a standard loaded needle will penetrate vertically in 5 seconds. Penetration values were

found to increase with an increase in the amount of rubber waste added.

0
Figure 4.8: Penetration (25 C) of Bitumen-Inner Tube Samples

4.3 FTIR Analysis

The below FTIR analysis shown in the tables 4.2-4.6 below indicates the functional groups of

each samples, the 5 samples absorption bands indicate that all samples are complex molecules.

The FTIR Spectra for sample A is shown in Table 4.2 which is a pure bitumen shows 1377.22

for the C-C bend, 1456.23cm-1 for C-H bending, 3439cm-1 for the O-H stretch and 1602.90cm-1

for N-H bend. The other samples have just a little differences in their absorption bands. For the

FTIR spectra of sample B shown in Table 4.3, 3443.05cm-1 shows the O-H stretch which is

42
broad, 2924.18 and 2852.81cm-1 shows C-H stretch, 1458.23cm-1 shows C-H bending and

1377.22cm-1shows C-H bending with sharp bend. For the FTIR spectra of sample C shown in

Table 4.4, 3443.05cm-1 shows the O-H stretch, 2924.18cm-1 and 2852.81cm shows the C-H

stretch, 1458.23cm-1 shows the C-H bend and 1377.22cm-1 shows the C-C bend. For FTIR

spectra of sample D shown in Table 4.5, 3439.19cm-1 shows the O-H stretch (broad), 2924.18cm-
1
and 2852.81cm shows C-H stretch, 1456cm-1 shows the C-H bending and 1377.22cm-1 shows

C- bending. While the FTIR spectra of sample E shown in Table 4.6, 3448.84cm-1 shows the O-

H stretch, 2924cm-1 and 2852.81cm-1 C-H stretch, 1458.21cm-1 shows the C-H bending and

1375.29cm-1 shows C-C bending.

The FTIR analysis result of pure bitumen and the modified samples is shown in Tables 4.2-4.6

indicates that the changes in the FTIR peaks can be attributed to the level of modification, hence

the changes in the peaks might be as a result of the waste tyre tube added to the bitumen.

Table 4.2: Results for FTIR Analysis for Sample A

IR WAVE LENGTH FUCTIONAL COMMENT
GROUPS
1377.22 C-C Bending Sharp
1456.23 C-H Bending Sharp
2924.18 and 2852.81 C-H Stretch (Alkane) Sharp
3439.19 O-H Stretch Broad
1602.90 N-H Bending Broad

Table 4.3: Results for FTIR Analysis for Sample B

CM-1 FUNCTIONAL COMMENT
GROUPS
3443.05 O-H stretch Broad
2924.18 C-H stretch Sharp
2852.81 C-H Stretch(Alkane) Sharp
1458.23 C-H Bending Sharp
1377.22 C-C Bending Sharp

43
Table 4.4: Results for FTIR Analysis for Sample C
IR WAVELENGTH FUNCTIONAL COMMENT
GROUPS
3443.05 O-H STRETCH Broad
2924.18 C-H STRETCH Sharp
2852.81 C-H(ALKANE) Sharp
STRETCH
1458.23 C-H bending Sharp
1377.22 C-C bending Sharp

Table 4.5: Results for FTIR Analysis for Sample D

IR WAVELENGTH FUNCTIONAL COMMENT

GROUP
3439.19 O-H stretch Broad
2924.18 C-H (Alkane) Sharp
stretch
2852.81 C-H (alkane) Sharp
1456.30 C-H bending Sharp
1377.22 C-C Bending Sharp

TABLE 4.6: Results for FTIR Analysis for Sample E

IR FUNCTIONAL COMMENT
WAVELENGTH GROUP
3448.84 O-H stretch Broad
2924.18 C-H (Alkane) stretch Sharp

2852.81 C-H (alkane) stretch Sharp

1458.21 C-H bending Sharp

1375.29 C-C Bending Sharp

44
 CHAPTER FIVE

CONCLUSION AND RECOMMENDATIONS

5.1 Conclusion
From the analysis conducted with different percentage of waste crumb rubber modified with

bitumen, the addition of waste inner tube to bitumen helped in producing modified bitumen with

some improved properties. The research therefore shows that CRMB provides a lot of

advantages over pure bitumen, These advantages include increased stability, improved bitumen

resistance to rutting due to high viscosity, high softening point and better resilience, improved

bitumen resistance to initiated cracks. It also indicates the reduction of maintenance cost of road

pavement and solves the disposal of waste inner tubes and thereby reduces environmental

pollution.

5.2 Recommendation

Polymer modification has been proven to be an effective way to improve bitumen

properties to some extent by many researchers and has been used widely in practice. However,

the currently popular polymer modifiers have various disadvantages limiting their application.

Some important problems with bitumen polymer modification are still not well understood. More

efforts are needed to promote a further development.

45
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 APPENDIX
FTIR Results

Figure 1: Sample A FTIR Results

Figure 2: Sample B FTIR Results

51
Figure 3: Sample C FTIR Results

Figure 4: Sample D FTIR Results

52
Figure 5: Sample E FTIR Results

53