Effects Of Trans-Polyoctenamer (TOR) On Properties Of Rubberized

Bitumen

WAN NOR YUSAIRAH BT WAN MOHD NASIR

CE093679

PROJECT SUPERVISOR :
PUAN HERDA YATI BINTI KATMAN

COLLEGE OF ENGINEERING
UNIVERSITI TENAGA NASIONAL
2015

L
I
T
E
R
A
T
U
R
E

R
E
V
I
E
W

2.1 LITERATURE REVIEW

Bitumen grade 80/100
Bitumen is a non-crystalline viscous material, black or dark brown, which is substantially soluble
in carbon disulphide (CS2), possessing adhesive and water-proofing qualities. It consists
essentially of hydrocarbons and would typically comprise at least 80% carbon and 15%
hydrogen, the remainder being oxygen, sulphur, nitrogen and traces of various metals. (Benzene
International, 2008).
In Malaysia, the term of bitumen refers to the binder material, which produces from refinery of crude oil.
The mixture of bitumen and aggregate is called asphaltic concrete. The chemical composition of bitumen
are listed as shown in Table 1:

Minerals

Percentage content (%)

Carbon

80-85

Hydrogen

10

Sulfur

1-5

Nitrogen

Oxygen

<1

Table 1: chemical composition of bitumen

Bitumen can be obtained from two main sources which are:

Natural sources bitumen which is located in geological stratum and can be obtained in

the hard and soft form.

Petroleum bitumen bitumen in colloidal form obtained from refinery process of crude
oil and has been widely used in the road construction.

PROPERTY

GRADES
BITUMEN
80/100

STANDARD
ASTM / AASHTO

Specification

1.01/1.06

D-70

C
Penetration @

80/100

D-5

25 C
Softening Point

45/52

D-36

C
Ductility @ 25

100 MIN

D-113

C CMS
Loss on Heating

0.5 MAX

D-6

(wt)%
Drop in

20 MAX

D-6 & D-5

%
Flash Point C

225 MIN

D-92

Solubility in

99.5 MAX

D-4

CS@ (wt)%
Spot Test

NEGATIVE

Density @25 C

1.01/1.06

D70

Gravity @25/25

Penetration
After Heating

Temperature

Max 90-100 above the soft

(C)
Table 2: Properties of bitumen 80/100

Crumb Rubber
Crumb rubber is produced by reducing scrap tires down to sizes ranging from 3/8 to 40 mesh
particles and removing 99 percent or more of the steel and fabric from the scrap tires. Crumb
rubber is manufactured from two tire buffings and scrap tire rubber. There are several processes
for manufacturing crumb rubber. Two of the most common are ambient grinding and cryogenic
processing. These processes from where that can be obtained.

Ambient scrap tire is obtained by the grinding of the ground tire rubber at or above ambient
temperature without the use of any cooling system to make the rubber brittle, through either
cracker mills or a granulator. By using granulator, the rubber particles will tend to form a cut
shape and rough particles. Meanwhile by using cracker mills, the particles will be long and
narrow in shape with a high surface.

Figure 1 : Ambient scrap tire procces (Reshner, 2006)

Cryogenic process is obtained through a process where the scrap tire rubber is frozen using
liquid nitrogen or other frozen method to a temperature below the glass transition temperature of
the rubber to make it brittle like glass, and then the rubber is put in a hammermill and reduced to
the desired particle size (Reschner, 2006). Typically, the size of the feed material is a nominal 2
inch chip or smaller. The material can be cooled in a tunnel style chamber, immersed in a "bath"
of liquid nitrogen, or sprayed with liquid nitrogen to reduce the temperature of the rubber or tire
chip.

Figure 2: cryogenic scrap tire process (Reshner ,2006)

Transpolyoctenamer
Transpolyoctenamer (TOR) is also known as Vestenamer is a mixture from butadiene by
dimerization to 1,5-cyclooctadiene, followed by selective hydrogenation to cyclooctene and
finally by a metathesis polymerization of this cyclic monomer. It contains one double bond for
every eight carbon atoms with prevalent trans conformations.It consists of linear and cyclic
macromolecules and is a low molecular weight polymer with a broad molecular weight
distribution (Kyung Eui Min and Han Mo Jeong,2012).

Figure 3: Synthesis of trans-polyoctenamer

Characteristics of TOR can conduct unique characteristics such as crystallinity, low viscocity
above the melting point, high proportion of macrocycles ( around 25%) and unsaturation. Low
initial viscosity during the initial mixing operation , increased viscosity after polymerization to
prevent drain down , chemical bonding of the ground tire rubber (GTR) to the asphalt , chemical
bonding of the final rubberized to the aggregate to reduce stripping and conversion of the
thermoset polymer which is can reduces cracking and rutting are four special features of TOR as
additives.(Evonik Industries, 2007)
It is believed that the addition of a binder additive like TOR will help decrease the viscosity of
asphalt rubber binder without negatively affecting its rheological properties.
TOR is a mixture of linear and macrocyclic polymers that exhibit special structural features
when added crumb rubber modified bitumen:

low initial viscosity

during the initial mixing
operation

increased viscosity after

polymerization to prevent
drain down

chemical bonding of the

final rubberized bitumen
to the aggreagte to reduce
stripping

chemical bonding of the

crum rubber to bitumen

conversion of the
thermoplastic bitumen to
a thermoset polymer
which reduces cracking
and rutting

Crumb Rubber Modified Bitumen With Polyoctenamer(Crmb-Tor)

Advantages:

Roads are less brittle at lower temperatures

Roads have better rutting resistance

Roads have higher stiffness

Roads live longer

Penetration Test
Penetration Test determines the hardness of Bitumen by measuring the depth ( in tenths of a mm)
to which a standard, and loaded needle will vertically penetrate in 5 seconds, a sample of
Bitumen maintained at a temperature of 25 C.Hence the softer the bitumen, the greater will be
its number of penetration units. A previous study (Hongying Liu,2013) The effect of rubber
content and TOR addition on the conventional physical properties of s presented in figure 4. It
was found that the penetrations of bitumen with increasing crumb rubber powder content present
a downward trend, especially the increase from 15% to 20%, which shows a significant decrease.
When the content increases from 20% to 25%, the extent of decreased penetrations of CRMB is
different from it increasing from the 15% to 20% increment. In addition, the penetrations of
CRMB with TOR show an obvious dropping trend, which implies that the penetrations of CRMB
would be improved further by TOR.

Figure 4 : penetration test result (Hongying Liu,2013)

Softening Point Test

This method is useful in determining the consistency of bitumen as one element in establishing
the uniformity of shipments or sources of supply. Softening point is the temperature at which the
bituminous binders have an equal viscosity which is the consistency of all the grades will be
same at the softening point.As an example if two samples have softening points of 40 C and 80
C respectively, both will have the same consistency at their softening point. The test gives an
idea of the temperature at which the bituminous materials attain a certain viscosity. Bitumen with
higher softening point may be preferred in warmer places.
Softening point should be higher than the hottest day temperature, which is anticipated in that
area otherwise bitumen may sufficiently soften and result in bleeding and development of ruts.
Based on previous study (Hongying Liu,2013) ,figure 5 shown clearly when CR concentration
increase, softening point also increase especially for CRMB-TOR graph. It can concluded that
TOR is very useful to high temperature performance of CRMB.

Figure 5: softening point test graph (Hongyin Liu, 2013)

Brookfield Viscosity Test
The objective of this test is to study the viscosities of crumb rubber bitumen modified with and
without TOR, The viscosity of bitumen binders at high temperature is considered to be an
important property because it represents the binders ability to be pumped through an bitumen
plant, thoroughly coating aggregates in the bitumen concrete mixing facility, and be placed and
compacted to form a new pavement surface. Based on latest study (Hongying Liu and Zhijun

Chen,2013) Figure 5 shown the viscosity values at 177 C and 190C for crumb rubber mixed
bitumen with and without TOR. A general trend was found from the results that the viscosity
values of crumb rubber mixed bitumen increase with increased crumb rubber concentration.
However, the addition of TOR resulted in reducing the viscosity, and this finding is equally true
for crumb rubber mixed bitumen at both testing temperatures. The increase in the viscosity of
crumb rubber mixed bitumen is thought to be caused by the addition of crumb rubber to the
binder, which makes the binder more stickier. In reality, TOR was added to the mixture to
increase the workability and compatibility of the mixture. As it is known that, the crumb rubber
mixed bitumen should be used within 24 hour inpractical engineering applications, should the
crumb rubber mixed bitumen be applied again after a long storage time, the crumb rubber mixed
bitumen needs to be tested as to whether the properties of crumb rubber mixed bitumen can still
meet the technical requirement or not of the specification in use.

Figure 6: Brookfield viscosity result

Dynamic Shear Rheometer
Dynamic Shear Rheometer (DSR) test is conducted to determine rheological properties of
bitumen binder. The complex shear modulus (G*) and the phase angle () of the samples are

measured in the DSR. G* is considered the total resistance of the binder to deformation
when sheared at a certain frequency and temperature and it is highly sensitive to the
morphological state of a heterogeneous system( Kyung Eui Min and Han Mo Jeong,2012) Two
components make the complex shear modulus, these are the storage modulus (G) and the loss
modulus (G); the first modulus is related to the elastic properties of the material, whereas, the
second modulus relates to the viscous properties of the material. The phase angle is then the
angle between the storage modulus (G) and the resultant complex shear modulus (G*),
the higher the phase angle the more viscous-like the material will behave; likewise the
lower the phase angle the more elastic-like the material will behave. The performance-graded
asphalt binder specification uses the values of G* and to determine the performance grade of
the binders. (Airey GD, 2009).
Multiple Stress Creep Recovery(MSCR)
Multiple stress creep recovery (MSCR) is a test that conducted to evaluate the binders potential
for permanent deformation by using DSR as the laboratory equipment. The MSCR mode of
loading at a pre-determine test temperature is subsequently adopted as the preferred test method(
S.E Zorro , 2012). Procedure conducted by applying a one second creep load to the bitumen
binder sample. After the one second load is removed, the sample is allowed to recover for 9
seconds then the test started with the application of a low stress (0.1 kpa) for 10 creep recovery
cycles then the stress is increased to 3.2 kpa and repeated for additional 10 cycles. Based on
previous study (S.E Zorro , 2012) low shear viscosity was shown to adequately characterize of
different type of bitumen but was deficient for a proprietary styrene-butadiene-styrene(SBS)
modified bitumen as no viscosity plateau could be observed at low shear rates.70C was used in
this test as pre-determined temperature. The 70 C MSCR results did not reveal any dramatic
differences in the failure stress levels between the unmodified bitumen and the modified
bitumen.
Based on MSCR test black diagram will produced. Black diagram is a complex modulus
(G*) versus phase angle (d) plot and has the advantage that the rheological characteristics
measured at
various temperatures are illustrated by means of a single curve,independent of the temperature
and frequencies. The minor discontinuities/mismatches in the Black space diagrams of the

straight run bitumen curves has been attributed in earlier research to the differing test plate
geometries used (8 mm versus 20 mm diameter) resulting in strain variations from one test to
another (experimental errors) (GD, 2002). Black diagrams are often used as a fingerprint
of the bitumen for quality control purposes. As example when monitoring the consistency of
delivered bitumen (T., 2000)

M
E
T
H
O
D
O
L
O
G
Y

3.1 INTRODUCTION
This project is conducted as a research and experiment base project. The research is including
effects on transpolyoctenamer (TOR) on properties of rubberized bitumen to improvised road for
better future. Objectives for this project are

1.

To determine
the physical
properties of crumb
rubber modified
bitumen(CRMB)
reinforced with transpolyoctenamer(TOR)
.

2.

To determine
the rheological
properties of crumb
rubber modified
bitumen(CRMB)
reinforced with transpolyoctenamer(TOR)
(CRMB-TOR).

3.
To study the
optimum content of
TOR and crumb
rubber.

4.
To determine
the relationship of
CRMB-TOR with the
rutting resistance.

For the laboratory test, penetration test, softening test , Brookfield viscosity test will be
conducted to investigate physical properties of crumb rubber modified bitumen(CRMB)
reinforced with trans-polyoctenamer (TOR). Meanwhile to determine the rhelogical
properties of crumb rubber modified bitumen(CRMB) reinforced with transpolyoctenamer(TOR) (CRMB-TOR),multiple stress creep recovery test and dynamic
shear rheometer will be tested.
The first section will explain the preparation process of CRMB- TOR sample, while the
second section will explain all the test that will be conducted. The third section will
explained about viscosity test and lastly the forth section will discuss about the method
and process.

 meeting with supervisor hhad been schedule

once a week to inform the project progress and
to make sure the project is always meeting the
objectives of the project

meeting with project

supervisor
preparation of sample and
testing equipment

crumb rubberrized modified and

transpolyoctenamer(TOR) will be mixed with
temperature 180C ,speed 500 RPM with one
hour duration for the test

laboratory testing

penetration test ,softening point test and

Brookfield viscosity test will be conducted to
test physical properties .
multiple stress creep recovery test and dynamic
shear rheometer will be tested to determine
rheological properties

analysis and data

interpretation

result that will be obtained from the test will then

in graph,compare and justify

journals and articles related to crumb rubberized

modified and transpolyoctenamer will be
recorded and used

literature studies
objectives.

The following approaches need to be conducted during the project to meet the project

Process of Final Year Project

Project Title Selection

Literature Studies

Crumb Rubber Modified,

TOR And Testing
Equipment Preparation

Laboratory Testing

Specification Of
Laboratory Test

Analysis And
Interpretation

Conclusion And
Reccomendation

Thesis Preparation

3.2 PREPARATION OF CRUMB RUBBER MODIFIED BITUMEN (CRMB) AND

TRANSPOLYOCTENAMER (TOR)
Bitumen grade 80/100 will be collected in the laboratory of civil engineering UNITEN. It should
be taken of bitumen from the same source to be used for each test. Bitumen poured into the
container is heated to melt the bitumen ago bitumen viscosity so that it is easily transferred into
the container.
After the move crumb rubber and transpolyoctenamer will be added to the tin.Method of mixing
binder used in this project will be a wet process, in which the CRMB and TOR mixing with the
base asphalt before introducing the bitumen into the aggregate. The mixing process will be used
Propeller mixer with duration one hour, 500 rpm of speed and temperature with 180C. The
percentage of the CRMB will be added are 0%, 5%, 15% and 20% by weight bitumen. Other
than that, the percentage of TOR is 0%, 2%, 4% and 6% by weight of crumb rubber.
Materials
Bitumen grade 80/100
Crum rubber
Transpolyoctenamer
Conducted test
Penetration Test
Apparatus
Penetrometer
Thermometer
Water bath
Container with 55mm diameter and 35mm depth
Bitumen speciemen
Procedure
Bitumen specimen is soften in a container to a temperature 75-100C. Stir constantly

until it became fluid state and absent of air bubbles.

From the top rim of distance 3mm , the bitumen will be poured sample into the

container.
The specimen will be cooled for 1 hour in a temperature less than 13C and will be
moved the sample to a constant water bath at temperature 25C for another 1 hour.

The penetration needle will be adjusted until its tip touched the surface of sample and

will be moved the dial reading penetrometer at zero.

The needle together will be released with 100g weight for a 5 seconds, the depth of

penetration will be recorded.

five readings on the surface of the sample will be recorded. The distance of each
penetration did not less than 10mm apart and not less than 10mm from the side of the

container.
Used the clean needle before next penetration proceed.
Repeated for other bitumen specimen.

Softening point test (ring and ball test)

Apparatus
Ring and ball testing equipment
Thermometer
Brass ring
Steel ball
Base plate
Procedure
Hot bitumen will be poured into the ring and will be cooled at room temperature for

about 30 minutes and the sample will be leveled.

The ring is will be placed on the ring holder and will be suspended in a bath that will

be filled with distilled water at 5C. Maintain such temperature for 15 minutes.
By using forceps, the ball will be placed in each ball-centering guide.
The bath will be heated and stirred at control rate of 5C/minute. The temperature

will be recorded at every minute and make sure it increase uniformly.

When the bitumen softens, the ball and bitumen sink toward the bottom of the beaker.
The temperature when the softened bitumen sinks and the ball touches the base plate

will be recorded.
The procedure will be repeated if the difference between the two temperatures
exceeds 1C.

Brookfield viscosity test

Apparatus
Rotational viscometer
Environmental Chamber
Temperature Controller
Procedure
Preheat spindle ,sample chamber and viscometer chamber to 135C.

The CRMB-TOR will be heated until fluid enough to pour. The sample will be stirred

and not to entrap air bubbles

The bitumen will be poured into sample chamber. The sample size varies according to

the selected spindle and equipment manufacturer.

The sample chamber will be inserted into Rotational Viscometer temperature

controller unit and carefully lower spindle into sample.

the sample will be brought to the desire test temperature which is typically 135C
within approximately 30 minutes and allow it to equilibrate at test temperature for 10

minutes.
The spindle will be rotated at 20 RPM, and will be made sure the percent torque as
indicate by the RV readout remains between 2 and 98 percent.

Dynamic Shear Rheometer

Apparatus
Dynamic Shear Rheometer
Computer
Plates
Trimming tool
Basic Procedure
The CRMB-TOR which the test specimens are will be selected until the sample is

sufficiently fluid to pour the test specimens.

The testing temperature will be selected according to the CRMB-TOR binder grade or
testing schedule. Heat the Dynamic Shear Rheometer will be heated to test
temperature. This preheats the upper and lower plates which allows the specimen to

adhere to them.
The bitumen binder sample will be placed between the test plates.
Move the test plates together until the gap between them equals the test gap plus

0.002 inches (0.05 mm) will be moved.

The specimen around the edge of the test plates will be trimmed using a heated

trimming tool.
The calculate complex modulus (G*) is proportional to the fourth power of the
bitumen binder specimen radius, therefore careful trim will insure more reliable

measurements
The test plates together will be moved to the desired testing gap. This will be created

a slight bulge in the bitumen binder specimens perimeter.

The specimen will be brought to the test temperature. The test will be started only
after the specimen had been at the desired temperature for at least 10 minutes.

The Dynamic Shear Rheometer software will be determined a target torque at which
to rotate the upper plate based on the material that will be tested. This torque will be
chosen to ensure that measurements are within the specimens region of linear

behavior.
The Dynamic Shear Rheometer conditions the specimen for 10 cycles at a frequency

of 10 rad/sec (1.59 Hz).

Movement of the test plates at 10rad/sec is so small that impossible to easily see it. If
movement is obvious, the bond between the asphalt binder sample and the test plates

will be broken.
The Dynamic Shear Rheometer will be takes test measurements over the next 10
cycles and then the software reduces the data to produce a value for complex modulus

(G*) and phase angle () .

Multiple Stress Creep Recovery ( To produce Black Diagram)
Apparatus
Dynamic Shear Rheometer
Computer
Plates
Trimming tool
Procedure
100 Pa Stress will be applied for a 1 second Creep period
Stress will be removed for a 9 second Recovery period
Then, the cycles will be repeated for 10 cycles
The 3200Pa Stress will be applied for a 1 second Creep period
The Stress will be removed for a 9 second Recovery period
10 cycles will be repeated