31

CHAPTER 2

EXPERIMENTAL DESIGN, MATERIALS

AND TESTING METHODS

This chapter presents the methods to be followed for the preparation

of PMB. Then, the materials - both the polymers and the bitumen used for the
preparation of the PMB are discussed. Finally, the characterization techniques,
the principle of the instrument, instrumentation, importance and the testing
procedures are analyzed. Note is also made on the importance of the polymers
used and the compatibility with the bitumen. Details about the scope and the
importance of the tests conducted are also depicted in this chapter.

2.1 EXPERIMENTAL DESIGN

The preparation of PMB depends upon certain parameters and

conditions. Polymers to be mixed with bitumen should possess special
characteristics to produce a homogeneous mixture with bitumen. The following
are the important conditions to be taken care, while preparing PMB
1. Temperature of Mixing
2. Type of mixer
3. Time of mixing.

2.1.1 Temperature of Mixing

Temperature conditions to be maintained for the preparation of PMB

is essential, since the properties of both polymer and bitumen are temperature
dependent. To find the optimum temperature of mixing, many trial have been
conducted and the following conditions are arrived.
 32

2.1.1.1 Polymer

1. It should not be more than the polymers decomposition temperature

2. It should not be more or less than the Tg of the polymer used
3. It should be more than the polymers softening temperature
4. The temperature should be more enough to soften the polymer and
allow the polymer to disperse in the bitumen medium.

2.1.1.2 Bitumen

1. The temperature should not be more than 200 °C

2. It should be more than the softening temperature of the bitumen.
3. The temperature should maintain the viscosity nature of the bitumen.

2.1.2 Type of Mixer

The mixer should be a shear mechanical mixer. There are two types of
mixers available they are high shear mixture and low shearing mixture. Using
low shear mixing which takes place in a simple mixing tank with a paddle stirrer,
the polymer will be swelled and dissolved by the bitumen. It produces
homogeneity of composition and uniformity of temperature. In high shear
mixing, the polymer particles added will be cut down by the shear blade itself
and it can also produce a uniform homogenous mixture. The only disadvantage is
that the high shear mixing when compared with the low shear mixtures is that it
requires high energy to drive the shear mixing motors which consumes more
energy. In this study a low shear mixture is used to avoid the increase in the
production cost.

2.1.3 Time of Mixing

The blending process of PMB is to be done at the lowest possible

temperature and in a shortest possible time, in order to get a complete
impregnation of the polymer into the bitumen. The blending conditions have an
important effect on the structure and on the properties of PMB. Suitable trial and
 33

error methods are followed to optimize the time required for mixing. It is found
that the longer mixing time will result in a finer mixture, with proper micro
structure. Optimum mixing time should be not less than 3 hrs.

2.2 PREPARATION METHODS

On considering the experimental designs and the conditions to be

followed for the preparation of PMB, two major methods are adopted widely for
the preparation of PMB (Gawandea et al 2012).
1. Dry Process or Indirect Modification of Bitumen by Polymer
2. Wet Process or Direct Modification of bitumen by polymer
Different series of polymer percentages starting from 1 %, 3 %, 5 % and 7
% are used in both the process of preparation of PMB.

2.2.1 Dry Process

Indirect modification or Dry process is the process of coating the

polymer over the aggregate at hot conditions and adding bitumen to the polymer
coated aggregate (Vasudevan et al 2012). Indirect modification process will
develop a thin layer of PMB over the aggregate. The dry process is in-situ and it
does not need any specific blending methods. This process has been well
established and patented by Thiagarajar College of Engineering (Vasudevan et al
2010). In dry process, only WP can be used for the modification of bitumen.

2.2.1.1 Process

The aggregate is heated to 170 C. The WP is shredded to the size

varying between 2.6 mm and 4.36 mm. These shredded WP are added over hot
aggregates with constant mixing to have a uniform distribution. The plastics get
softened and coated over the aggregate. The hot WP coated aggregate is mixed
with hot bitumen 60/70 or 80/100 grade (160 C) (Vasudevan et al 2010). The
WP and the bitumen will mix together at their molten state around 140 C – 160
 34

C and then form a thin layer of PMB over the aggregate. By this process the
plastic coated aggregate and bitumen can be mixed to produce an in situ layer of
PMB. The flow chart for the preparation of dry mix is given in Figure 2.1.

WASTE PLASTICS COATED AGGREGATE- BITUMEN MIX

170 C
AGGREGATES HOT AGGREGATES
Waste
plastics

POLY.COATED
AGGREGATES

HOT
BITUMEN
160 C

POLYMER –BITUMEN –
AGGREGATES MIXTURE ROAD LAYING (140 .C)

Figure 2.1 Flow chart of PMB preparation process using dry process

2.2.1.2 Advantages of dry process

The scholar of this thesis is the co finder of the Dry Process. On

reviewing the studies carried out, the following advantages are found out while
using dry process
Before the formation of PMB, the waste plastic is coated over the
stones to form a plastic coated aggregate. The hot bitumen is added
next to form PMB, thus, by this process, the properties of the
aggregate can be improved
Easy Coating and no modification in temperature
Use of waste plastic more than 15% is possible, due to homogeneity
Flexible films of all types of plastics can be used
Doubles the binding property of aggregates
No new equipment is required
Bitumen bonding is stronger than normal
 35

The coated aggregates show increased strength

No degradation of roads even after 5 -6 yrs after construction
Can be practiced in all type of climatic conditions
No evolution of any toxic gases, as the maximum temperature is 180 º
C.
The only limitation of this process is that usage of WP is only being
tried. More researches are to be carried out for using virgin polymer for the dry
process.

2.2.2 Wet Process

Wet process is the process of modifying the bitumen directly by

mixing the polymer materials in the bitumen at hot condition, with fixed
temperature and rpm of mixing (Yildrim 2007). This process is also called as
direct modification process. Figure 2.2 shows the experimental setup of wet
process. The steps followed for the preparation of PMB using this process are as
follows.
1. Blends of PMB are prepared in an open container using mechanical
shear mixer.
2. Bitumen is heated in an open container to 160-170 °C in a hot plate
fixed with a mechanical stirrer.
3. Calculated quantity of powdered polymer is added to the hot bitumen
4. Different percentages of polymers starting from 1% to 7% are mixed
to prepare different samples.
5. The samples are mixed for three hours at 180 °C in 600 rpm.
 36

Figure 2.2 Experimental set up of producing PMB

When compared with dry process, this process has the following
disadvantages.
It is a time consuming process
The maximum amount of polymer can be added is 5 % -7 % with
respect to the weight of bitumen due to heterogeneity
External industrial involvement is needed for the preparation of PMB
Storage of PMB needs some special containers
Optimization of this process is very difficult in laboratory applications
Mechanical shearing is needed.

2.2.2.1 Materials

Materials used for the preparation of PMB are as follows.

1. Bitumen
2. Polymer

2.2.2.2 Bitumen

Bitumen of penetration grade 80/100 is used in this study. The

bitumen is obtained from IOCL, Madurai. The basic properties of the bitumen
have been studied before it is used for the preparation of PMB. Moreover
bitumen used for the preparation of PMB should have compatibility with the
 37

polymer and hence selecting bitumen material is very essential in the preparation
of PMB.

2.2.2.3 Polymers

Following different polymers are used for the preparation of PMB in

the present study.
1. Polypropylene
2. Polyvinyl alcohol
3. Poly Ethylene
4. Acrylo Nitrile butadiene styrene (ABS) form e- WP and
5. Waste Plastic
6. PVP

2.2.2.3.1 Acrylo nitrile-butadiene-styrene

Acrylonitrile Butadiene Styrene (ABS) is a common thermoplastic.

ABS has good impact strength, chemical resistance, toughness, and rigidity.
Its glass transition temperature (ABS is amorphous and therefore has no true
melting point) is approximately 105 °C (Gowariker et al 2011). Since ABS is
used for making many such plastic products, the content of ABS in e-waste is
also high (Cheng et al, 2006). Hence, by making use of ABS for the purpose of
modification of bitumen, e-waste can be reduced. Therefore, e-waste reduction is
the main motive of choosing ABS as the modifier. The proportions of ABS can
vary from 15 to 35% acrylonitrile, 5 to 30% butadiene and 40 to 60% styrene as
shown in Figure 2.3. The nitrile groups from neighboring chains, being polar,
attract each other and bind the chains together, making ABS stronger than
pure polystyrene. The styrene gives the plastic a shiny and impervious surface.
The butadiene, a rubbery substance, provides resilience even at low temperatures.
From the properties of the ABS polymer it is believed that the polymer is suitable
for the modification of bitumen.
 38

Figure 2.3 Structure of ABS

2.2.2.3.2 Polypropylene

Polypropylene is a thermoplastic categorized polymer which is used in

a variety of applications like packaging, textiles , stationery materials, plastic
products and various types of lab equipment. Polypropylene is iso tactic and its
structure is in between HDPE and LDPE (Gowariker et al 2011). Structure of PP
is given in Figure 2.4. It is tough and flexible in nature. These natures of PP
make it useful in various applications. Melting point of PP is at 171 °C. From the
above details, it is observed that the PP is tough and flexible, especially
when copolymerized with ethylene. It also has a good resistance to fatigue
failure. With all the above properties we found that this may be used for the
modification bitumen.

Figure 2.4 Structure of PP

 39

2.2.2.3.3 Poly vinyl alcohol

Poly vinyl alcohol a type of water-soluble but synthetic polymer. The

formula of PVA is [CH2CH (OH)]n. The structure of PVA is given in Figure 2.5.
Major commercial application of PVA is in paper industry, textile industry , and
in coatings. It is white in colour and odourless. PVA is an atactic polymeric
material which shows crystalline in nature. PVA has an excellent film forming
capacity, and it can be aemulsifying agent and adhesive in nature. The Physical
property shows it has high tensile strength and flexibility, the melting point of
PVA is 230 °C and 180–190 °C It decomposes above 200 °C (Gowariker et al
2011). Choosing a water soluble polymer for the modification of bitumen is a
very big challenge. But the PVA was chosen because of it unique quality of
being more resistant towards oxidation than and as well as its emulsifying and
film forming nature. Though the polymer is water soluble in nature, it is believed

that mixing it with bitumen will not allow the moisture to affect the polymer.

Figure 2.5 Structure of PVA

2.2.2.3.4 Poly ethylene

Polyethylene is the most common available plastic for commercial

applications. The major use of PE is in packaging industry. The chemical
formula is (C2H4)n.. Structure of PE is given in Figure 2.6. PE is thermoplastic in
nature and it consists of long hydrocarbon chains. The melting point of PE is in
the range 120 to 180 °C (Gowariker et al 2011). It also has an excellent resistant
 40

to chemicals. It is also resistant to oxidants and reducing agents. This natures of

PE makes us interest in using PE in the modification bitumen.

Figure 2.6 Structure of PE

2.2.2.3.5 Waste plastics

Waste plastics materials are bags, cups and thermocoles made up of

polyethylene, polypropylene or polystyrene. In addition to this, there are other
molded plastics. Most used materials are bags, cups, films and foams, made up of
PE, PP or PS. Disposal of WP in an eco friendly way is the thrust area of today‟s
research. Development of PMB using WP is a well established process and in
here in this research, it is studied again using a different technique of preparation
of PMB. The research scholar of this thesis is one of the members of the group
which has innovateda technique to use the WP for the construction of asphalt
pavement (Vasudevan et al 2012). This process helps to dispose the waste by eco
friendly method.

2.2.2.3.6 PVP- poly vinyl pyrrolidone

Figure 2.7 Structure of PVP

 41

The structure of PVP polymer is given in Figure 2.7 PVP was used as
a blood plasma substitute in earlier stages, since it is a water soluble polymer and
later it was used in different applications in medicine, pharmacy, cosmetics and
industrial production. The melting point of PVP is around 150 °C to 180 °C and
its Tg is around 150 °C (Gowariker et al 2011). The major application of PVP is
in film forming industries. It is also used as an adhesive. PVP can also be used as
a viscosity enhancer. The use of PVP in the preparation of modified bitumen is
also quite interesting because of its water soluble nature.

2.3 TESTING METHODS

Characterization of the PMB prepared as per the discussion earlier is

subjected to various testing. The characterization is done to test the prepared
modified bitumen‟s major properties. The following are the properties discussed
in this thesis for better understanding of the nature of the PMB.
1. Empirical Properties –Softening point, Ductility, Penetration point,
Penetration Index, storage stability test, stripping value test and MSV.
These tests are mainly carried out to find out the compatibility of the
polymer with the bitumen and to know the basic rheological behavior
of the PMB.
2. Spectroscopic study- The chemical composition and elemental
analysis are done for the PMB. The best analytical tool which fits for
this test is the FTIR measurement.
3. Thermal Property - A study on the thermal properties of the bitumen
is essential to check the nature of the modified bitumen sample at
different temperature ranges.
4. Viscosity Nature- Viscosity of the bitumen is the measure of its
resistant to flow at different temperatures. The viscous properties of
the modified bitumen are studied using Brookfield Rotational
viscometer.
 42

5. Image Analysis - The image analysis of the PMB is done to find the
nature of dispersion of the polymers in the bitumen substrate. These
studies are carried out using Optical Fluorescent Microscopy
technique.

2.4 INSTRUMENTATION TECHNIQUES AND PROCEDURE

FOR CHARACTERIZATIONOF PMB

2.4.1 Softening Point (ASTM D 36-76)

Softening point is the measurement of the softening nature of the

bitumen. Generally, bitumen on heating does not transfer from its solid to liquid
state suddenly. On heating, it gradually softens until it flows steadily and then, it
becomes liquid. For bitumen to be used in the field for laying roads, it should
possess fluidity so that, it can be coated uniformly over the aggregate.

2.4.1.1 Principle

The principle behind this test is that softening point is the temperature
at which the substance attains a particular degree of softening under specified
condition of the test. The determination of softening point indicates the
temperature ranges to which the bitumen to be heated and also to find the
application of bitumen in different temperate zones like hot or cold regions.

2.4.1.2 Instrumentation

Softening point is found by ring and ball apparatus as shown in the

Figure 2.8

The instrument consists the following parts

1. Two steel balls of diameter 9.5mm and it weigh around 3.5g
2. Two brass rings to hold the steel ball
3. Ball guides which allows the steel balls to move down.
 43

4. Supporting rods, in which we place the ring and ball setup and also to
place the thermometer. This rod consists of two parallel plates of
space difference 25mm.
5. A thermometer and a container with water to place the whole setup

Figure 2.8 Softening point apparatus; Source (Shell Hand Book of Bitumen)

2.4.1.3 Procedure for softening point

The sample is heated up to 100. °C until it is fluid and the liquid

bitumen sample is poured in to the small ring and left for cooling. The apparatus
is assembled as per the illustration given in the Figure 2.8. The container is filled
with water and the ring and ball setup is placed inside the water. The whole setup
is heated with continuous stirring. As the temperature increases the bitumen gets
softened and the ball in the ring will start falling down, and it touches the bottom
plate of the rod. The temperature at the touching point is noted for both the balls.
The average value of the temperature is noted as the softening point of the PMB.
The softening point set up is shown in the Figure 2.9
 44

Figure 2.9 Softening point set up

2.4.1.4 Importance of SP

The softening point value is always related with the rheological

property of the bitumen. The softening point indicates the temperature at which
the bitumen attains viscous flow. Bitumen with higher SP is use in high
temperate regions and low SP in colder places. Moreover when bitumen with
lower softening point is used in warm areas, the atmospheric temperature itself
makes the bitumen soften and it results in bleeding. Hence by knowing the SP,
the use of bitumen with respect to the temperate zones can be fixed.

2.4.2 Ductility Test (ASTM D113) – 07

Ductility test is testing of the elasticity of bitumen. The ductility test

gives a measure of adhesive property of bitumen and its ability to stretch.

2.4.2.1 Principle of ductility

In road constructions, the binder bitumen used will form a thin film
over the aggregate and this film helps in binding between the aggregates
(Tabtabaee et al 2013). The binder bitumen which do not posses adequate
ductility (stretching) and the film formed will be easily broken, which in turn
reduces the binding nature of the bitumen. Bitumen with less ductility will be get
 45

cracked down, when subjected to traffic loads and it also makes the continuous
pavement surface. Ductility of a bituminous material is measured by the distance
in centimetres to which it will elongate before breaking, when two ends of
standard briquette specimen of material are pulled apart at a specified speed and
specified temperature.

2.4.2.2 Instrument

The ductility testing machine comprises of two different parts

1. Briquette Mould
2. Water Bath with fixers for the mould and it‟s also acts as temperature
bath for maintaining temperature while doing the test.
Briquette Mould- This is a brass mould of length 75 mm, with
two clips on either side, which can be screwed. The mould
picture shown in the Figure 2.10

Figure 2.10 Ductility machine

Water Bath – This is the main part of the equipment where the
mould will be fixed inside the water bath and tested for its
stretching. The water bath should be maintained at constant
temperature of 27 °C and it should be constantly stirred. It
should contain enough water to immerse the mould completely.
This part also contains the fixing Table where the mould is fixed.
 46

The one arm of the mould is movable at a constant speed using a

centre rod, which is threaded.

2.4.2.3 Procedure

The sample PMB was melted by heating it up to 75 °C until it

becomes a fluid. The fluid is then carefully poured in to the brass mould as in
Figure 2.9 precautions to be taken to avoid sticking of bitumen in the mould by
proper cleaning. Then the sample is allowed to cool, after cooling, the sample
was be removed from the mould and the removed structure as shown in Figure
2.11. Then place the mould in the water bath and screw it tightly and adjust the
scale point to zero and switch on the motor. The mould in one side fixed and the
movable side starts moving with the bitumen stretched at that end. The stretched
bitumen breaks at some length. The distance at which the stretch breaks is noted
as the ductility value in cm

Figure 2.11 Ductility model

2.4.2.4 Importance

As per the principle, the ductility value is very important for bitumen
for satisfactory pavement performance (Naskar et al 2010). If the PMB has a low
ductility cracking occurs due to the influence of load and temperature in the
pavement. The ductility of PMB should be in the range of 50 cm to 75 cm.
uctility indicates the stretching property of the PMB (Morgan and Mulder 1995).
 47

2.4.3 Penetration Test (ASTM D5 / D5M - 13)

2.4.3.1 Principle

Penetration measurement is an indirect measurement of absolute

viscosity of the bituminous materials. Penetration value is a measure of hardness
or consistency of bituminous material. It is the vertical distance traversed or
penetrated by the point of a standard needle in to the bituminous material under
specific conditions of load, time and temperature. Distance is measured in one
tenths of a millimeter.

2.4.3.2 Instrumentation

The instrument used for finding the penetration point of the bitumen is
called as penetrometer. The penetrometer contains the following components as
shown in Figure 2.12.
1. Bitumen sample container
2. Needle
3. Penetration apparatus- which consist of a needle holder with a 50 g or
100 g weight. It also consists of reading circular dial with reading
starting from 300 to 300 mm.
4. Stop watch to calculate five second
5. Now a day‟s digital penetrometers are also available for fixing the
time.
6. Sampling apparatus like water bath and thermometer.

Figure 2.12 Penetration point instrument - Penetrometer

 48

2.4.3.3 Procedure
Prepared specimen is allowed to cool to room temperature and the
cooled sample container is place inside incubator where the temperature is
maintained at 25 °C for one hour. The sample is then taken out form the
incubator and placed in the penetration apparatus. Adjust the needle in the needle
holder so that it can touch the top layer of the sample. Release the needle to
penetrate in to the bitumen sample for five seconds. The reading in the dial by
adjusting the reading needle is noted and the value gives us the distance travelled
by the needle inside the bitumen layer. This reading is noted as the penetration
point in mm. Mark at least five readings at different points above the bitumen
layer and the average will give the PP

2.4.3.4 Importance

PP decides the appropriate grade of bitumen to be used for road

construction. In warm regions, harder grade of bitumen (low penetration) is used
to avoid bleeding of the surface layer due to heavy load and high temperature
(Morgan and Mulder 1995). In colder regions, softer bitumen (high Penetration)
is used to avoid stiffness in bitumen. Polymers used can modify the stiffness of
the bitumen.

2.4.3.5 Penetration index calculation

In addition to the above tests, the temperature susceptibility of the

prepared PMB is found in terms of the penetration index PI (Morgan and Mulder
1995). The PI is calculated using the results obtained from the Softening point
and penetration point tests. The formula used for the calculation of PI is as
follows (Read and Whiteoak 2003)

P.I. = 1952-500 *log (PEN 25) – 20 * SP

50 * log (PEN 25) –SP-120
 49

2.4.4 Storage stability Test (ASTM D7173 – 14)

Storage stability test is performed to find the compatibility of the

bitumen with the polymer. It is used mainly to test the homogeneity of the PMB
under storage. This test is done only for PMB

2.4.4.1 Principle of Storage Stability Test

In modified bitumen, there is a possibility of phase separation between

the polymer and the bitumen. This will happen, when the mixture has a poor
compatibility. The measurement of separation point is done by measuring the
difference in the softening point values of the bitumen samples obtained from the
top and bottom portion of a pre conditioned sealed tube.

2.4.4.2 Instrumentation

1. Aluminum Tube: Tubes of diameter 25.4 mm and 13.67 cm length to

hold the samples
2. Ring and Ball Apparatus to test the softening point
3. Oven – for heating
4. Freezer for cooling
5. Knife for cutting the tube

Figure 2.13 shows the storage stability test tube which has three
different regions

Figure 2.13 Storage stability test tube

 50

2.4.4.3 Procedure to find storage stability

The modified bitumen pre heated in an oven is poured in to the tube.

The tube is then sealed at the top and the kept vertically in a rack. The rack is
placed in an oven at 165 °C for a period of 24hrs; the rack is removed from the
oven and placed in a freezer at 6.7 °C for 4 hrs. After 4 hrs, the tube is taken out
of the freezer and it is cut down to three pieces – top, middle and bottom. The
middle portion is discarded; the bitumen present in the top and the bottom
portion is separately recovered and the recovered bitumen is then subjected to
the softening point test using the Ring & Ball apparatus and as per the standard
ASTM D 36M-12. The difference in the softening points of the top and bottom
level is reported as the separation point.

2.4.4.4 Importance

As discussed in the principle, the separation point is vital to know

whether the bitumen polymer mix is homogeneous in nature or not and also to
know the storage stability of the PMB. If a mix fails the separation test, the PMB
is considered to be a heterogeneous mix and cannot be used to for pavement
applications.

2.4.5 Stripping Value

This value is determined to know the binding nature of the bitumen

with aggregate when exposed to wet conditions. It is a measurement of a problem
related with bituminous mixtures, which are permeable to water. This test is very
basic and the results are observatory only. The flow chart for the sample
preparation is given in Figure 2.14
 51

Figure 2.14 Flow chart of sample preparation for stripping value test

2.4.5.1 Instrumentation

The apparatus required for finding the stripping test are

1. Water bath which can be controlled thermostatically
2. Aggregate sieves of size 12.5 mm
3. Containers to be used for heating
4. Bitumen samples
5. Cotton cloth

2.4.5.2.1 Procedure

Known weigh of aggregate is heated to 160 °C and hot bitumen at 150

°C is added to the aggregate and mixed. The mixture is then transferred to a
container and allowed to cool to room temperature. The sample is then immersed
in water. The container is placed in a water bath maintained at 40 °C for 24 hrs.
After that the beaker is taken out and cooled to room temperature. The stripping
of bitumen is visually examined and noted as percentage.
 52

2.4.5.3 Importance

Certain types of aggregates have lower affinity towards bitumen when

comparison with water. This results in the stripping of bitumen layer from the
aggregate, when the aggregate is exposed to water. The problem of stripping in
the case of PMB coated aggregate, is needed to be studied in order to find out the
affinity of the PMB over aggregate. Hence, an adhesion test like stripping test
would be suitable to assess whether the binder would adhere to the aggregate
when immersed in water (Majidzadeh et al 1968).

2.5 MARSHALL STABILITY TEST

The Marshall Stability and flow test provides the performance

prediction measure for the Marshall Mix design method (Vasudevan et al 2012).
The stability portion of the test measures the maximum load supported by the test
specimen at a loading rate of 50.8 mm/minute. Load is applied to the specimen
till failure, and the maximum load is designated as stability. During the loading,
an attached dial gauge measures the specimen's plastic flow (deformation) due to
the loading.

The flow value is recorded in 0.25 mm (0.01 inch) increments at the

same time when the maximum load is recorded. The Marshall quotient is the
ratio of the Marshall stability to the flow value. The Marshall Quotient may be
used to give an indication of mixture stiffness and increased stiffness of the
rolled asphalt which will results in increased resistance to deformation and
fatigue.

The optimization of polymer in binder content is done based on

empirical tests (Pawan Kumar et al 2003). Positive results are obtained at 5 %
polymer modification. Hence in the present study Marshall Stability test is done
for 5 % PMB. Moreover as per Indian Road Congress (IRC) recommendations,
 53

maximum positive results would be obtained for binder content of 5.2 %

to 5.8 %.

2.5.1 Selection of Aggregates

Aggregates which possess sufficient strength, hardness, toughness and

soundness are chosen keeping in view the availability and economic
considerations. Crushed aggregates will produce higher stability of the mix when
compared with gravel and rounded aggregates. As higher, the maximum size of
aggregates gives higher stability and it is adopted based on the thickness of
pavement layer as mentioned in Table 2.1.

Table 2.1 Aggregate grading and bitumen content (Khanna and Justo 2001)

Note: * The nominal maximum particle size is the largest specified sieve
size up on which any of the aggregate is retained.
** Corresponds to specific gravity of the Aggregate being 2.7. In case
of aggregates have specific gravity more than 2.7, bitumen content
can be reduced proportionately.
 54

Based on this a job mix formula is produced,

Coarse aggregate (W1): 50 % [passing 9.5 mm sieve]
Fine aggregate (W2): 35 % [passing 2.36 mm sieve]
Filler (W3): 15 % [Quarry dust of micron size]
Binder (W4): 5 % [60/70 PG]

2.5.2 Specimen Preparation

Approximately, 1200 gm of aggregates and filler are heated to a

temperature of 175-190 °C. Bitumen is heated to a temperature of 121-165 °C
with 5 % of bitumen. The heated aggregates and bitumen are thoroughly mixed
at a temperature of 175-190 °C. The mix is placed in a preheated mould and
compacted by a rammer with 75 blows on either side at temperature of 138-159
°C. The weight of mixed aggregates taken for the preparation of the specimen
may be suitably altered to obtain a compacted thickness of 63.5 +/- 3 mm. The
Marshall specimen is prepared as per flow chart shown in Figure 2.15.

Figure 2.15 Marshall specimen preparation

 55

2.5.3 Properties of the Mix

The properties that are of interest include the theoretical specific

gravity Gt, the bulk specific gravity of the mix Gm , percent air voids Vv , percent
volume of bitumen Vb, percent void in mixed aggregate VMA and percent voids
filled with bitumen VFB. These calculations are discussed further. To understand
these calculations a phase diagram is given in Figure 2.16.

Figure 2.16 Phase diagram of a bituminous mix

2.5.4 Theoretical Specific Gravity of the Mix Gt (Khanna and Justo

2001)

Theoretical specific gravity Gt is the specific gravity without

considering air voids, and is given by:

(2.2)

where, W1is the weight of coarse aggregate in the total mix, W2is the weight of
fine aggregate in the total mix, W3is the weight of filler in the total mix, Wbis the
weight of bitumen in the total mix, G1 is the apparent specific gravity of coarse
aggregate, G2is the apparent specific gravity of fine aggregate, G3is the apparent
specific gravity of filler and Gbis the apparent specific gravity of bitumen,
 56

2.5.5 Bulk Specific Gravity of Mix Gm (Khanna and Justo 2001)

The bulk specific gravity or the actual specific gravity of the mix Gmis
the specific gravity considering air voids and is found out by:

(2.3)

where, Wmis the weight of mix in air, Wwis the weight of mix in water, Note that
Wm- Wwgives the volume of the mix. Sometimes to get accurate bulk specific
gravity, the specimen is coated with thin film of paraffin wax, when weight is
taken in the water. This, however requires to consider the weight and volume of
wax in the calculations.

2.5.6 Air Voids Percent Vv (Khanna and Justo 2001)

Air voidsVv is the percent of air voids by volume in the specimen and
is given by the formulae:

(2.4)

whereGt is the theoretical specific gravity of the mix and Gm is the bulk or actual
specific gravity of the mix.

2.5.7 Percent Volume of Bitumen V b (Khanna and Justo 2001)

The volume of bitumen Vbis the percent of volume of bitumen to the

total volume and given by:

(2.5)

where, W1 is the weight of coarse aggregate in the total mix, W2 is the weight of
fine aggregate in the total mix, W3is the weight of filler in the total mix, Wb is the
weight of bitumen in the total mix,Gtis the apparent specific gravity of bitumen
andGmis the bulk specific gravity of mix.
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2.5.8 Voids in Mineral Aggregate (Khanna and Justo 2001)

Voids in Mineral Aggregate are the volume of voids in the aggregates,

It is the sum of air voids and volume of bitumen, and is calculated from

(2.6)
where, Vv is the percent air voids in the mix and Vbis the percent bitumen
content in the mix.

2.5.9 Voids Filled with Bitumen (Khanna and Justo 2001)

Voids Filled with Bitumen is the voids in the mineral aggregate frame
work filled with the bitumen, and is calculated as:

(2.7)

where, Vb is percent bitumen content in the mix. And VMA is the percent voids
in the mineral aggregate.

2.5.10 Applying Stability Correction to MSV

It is possible while making the specimen, the thickness slightly varies

from the standard specification of 63.5 mm. Therefore, measured stability values
need to be corrected to those which would have been obtained, if the specimens
have been exactly 63.5 mm. This is done by multiplying each measured stability
value by an appropriated correlation factors as given in Table 2.2.
 58

Table 2.2 Correction factors for Marshall Stability values

Volume ofSpecimen Thicknessof specimen Correction

(cm ) (mm) Factor
457 – 470 57.1 1.19
471 – 482 68.7 1.14
483 – 495 60.3 1.09
496 – 508 61.9 1.04
509 – 522 63.5 1.00
523 – 535 65.1 0.96
536 – 546 66.7 0.93
547 – 559 68.3 0.89
560 – 573 69.9 0.86

2.5.11 Data Needed for Calculation

Specific Gravity of Coarse Aggregate (G1): 2.731

Specific Gravity of Fine Aggregate (G2): 2.691
Specific Gravity of Filler (G3): 3.120
Specific Gravity of Bitumen (G4): 1.03
Theoretical Specific Gravity (Gt): 2.44

2.6 SPECTROSCOPIC STUDY

The chemical composition of the PMB and its elemental analysis are
done for the PMB. The best analytical tool which fits for this test is the Fourier
Transformed Infrared (FTIR) measurement

2.6.1 Fourier Transformation Spectroscopy

The FTIR studies are carried out to find out the functional materials
present in any materials. In case of bitumen samples, it is applied to find out the
chemical constituents present in the bitumen. A detailed explanation of the FTIR
 59

spectroscopy is given below for better understanding of the technique. Infrared

spectroscopy is one of the analytical tools, presently available (Griffiths and
Haseth 2007). Advantage of using infrared spectroscopy is that it is a perfect
study without any stimulation. Samples like Liquids, solutions, pastes, powders,
films, fibers, gases and surfaces can be studied under IR spectrum (Griffiths and
Haseth 2007). FTIR spectroscopy is the advancement in IR which has many
improved quality over infrared spectra.

2.6.2 Theory and Principle

The basic principle of Infrared spectroscopy is based on the vibrations

of the atoms of a molecule as given in Figure 2.17. IR spectrum is recorded by
passing infrared radiation through a sample and observing the fraction of the
incident radiation is absorbed at a particular energy. The energy level where any
peak in an absorption spectrum appears corresponds to the frequency of a
vibration of a part of a sample molecule.

Figure 2.17 Vibration of Ions

2.6.3 Instrumentation

The basic components of an FTIR spectrometer are shown

schematically in Figure 2.18. The FTIR spectrometer consists of the following
components
1. Source- Light source for IR
2. The Michelson interferometer
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3. Sample holder
4. The detector- where the IR after passing through the sample will be
detected and analyzed whether the passed intensity of the IR light is
observed or transmitted by the sample.
5. Amplifier and the convertor
6. Result – computer

Figure 2.18 Basic components of FTIR

2.6.4 Testing Procedure

The FTIR measurements for the PMB samples are done using
Attenuated Total Reflection (ATR) technique which is an advanced technique in
which no sampling of the compound is required for testing. ATR is a method
adopted in FTIR spectrometer for recording IR spectrum for any type of samples.
In this technique we the sampling methods by making KBr pellets are not done
(Griffiths and Haseth 2007). The ATR-IR works under the phenomenon of
complete reflection as given in Figure 2.19

Figure 2.19 Schematic representation of IR beam reflected on the crystal -

sample interface in FTIR-ATR spectrometer
 61

In this work, the FTIR-ATR technique is used to analyze the surfaces

of modified bitumen and to test the polymeric layers deposited on bitumen.

2.6.5 Importance

The FTIR-ATR technique is a relevant technique to examine PMB in

a simple, fast procedure by avoiding sample destruction. FTIR creates many
opportunities for application to the chemical identification of the surface layer of
polymers in bitumen and its constituents. The analyses of this test will provide us
a clear data about the modification provided by the polymer in the bitumen.

In the present study FTIR spectrum of PMBs are measured using

SHIMADZU, Japan make FTIR model IR Prestige – 21 with ATR.

2.7 THERMAL STUDIES

A study on the thermal properties of the bitumen is essential to know

the behavior of PMB at different temperatures. Thermal analysis is a class of
techniques to measure chemical or physical properties of a substance as function
of temperature or time. There are different methods available to study the thermal
properties like TGA, DTA and DSC, in which the TGA method has been
adopted.

These methods work under the following principle

Thermal technique Output

TGA Mass change Vs temperature
DTA ΔT (Sample – Ref) Vs temperature
DSC Power Vs Temperature

The PMB prepared is subjected to the TGA. A detailed description of

the methods followed is given below.
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2.7.1 Thermo Gravimetric Analysis (TGA)

2.7.1.1 Principle

TGA is an analytical technique used to find the thermal nature of

different materials. Results on thermal stability and decomposed fraction of
components will be shown by recording the weight loss that happens when the
specimen is heated. The TGA measurement is carried out either in air or in an
inert atmosphere, such as Helium or Argon or in a nitrogen atmosphere. Pictorial
representation of TGA is given in Figure 2.20. The weight loss is measured as
parameter of temperature (Benbouzid and Hafsi 2008). The Thermo gram is the
important component of the TGA. By using the results obtained from TGA one
can easily study about the thermal nature of the material.

2.7.1.2 Instrumentation

Figure 2.20 Thermo gravimetric analyzer

The TGA works mainly with the thermo couple and a micro balance
called as thermo balance.
Sample holder (metallic/ceramic pans)
Microbalance – Thermo Balance
 63

Programmable heater (furnace)

Gas flow control
Temperature control (thermostat)
Temperature sensor (thermocouple)
Read-out

2.7.1.3 Procedure

The working procedure of TGA depends upon the thermo balance.

The instruments should be calibrated as per the procedure to get zero errors and
the balance should be nullified with a empty crucible in the back side of the pan.
Place the sample in the working side of the balance pan which is inside the
furnace. Program the run by fixing the temperature and time using the software.
The instrument will measure the weight loss/gain occurred at the thermo balance
and the values are recorded. The mass loss is recorded as a plot with respect to
the time and temperature. The graph thus obtained will provide numerous
number of information regarding the thermal behavior of the sample.

2.7.1.4 Importance

The TGA results will provide data on the behaviour of the bitumen,
when the sample is subjected to heating. It shows the rate of decomposition of
the bitumen, impurities present and also the role of the polymer in disturbing the
thermal properties of the bitumen. Since the PMB will be used in pavement
construction after pre heating, the behaviour of the samples at high temperature is
essential. The TGA graph of the plain bitumen will also give an idea to fix the
blending temperature of the bitumen and polymers to be used (Naskar et al
2010).

In the present study TGA of PMBs are measured using SHIMADZU,

Japan make TGA model TGA – 50 with TA – 60- WS software.
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2.8 VISCOSITY STUDY

In the present study viscosity of PMBs are measured using Brookfield

viscometer, US make - model DV2THA, with rheocalc software.

2.8.1 Viscosity

Viscosity of a liquid is the property that resists the flow of the liquid
due to the internal friction produced by the liquid itself when it behaves in a
medium. The viscosity of liquids differs with different temperature. Numbers of
methods have been developed for testing the viscosity of plain as well as the
modified bitumen (John Read & David Whiteok 2003). Some methods are
indirect measurements like orifice type of viscometers. There are certain types of
methods like rotational viscometers which are used to measure the viscosity of
the liquid directly. Advanced techniques are also available to measure the
viscosity of any liquid at different shear rate, temperature and so on. One such
method is the Brook field Rotational Viscometer (John Read & David Whiteok
2003).

2.8.2 Principle

The viscous properties of the modified bitumen are measured using

Brookfield Rotational viscometer. Viscosity is the property which decides the
workability of the bitumen and its resistance to permanent deformations. The
study on the viscosity of the PMB provides valuable data in changes of the
parameters like stiffness and flow, due to the change in microstructure of the
bitumen chain influenced by the polymer.

Principle derived from viscopedia – in rotational viscometers, the instrument

uses a rotational motor drive. The rotational viscometers provide dynamic or
shear viscosity results. A rotational viscometer consists of a sample-filled cup
and a measuring spindle which is immersed into the sample and on operation,
 65

this spindle will be rotated with the help of the motor. The resistance on the
rotation of the spindle will be measured as a factor of viscosity. The shear ratio,
speed of spindle, etc. can be fixed using the rotational viscometer.

2.8.3 Viscosity of Bitumen

The viscosity of bitumen is the internal resistance of flow. The

viscosity of bitumen gives mixed responses under different temperatures, shear
and stress conditions. This property of bitumen directly affects the performance
of the binder. . Thus, viscosity measurements of PMB have been used to
characterize the classification of bitumen. Nowadays, the bitumen samples are
classified on the basis of the viscosity nature of the bitumen like Viscosity Grade
(VG) VG-10, VG -20 and VG -30.

2.8.4 Instrumentation

The Brookfield viscometer consists of the following instruments. The

representation of the instrument is given Figure 2.21 and Figure 2.22
1. Brookfield viscometer – is a machine with driven motor whose rpm
can be fixed by the user- it also consists of a spindle holder, where we
can fix the spindle can be fixed.
2. Spindle- it is cylindrical structure of different diameter and length. It
is very important to use a correct spindle recommended for the liquid
to be examined for viscosity as given in Figure 2.20.
3. A cup or container- it is also cylinder in shape in which the sample is
placed /poured.
4. Thermosell – it is a heating furnace where the sample is heated to a
prefixed temperature.
5. Rheocalc software – to fix the shear rate, rpm, temperature, etc.
 66

Figure 2.21 Rotational motor action

Figure 2.22 Brook field viscometer

 67

2.8.5 Procedure

The following is the procedure to be followed for finding the viscosity

nature of the bitumen using Brookfield viscometer. 10g of the bitumen sample is
taken in the aluminium container. The container is then place in the thermosell
which is preheated up to measuring temperature. The sample is maintained
undisturbed inside the thermosell for a period until the sample attains the fixed
temperature. The spindle is then inserted into the sample container until it is
completely immersed inside the container. The rotation of the spindle which is
connected with the Brookfield viscometer will show the viscosity value. In the
present study Spindle no 22 is used.

2.8.6 Importance

Viscosity measurement for a modified bitumen sample is very

essential in such a way that the viscosity of a PMB will provide the effect of the
polymer over the bitumen. It is also a measurement of the influence of the shear
and stress over the bitumen material. By knowing the shear and stress of the
PMB, the behavior of the modified bitumen can be found at different levels. The
viscosity measurements are also the measurement of the rheological
measurement of the modified bitumen sample (Sybilski, 1997). The viscoelastic
response of a material is given in Figure 2.23. The bitumen to be used for road
application should possess the following viscous nature: at high temperatures
such as it should flow enough to form a uniform coating over the aggregate and
at low temperature, it should flow enough to avoid cracking under load. Since
bitumen is a viscoelastic material, it possesses the above said nature to some
extent, but when the condition differs, the unmodified bitumen fails. But in the
case of PMB‟s viscosity measurement, it is observed that the bitumen behaves
positively in extreme failure conditions both in high and low temperature
regions.
 68

Figure 2.23 Viscoelastic graph

2.9 OPTICAL FLUORESCENT MICROSCOPY

Optical Fluorescent Microscopy (OFM) is used to study the

morphological nature of the PMB. The OFM studies will give an idea about the
phase modification of the bitumen, when mixed with the polymer phase. The
image analysis of the PMB is done to find the nature of dispersion of the
polymers in the bitumen substrate. These studies are carried out using Optical
Fluorescent Microscopy technique. In the present study morphology of PMBs are
measured using OFM, Lawrence and Mayo, US make - model LM-52-3000;
LYNX.
 69

2.9.1 Principle

The OFM works under the basic principle of the optical microscopy
and the advantage here in OFM is that the fluorescent light can be passed through
the sample and fluorescence images can be recorded. There are different lights/
filters which can be used to find the fluorescent activity of the sample also. The
image obtained can be used for further studies. In the case of PMB the analysis
of microscopy studies of bitumen is very important to find the quantitative effect
of the polymer over the bitumen.

2.9.2 Instrumentation

The following picture predicts the instrumentation of the OFM.

Figure 2.24 Optical fluorescent microscope

In the Figure 2.24 the major components of the OFM are given.
Figure 2.25 depicts the model of OFM.

2.9.3 Procedure

The following are the steps to be followed in studying the OFM for
the bitumen samples.
1. The samples to be tested are heated and a drop of the PMB is placed
in between the glass slides
 70

2. The slides are rubbed together to obtain a thin film of the PMB in the
substrate
3. The formed film is then placed in the sample holder and the sample is
observed through different magnifying range of objectives to obtain a
clear image on the eye piece.
4. These images are also captured using camera and the image is stored
for further interpretations.

2.9.4 Importance

Images captured using OFM technique for different samples reveals

that the morphology of the PMB, depends upon the percentage of polymers used
and as well as on the type of polymer used. On mixing the polymers to the
bitumen, one of the following reactions can happen
1. swelling of polymers in bitumen
2. absorption of polymers in bitumen
3. dissolving of polymers in bitumen

By forming this type of linkages, these polymers can alter most of the
properties of the bitumen by changing the basic matrix of the bitumen structure.
The discussion in this part concludes that the nature of dispersion should be
homogeneous in nature, if phase separation occurs, the PMB cannot perform as a
binder, and it loses its basic qualities (Visco elasticity). (Stastna et al 2003) have
found that, when small amount of polymers is mixed, the morphology shows
polymer dispersed in the continuous bitumen phase, rather at higher percentage
polymer dispersion, is continuous.
 71

Figure 2.25 OFM