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Properties of Polymer Modified Bitumen after Rubber-Bitumen Interaction

Article  in  Journal of Materials in Civil Engineering · August 2002

DOI: 10.1061/(ASCE)0899-1561(2002)14:4(344)

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 1

Journal of Materials in Civil Engineering

Properties of Polymer Modified Bitumen after

Rubber-Bitumen Interaction

G. D. Airey, T. M. Singleton and A. C. Collop

School of Civil Engineering, University of Nottingham, University Park, Nottingham, NG7
2RD UK

To cite this article: G. D. Airey , T. M. Singleton & A. C. Collop (2002): Properties of

Polymer Modified Bitumen after Rubber-Bitumen Interaction, ASCE Journal of Materials in
Civil, 14:4, 344-354

To link to this article: http://dx.doi.org/10.1061/(ASCE)0899-1561(2002)14:4(344)

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Properties of Polymer Modified Bitumen after Rubber-

Bitumen Interaction

By G. D. Airey1, T. M. Singleton2 and A. C. Collop3

Abstract: This paper describes results from a laboratory investigation into the effects

of the interaction between an SBS modified bitumen and recycled crumb rubber on

the mechanical performance of Impact Absorbing Asphalt (IAA), an asphaltic

material that has applications as a sports and safety surface. Curing tests at high

temperatures have been undertaken using different rubber-bitumen ratios to assess the

amount of bitumen absorbed by the rubber. The changes in bitumen constitution

through this interaction have been monitored and related to changes in the rheological

characteristics of the residual bitumen. The results show that significant absorption

takes place and that the residual bitumen undergoes alterations in terms of its stiffness

and viscoelastic balance, together with a reduction in cohesion. A significant finding

has been the loss of the polymeric nature of the residual SBS PMB. This has been due

to the precipitation of the SBS polymer as the compatibility between the base bitumen

and polymer has decreased following the absorption of the lighter, solvating fractions

of the binder. To assess the effect of the rubber-bitumen interaction on the mechanical

durability of IAA, an abrasive wear test has been developed to simulate the contact

between a twisting foot and the surface. This test has been used to compare the

mechanical durability of laboratory prepared specimens that have been artificially

1
Lecturer, Sch. of Civil Engrg, Univ. of Nottingham, University Park, Nottingham, NG7 2RD, U.K.
2
Research Assistant, Sch. of Civil Engrg, Univ. of Nottingham, University Park, Nottingham, NG7
2RD, U.K.
3
Senior Lecturer, Sch. of Civil Engrg, Univ. of Nottingham, University Park, Nottingham, NG7 2RD,
U.K.
 3

aged at high temperatures (to simulate the mixing and transportation period before the

material is laid and compacted). Results show that there is a detrimental effect on the

mechanical durability of the aged material due to the interaction between the rubber

and the bitumen.

Key Words: Crumb rubber, polymer modified bitumen, absorption, rheology,

cohesion, abrasion, asphalt cement, rubber modified asphalt

INTRODUCTION

Impact Absorbing Asphalt (IAA) is a patented technology consisting of a

relatively conventional, continuously graded bituminous material with a proportion of

the aggregate replaced by dry crumb rubber obtained from the recycling of truck

tyres. It has many potential applications and, to date, has been used as a surface layer

for play areas and a shock-pad beneath artificial sports surfaces. The technology is

based on the dry process developed in the late 1960's in Sweden (Green and Tolonen

1977; Takallou 1988; Heitzman 1992). Production of the material involves the

addition of crumb rubber to the hot aggregate prior to mixing with an elastomeric

styrene-butadiene-styrene (SBS) polymer modified bitumen (PMB). A modified

binder is used as it imparts improved elasticity to IAA, thereby improving the elastic

recovery of the material when deformed. The mixed material is then held at a high

temperature until compaction, which is carried out using conventional paving

techniques and equipment.

Preliminary production trials of the material have indicated that the bonding of

the material when laid is poor, resulting in loose particles of rubber and aggregate

being distributed on the surface. In addition, laboratory testing of the material has

indicated that the rubber retains a larger proportion of the bitumen than the aggregate,
 4

suggesting an interaction between the bitumen, regarded as a solvent, and the rubber,

which is a polymer.

The intention of this paper is to describe the interaction between the rubber and

the bitumen and the effect it has on the chemical composition, rheological properties

and cohesion of the residual bitumen and consequently the performance and durability

of IAA. The residual bitumen is regarded as the bitumen that has not been absorbed

by the rubber. In IAA, or any other crumb rubber modified bituminous material, the

residual bitumen can be considered to be the medium which binds the aggregate and

rubber particles together. Any change in the performance of the residual bitumen will

therefore result in a change in performance of the bituminous material.

Dynamic Shear Rheometer (DSR) and Vialit Pendulum Cohesion Tests have

been used to monitor the effect of the rubber-bitumen interaction on the performance

of the residual bitumen. The results from these experiments have also been correlated

with changes in chemical composition of the residual bitumen as measured by

chromatographic techniques. In addition, the changes in the mechanical and

rheological properties of the residual bitumen have been compared to the changes in

these properties following identical ageing (curing) of the SBS PMB bitumen without

the presence of crumb rubber. In parallel with the investigation into the rheological

and mechanical performance of the residual bitumen, an abrasion test has been

developed to investigate the resistance to mechanical wear (termed mechanical

durability) of IAA laboratory test specimens.

 5

CONSTITUENT MATERIALS

Crumb Rubber

Polymers are known to absorb liquids and swell with the amount they absorb

being dependent on the nature, temperature and viscosity of the liquid/solvent and the

type of polymer (Treloar 1975). Polymers can be divided into two classes, those

which swell in water and those which swell in organic solvents. The first class

consists of polymers such as cellulose (cotton, wood etc.) and protein (gelatine, wool

etc.), while the dominant group in the second class is rubber, both synthetic and

natural (Treloar 1975).

The swelling of rubber in organic solvents is a diffusion process. The solvent

diffuses into the bulk of the rubber, increasing the dimensions of the rubber network

until the concentration of liquid is uniform and equilibrium swelling is achieved. The

amount of solvent that will diffuse into the rubber depends on the number of cross-

links in the rubber and the compatibility of the solvent and rubber on a molecular

scale. The greater the number of cross-links in the rubber, the shorter the average

length of rubber chains between cross-links and the lower the rate of diffusion. In

addition, the lower the molecular weight of the solvent, the more readily it will diffuse

into the rubber (Treloar 1975 ).

The crumb rubber used in IAA is obtained from the recycling of truck tyres.

Tyres are shredded into sequentially smaller grades to remove wire and fabric

reinforcement, producing an end product of rubber crumb. The actual chemical

composition of the crumb rubber is difficult to assess because of the large variability

of tyre makes and re-treading processes. However, the generic form can be treated as

a vulcanised rubber containing natural and man-made rubber. An important factor is

 6

that the rubber is vulcanised and therefore its molecular structure contains a large

number of cross-links (Blow 1971).

Bitumen

Bitumen is a complex mixture of organic molecules that vary in chemical

composition and molecular weight. As bitumen is produced from crude oil, with its

large variability in composition according to its origin, the precise breakdown of the

hydrocarbon groups in bitumen is difficult to determine (Airey 1997). However,

despite the complexity of bitumen, techniques have been established to separate

bitumen into four major groups, namely (Whiteoak 1995; Isacsson and Lu 1995):

 Asphaltenes,

 Resins,

 Aromatics, and

 Saturates.

Asphaltenes are considered as highly polar, complex aromatic materials, having

the heaviest molecular weight of all the other groups present in the bitumen. They

form micelles that are peptised by the polar resins within a dispersion medium

consisting primarily of aromatics and saturates, representing the fractions of the

bitumen with the lowest molecular weight. In general bitumen can be divided into two

broad chemical groups, namely asphaltenes and a second group consisting of the

resins, aromatics and saturates termed the maltene fraction of the bitumen. In

bitumens with sufficient quantities of resins and aromatics of adequate solvating

power, the asphaltenes are fully peptised, well dispersed and do not form extensive
 7

associations. These bitumens are known as solution of “SOL” type bitumens (Labout

1950). However, if the quantity of the aromatics/resin fraction is insufficient to

peptise the micelles or has insufficient solvating power, the asphaltenes can associate

to form large agglomerations or even a continuous network throughout the bitumen.

These bitumens are known as gelatinous or “GEL” type bitumens (Labout 1950).

Therefore, increasing the asphaltene content and reducing the maltene content of

bitumen will result in a harder, more viscous “GEL” type of binder.

Bitumen is an organic solvent, that is liquid at high temperatures and will

diffuse into rubber particles at a rate determined by its temperature, viscosity and

molecular composition. Through development of polymer modified bitumens, Vonk

and Bull (1989) discovered that when rubber is added to bitumen, the elastomer

absorbs all the components of the bitumen apart from the asphaltenes. This implies

that when recycled crumb rubber is added to bitumen it will absorb the maltenes and

leave the residual bitumen containing a higher proportion of asphaltenes.

SBS polymer modified bitumen

For certain applications, bitumen can be modified by the addition of either

liquid or solid components that are used to improve one or more of the mechanical

properties of the bitumen. One such modifier is the polymer, styrene-butadiene-

styrene (SBS) which is a synthetic thermoplastic elastomer used in many applications,

such as in the soles of running shoes, as well as an additive to bitumen. The

advantages of SBS PMBs are that they exhibit improved high temperature flow

resistance and low temperature flexibility compared to conventional, unmodified,

straight run bitumen.

 8

A characteristic of SBS PMBs is their ability to maintain their high strength and

elasticity at elevated service temperatures, due to the physical cross-linking of their

polymer blocks into a three-dimensional network. Cross-links form because the

butadiene and styrene copolymers are incompatible and each try to form links within

their own polymer group. The styrene, referred to as the end-block, provides the

strength of the material while the butadiene, the mid-block, contributes to the

elasticity of the material (Whiteoak 1995). At temperatures above 100oC, the

polystyrene softens thereby weakening the links, which may even break under stress.

Further softening occurs at temperatures above 150C where the polybutadiene starts

to melt. At these elevated temperatures the SBS PMB behaves as a viscous liquid

allowing uniform coating of any aggregates and/or rubber crumbs during asphalt

mixture production. Upon cooling, the links reform and the strength and elasticity of

the SBS PMB is restored.

When SBS is blended with bitumen a portion of the maltene fraction of the

bitumen is absorbed by the polymer causing it to swell to approximately 6 to 9 times

its initial volume. The swelling and extension of the rubber at contents of 4 to 8%

SBS is sufficient to form a two phase system consisting of a continuous network of

SBS polymer with the bitumen dispersed within the network. This is a particularly

desirable state that gives the SBS PMB its characteristic properties.

It is important that the bitumen and SBS polymer are compatible to ensure that

the PMB blend is stable and able to maintain its properties. When the PMB blend is

compatible the two-phase system will be well dispersed and the PMB will be stable at

high temperatures. However, when the bitumen is incompatible, the polymer will not

disperse well within the bitumen reducing its effect as a modifier. If the asphaltene

content in the blend is too high, the loss of maltenes to the polymer causes larger
 9

asphaltene micelles to form allowing gelation to take place in the bitumen blend

thereby reducing the compatibility of the system. A low asphaltene content is

therefore more desirable as this allows a beneficial interaction between the polymer

and the asphaltenes, both of which require the solvating power of the maltenes

fraction.

BINDER ABSORPTION TESTS

Test Procedure

Curing tests were carried out to investigate the maximum amount of SBS PMB

that could be absorbed by the rubber. The rate of absorption of the rubber was also

monitored to give an indication of the speed of the interaction. The tests consisted of

placing 5 g samples of crumb rubber particles (6 to 9 mm in size) into a 50 ml glass

beaker, while the SBS PMB was heated to a temperature of 180C in a fan assisted

oven. Fixed quantities of SBS PMB were then poured into each beaker and the

rubber-bitumen mixture cured in a fan assisted oven at 155oC for different periods of

time. The temperature regime was chosen to simulate mixing and transportation of the

IAA material, which is typically mixed at 180oC and then placed in insulated trucks

where the average temperature, maintained for up to 6 hours, is approximately 155 oC.

Different rubber-bitumen proportions were tested to investigate the sensitivity of the

rubber-bitumen interaction to the ratio of these two components. The crumb rubber

was then drained, allowed to cool and weighed to determine the increase in the mass

as a percentage of its original mass.

The proportion of rubber to bitumen in the beaker (termed the rubber-bitumen

ratio) was altered by changing the mass of bitumen that was poured into each beaker

containing the rubber crumbs. Six quantities (5, 7.5, 10, 20, 30 and 40 g) of bitumen
 10

were added to the 5 g of rubber to give rubber-bitumen ratios between 0.125 and 1.0.

Sets of seven beakers were prepared for each rubber-bitumen mixture and within each

set, each beaker was allowed to cure for a different time period. After curing, the

beaker was removed from the oven, turned upside down onto a 2 mm aperture wire

gauze and placed over a tin which collected the residual bitumen. The whole system

was then placed back in the oven for a further hour, to allow the excess residual

bitumen to drain off the swollen rubber. Upon completion of the draining process, the

system was removed from the oven and allowed to cool. The swollen rubber was then

removed from the gauze and weighed, while the residual bitumen was stored at 5 oC

for further testing.

Binder Absorption Results

The results for the curing tests are shown in Fig. 1 where the percentage

increase in the mass of the rubber is plotted against curing time. It can be seen from

the figure that for each of the six rubber-bitumen ratios the amount of swelling

increases with time but at a decreasing rate as shown by the logarithmic trend lines

(solid lines). These results are similar to the logarithmic swelling trends identified for

rubber cured in conventional penetration grade bitumen (Singleton et al. 2000a), and

confirms that the rubber is absorbing some of the SBS modified bitumen resulting in

an increase in mass.

An important observation, based on the swelling data in Fig. 1, is that there is a

decrease in the maximum amount of swelling corresponding to an increase in the

rubber-bitumen ratio. In addition, the maximum amount of swelling (increase in mass)

seems to approach a limiting value of approximately 110% (after 72 hours curing) for

the three lowest rubber-bitumen ratios (0.125, 0.17 and 0.25). The negligible
 11

differences in the swelling amounts for these three rubber-bitumen ratios is indicative

of a maximum threshold in terms of the amount of bitumen that the rubber is

physically able to absorb as a proportion of its own mass (i.e. maximum amount of

swelling). This suggests that, although there may be more bitumen available for

absorption, the maximum increase in mass of this type of rubber is approximately

110% at 155oC. Or stated differently, provided that there is a sufficient quantity of

SBS modified bitumen available for absorption, the rubber will swell to

approximately 110% of its original mass.

Fig. 2 shows the same results plotted in terms of the percentage of available

bitumen that is absorbed by the rubber. It can be seen from this figure that the two

highest rubber-bitumen ratios (0.67 and 1.0) show that a maximum amount of

approximately 65% of the total bitumen is absorbed. This suggests that the crumb

rubber is only able to absorb certain fractions of the SBS PMB at 155oC, probably

consisting of the lighter, more volatile components of the bitumen. The relationship

between the swelling of the rubber and the percentage of the available bitumen that is

absorbed is shown in Fig. 3. The figure shows the interaction between the rubber’s

ability to swell to its maximum value and the availability of bitumen to allow this

swelling to occur. The results show that during the early stages of bitumen absorption

(1 to 6 hours) the different rubber ratios all demonstrate similar amounts of swelling

due to the ample supply of bitumen for absorption. However, as the interaction

between the rubber and bitumen progresses with time, the available bitumen for

absorption begins to influence the potential swelling of the rubber resulting in a

reduction in the percentage increase in rubber mass as the rubber ratio increases. This

is particularly noticeable at the higher rubber concentrations and longer curing times.
 12

To investigate which proportions of the bitumen are being absorbed by the

rubber, the constituents of the base bitumen, used to produce the SBS PMB, were

measured following a similar curing regime.

BITUMEN CONSTITUTION

It has been reported that rubber will more readily absorb the lighter (maltene)

fractions of the bitumen (Vonk and Bull 1989), leaving a higher proportion of

asphaltenes in the residual binder thus changing its rheological properties. Samples of

the unmodified base bitumen used to produce the SBS PMB were cured at 155oC in a

two parts bitumen to one part rubber mixture (rubber-bitumen ration of 0.5) for 1, 6

and 24 hours. The effect of the interaction between the rubber and bitumen was

monitored and compared with control samples cured for the same period but without

any rubber. The residual samples of both the control and the rubber interacted binders

were analysed by means of thin layer chromatography to separate the bitumen into its

constituents, namely saturates, aromatics, resins and asphaltenes. The quantities of

each constituent were then calculated using flame ionisation detection (SARA

analysis). The SARA analysis for the base bitumen is shown in Fig. 4.

It can be seen from this figure that the samples cured without rubber

demonstrate a decrease in aromatics and an increase in resins while the saturate and

asphaltene contents are relatively constant. These changes can be attributed to

oxidation of the sample at the high temperature associated with the curing test. The

bitumen cured in the rubber shows a decrease in the aromatic and saturate contents

and an increase in the resin and asphaltene contents. Assuming that any changes from

those seen for the samples cured without rubber can be attributed directly to the

influence of the crumb rubber, it can be deduced that the crumb rubber is absorbing an
 13

additional portion of the saturate and aromatic fractions. These fractions represent

those molecules with the lowest molecular weights and substantiates the hypothesis

that the crumb rubber more readily absorbs these lighter, more volatile molecules.

Therefore, the consequence of the rubber-bitumen interaction is that there is a

reduction in the amount of lighter solvating fractions available to support the SBS

sub-structure in the modified bitumen. To investigate what effect this may have on the

rheological properties of the residual SBS PMB, samples of the binder were subjected

to dynamic mechanical analysis using a Dynamic Shear Rheometer (DSR).

RHEOLOGICAL CHARACTERISATION

Testing Procedure

The DSR is an apparatus used to undertake dynamic oscillatory testing, the

results of which can describe the linear visco-elastic properties of bituminous binders

over a range of temperatures and loading times. During testing a sinusoidal shear

stress or strain is applied to a sample of bitumen sandwiched between two parallel

disks as shown schematically in Fig. 5. The resulting sinusoidal shear stress or strain

is monitored as a function of temperature and frequency. Based on these stress and

strain measurements, stiffness and viscosity can be obtained at different temperatures,

frequencies and strain levels for samples of bitumen (Goodrich 1988).

The main rheological measurements obtained with the DSR are complex shear

modulus and phase angle. The absolute value of the complex shear modulus, |G*|, is

the ratio of peak stress divided by peak strain. It represents the shear stiffness of the

bitumen under the conditions of testing. The phase angle, defined as the phase

difference between the peak stress and strain, represents the time delay between the

applied stress and the measured strain with limiting values of 0 o for purely elastic
 14

behaviour and 90o for purely viscous behaviour. The schematic DSR configuration in

Fig. 5 shows that the two disks are submerged in a water bath to control the

temperature of the specimen.

Sample preparation is based on the SHRP procedure (AASHTO TP5, 1994) and

consists of heating the residual or cured bitumen to 185oC and then pouring the binder

onto the bottom disk of the DSR, which is set at a temperature of 50C. The top disk

is then lowered to produce a bitumen sample, 1.05 mm in thickness, sandwiched

between the upper and lower disks of the DSR. The excess bitumen, squeezed out

during sample preparation, is then trimmed around the circumference of the disks by

means of a heated blade. The upper disk is then lowered a further 0.05 mm so that the

distance between the disks is 1 mm and the open edge of bitumen is slightly concave

in profile. Each bitumen sample was tested under the following conditions:

 Spindle Geometry: 25 mm diameter parallel disks

 Temperatures: 35, 45, 55 and 65oC

 Frequencies: 0.1, 0.2, 0.5, 1, 2, 5 and 10 Hz

 Maximum Strain Level: 0.1% (within the linear visco-elastic region of

behaviour)

The data for each sample were then collected, analysed and, based on the time-

temperature superposition principle (TTSP) (Ferry 1971), presented in the form of

manually shifted master curves of complex modulus and phase angle at a reference

temperature of 35oC.
 15

Results

SBS PMBs differ in their rheological properties compared to conventional

penetration grade bitumens, particularly at high temperatures and low frequencies

(Heitzman 1992). The two phase system of an SBS PMB means that at low

temperatures and high frequencies, where the base bitumen is relatively stiff, the

mechanical performance of the polymer-bitumen blend is dominated by the properties

of the base bitumen. However, whereas a conventional bitumen becomes more fluid

in behaviour with a decrease in complex modulus and an increase in phase angle at

high temperatures and/or low frequencies, an SBS PMB does not exhibit a reduction

in complex modulus to the same degree and generally exhibits a decrease in phase

angle representing more elastic behaviour. This is due to the action of the SBS

polymer in the PMB blend; as the bitumen becomes more fluid, its mechanical

properties become less dominant with the elastomeric properties of the SBS polymer

substructure becoming more prevalent. It is therefore possible to investigate the effect

of the rubber-bitumen interaction on both the polymer and base bitumen dominate

areas of behaviour by analysing the mechanical behaviour of the PMB under these

two extreme conditions. In terms of the complex modulus and phase angle master

curves, a high frequency response represents the bitumen dominant phase while the

polymer response is dominant at low frequencies.

The master curves of complex modulus and phase angle for the air cured

samples of SBS PMB are presented in Figs. 6 and 7, while the rubber cured samples

for the same bitumen are shown in Figs. 8 and 9. Figs. 6 and 7 show the complex

modulus and phase angle master curves for two samples of SBS PMB, one cured for 1

hour and one for 24 hours at 155oC. The results in Fig. 6 show that curing the SBS

PMB at a high temperature increases the complex modulus at high loading

 16

frequencies where the properties of the base bitumen are dominant. This behaviour is

due to oxidative age hardening of bitumen. However, at low loading frequencies,

where the properties of the polymer structure are dominant, the curing slightly

decreases the complex modulus due to the combined effects of a reduction in the

molecular size of the SBS polymer structure and a possible reduction in compatibility

of the PMB system following oxidation. The degradation of the SBS polymer phase is

linked to the oxidation of the sensitive double bonds of the polybutadiene chains when

the SBS PMB is exposed to high temperatures with access to air (Airey and Brown

1998; Cotte and Such 1996; Linde and Johansson 1992; Kuppens 1995; Brule et al.

1988). The reduction in compatibility of the two phase, polymer-bitumen system is

due to the loss, following oxidative ageing, of the maltenes (oil fractions) required to

solvate the SBS polymer. Thermoplastic rubbers, such as SBS, have molecular

weights similar to, or greater than, that of the asphaltenes. Consequently, they

complete for the solvency power of the maltene phase and phase separation can occur

if insufficient maltenes are available.

The rheological measurements in Fig. 7 show that, at high frequencies, there is a

slight reduction in phase angle and therefore a more elastic response in the bitumen

dominant region. However, at low frequencies, the PMB tends towards a more

viscous response following oxidative ageing, again due to the combined effects of a

reduction in molecular size of the SBS polymer and a slight reduction in compatibility

of the modified system.

Fig. 8 presents three complex modulus master curves that were produced from

DSR measurements on the residual bitumen aged in crumb rubber (rubber-bitumen

ratio of 0.5) for 1, 6 and 24 hours. Similar trends to those seen in Figs. 6 and 7 can be

seen in Figs. 8 and 9 where at high frequencies ageing of the bitumen in rubber results
 17

in a more elastic response, while at low frequencies the behaviour becomes more

viscous with ageing (curing). The significant differences between Figs. 6 and 8 and

Figs. 7 and 9 are the more pronounced changes in complex modulus and phase angle

following ageing of the SBS PMB in rubber. Assuming that the degradation of the

SBS PMB and the oxidation of the base bitumen will be similar for both the air cured

and the rubber cured samples, these more pronounced changes in complex modulus

and phase angle can be attributed directly to the increased loss of the maltene fraction

following the interaction with the rubber.

The absorption of these lighter molecular weight fractions of the bitumen into

the rubber has a significant effect on the rheological behaviour of the residual

bitumen. At high frequencies, where the response is dominated by the base bitumen,

the combined effects of oxidative ageing, together with the absorption of the lighter

fractions of the bitumen by the rubber, result in large progressive increases in stiffness

and reductions in phase angle with curing. The decrease in stiffness and significant

increase in phase angle, within the polymer dominant area, can be attributed to the

reduction of the maltenes fraction in the bitumen leading to an incompatible polymer-

bitumen system, the precipitation of the SBS modifier and subsequent reduction in the

polymeric nature of the binder.

COHESION TESTING USING THE VIALIT PENDULUM

In addition to changes in rheological behaviour, the effect of the bitumen-rubber

interaction on the cohesive properties of the residual bitumen were investigated.

Cohesion and adhesion are two parameters that represent the ability of bitumen to

bind aggregate and rubber together into a strong matrix. Cohesion can be considered

to be the ability of a material to 'stick' to itself and adhesion can be considered to be

 18

the ability of the material to 'stick' to another material i.e. aggregate and rubber.

Adhesion is dependent on the properties of both the materials in contact and is a

difficult parameter to measure. However, cohesion, which is a measure of the

materials ability to 'stick' to itself, can be measured empirically using the Vialit

Pendulum. Cohesion is defined as "the energy per unit area which is needed to break a

film of bituminous binder under specified conditions of impact" (MCDHW 1992).

Test Method

The Vialit Pendulum Cohesion apparatus consists of a pendulum that is raised

to the vertical and allowed to drop through its arc to strike a steel cube (see Fig. 10).

The steel cube is fixed to a plate by a 1 mm thick layer of bitumen that binds the cube

and the plate together over a 1 cm2 area. The steel block is dislodged by the impact of

the pendulum striking the block, rupturing the bitumen and absorbing a proportion of

the kinetic energy of the pendulum. The amount of energy absorbed is determined by

the angle swept by the pendulum after breaking the cohesive bonds of the bitumen. To

ensure that the cohesion of the binder is measured, the surfaces of the block and the

plate are serrated with grooves to increase the contact surface area between the

bitumen and the steel, thereby increasing the adhesive strength of the steel/bitumen

bond. The purpose of the test is to find the peak energy absorbed by the bitumen in

the impact. The test is carried out over a range of temperatures and the cohesion

values are plotted on a linear scale against temperature.

Cohesion Test Results

The samples of residual bitumen, collected from the curing tests at 155C, were

tested in the Vialit Pendulum Cohesion Test. Fig. 11 shows three cohesion curves for
 19

the SBS PMB, one cured for 1 hour without rubber, one for 24 hours without rubber

and one for 24 hours with rubber (rubber-bitumen ratio of 0.5).

The curves illustrate a slight change in cohesion and temperature at which the

peak cohesion occurs due, firstly, to oxidative ageing and, secondly, to the interaction

of the bitumen with rubber. Compared to the sample aged without rubber for 1 hour,

the sample aged without rubber for 24 hours shows no change in the maximum

cohesive energy, but the temperature at which it occurs is increased. Generally, below

the temperature at which the maximum cohesive energy occurs, the bitumen fails

through a brittle fracture while above this temperature, the failure tends to be more

viscous in nature. Therefore, an increase in the temperature of maximum cohesive

energy suggests that the bitumen is becoming more brittle which is consistent with the

oxidative ageing of the binder.

The interaction of the bitumen with rubber for 24 hours also increases the

temperature at which the peak cohesion occurs, but in addition reduces the maximum

cohesive energy. This illustrates that the interaction between the rubber and the SBS

PMB reduces the cohesive properties of the bitumen, although the peak cohesive

value is still considerably greater than the peak cohesion for a penetration grade

bitumen which is typically less than 1 J/cm2 (Singleton et al. 2000a). The resultant

effect of the reduction in cohesion and changes in rheological characteristics can be

determined by investigating the changes in mechanical durability of the IAA material.

MECHANICAL DURABILITY OF IMPACT ABSORBING ASPHALT

A test was devised to assess the mechanical durability of IAA material, as an

empirical quantitative measure of the adhesion/cohesion of the bitumen within the

IAA mixture. The test was designed to abrade the material by 'plucking' out particles
 20

of rubber and aggregate from the surface of the compacted material, thus giving an

approximate measure of the strength of the adhesive/cohesive properties of the

bitumen (Singleton et al. 2000b). The test was used to compare the change in

mechanical durability of the material after simulated short-term laboratory ageing in a

force draft oven prior to sample compaction compared to conventional asphalt

mixture.

Method

The test apparatus is shown schematically in Fig. 12. The test was developed to

represent the twisting and turning motion due to a person moving on the surface. A

simple abrasive tool with an abrading surface, comprising a series of pyramid shaped

studs (5 mm high) arranged in a grid formation, was rotated on the surface of the

material under the action of a normal load. The normal load was chosen to be 1 kN

and the dimensions of the abrading tool were chosen to simulate the front part of the

sole of a typical sports shoe. After placing a weighed test specimen in the testing jig,

the abrasion tool was rotated through an arc of 60o for a period of 1000 seconds at a

frequency of 0.1 Hz (100 cycles) at a temperature of 20oC. After completion of the

test the sample of material was weighed, the loose particles removed and the

remaining sample re-weighed. The loss in mass was noted and calculated as a

percentage of the initial mass of the test sample.

A mixture of IAA containing 15% rubber, 10% SBS PMB and 75% aggregate

(by mass) was compared to a control material consisting of a bituminous mixture of

comparable grading containing no rubber, to investigate the effect of curing the

material in the oven at 155oC. Each specimen was mixed in the laboratory, then

placed in the oven for 1, 3 and 6 hours (6 hours being the maximum storage time
 21

associated with IAA production). Each batch was then compacted into a 20 mm thick

slab using a roller compactor. The slab was then cut into 6 samples measuring 135

mm by 140 mm to fit the internal dimensions of the testing jig. Each sample was then

tested and the mass loss recorded.

Abrasion Results

The abrasion results for both the control and IAA mixtures are presented in Fig.

13. It can be seen from the figure that curing the material in a force draft oven causes

an increase in mass loss for the IAA mixture. The results indicate that oxidative

ageing of the control mixture at high temperatures has a lesser effect on the material’s

resistance to degradation. However oxidative ageing coupled with the interaction

between the rubber and bitumen and the associated absorption of the lighter fractions

of the bitumen by the rubber has a more significant effect on the mechanical

durability of the IAA material. As the rubber absorbs the lighter fractions of the

bitumen it reduces the amount of residual binder in the mixture as well as altering the

rheological and cohesive properties of the residual binder. The effect of this is to

drastically reduce the mechanical durability of the material. For example, it can be

seen from Fig. 13 that from 1 to 6 hours there is approximately a 300% increase in

mass loss compared to approximately 50% for the sample containing no rubber.

SUMMARY AND CONCLUSIONS

This study has showed that when crumb rubber is added to a bituminous

mixture, such as Impact Absorbing Asphalt, to impart elastomeric inclusions into the

matrix, using the dry crumb rubber modified (CRM) process, it absorbs fractions of
 22

the bitumen when held at elevated temperatures. Based on the data collected from this

study, the following conclusions are warranted:

 In addition to traditional oxidation of bitumen at high temperatures in air, the

residual bitumen in IAA experiences further changes in its constitution as a

result of the interaction between the SBS PMB and crumb rubber due to the

absorption, by the rubber, of the lighter, more volatile fractions of the bitumen.

 In addition to the alterations in the rheological properties, caused by

conventional oxidation of the bitumen and degradation of the SBS polymer to

lower molecular sizes, the residual bitumen experiences more exaggerated

changes in its rheological properties due to the progressive absorption of the

lighter fractions of the bitumen following high temperature curing of the SBS

PMB with rubber. These extensive changes in the rheological properties of the

residual SBS PMB can be seen as an increased stiffness and elastic response in

the bitumen dominant areas of behaviour (low temperatures and/or high

frequencies) and a loss of the polymeric nature of the binder in the polymer

dominant areas of behaviour (high temperatures and/or low frequencies). These

rheological changes are consistent with the absorption of the lighter molecular

weight fractions of the bitumen, reducing the compatibility between the base

bitumen and SBS polymer and causing the polymer to precipitate out of solution

thereby reducing the efficiency of the polymer in the PMB network.

 The absorption of the lighter fractions of the bitumen into the crumb rubber and

the subsequent changes in the rheology of the bitumen also has a detrimental

effect on the cohesion of the residual bitumen following curing of the SBS PMB

in rubber.
 23

 Finally, the mechanical durability of Impact Absorbing Asphalt is reduced with

short-term laboratory ageing of the uncompacted material compared to

conventional asphalt mixtures.

ACKNOWLEDGEMENTS

This project was funded by the Engineering and Physical Sciences Research

Council (EPSRC), Shell Bitumen UK, SARCO Ltd., Tarmac Central and Scott

Wilson Pavement Engineering Ltd. In particular, thanks must go to the individuals

whose work has contributed to this publication; Daphne Ellams and Dave Nelson of

Shell Bitumen UK who kindly carried out the SARA analysis and Corina Hill of Scott

Wilson Pavement Engineering for the work on the Vialit Cohesion Test.

APPENDIX. REFERENCES

AASHTO Designation: TP5 (1994). “Standard Method of Test for Determining the

Rheological Properties of Asphalt Binders – Dynamic Shear Rheometer

(DSR).”

Airey, G.D. (1997). “Rheological Characteristics of Polymer Modified and Aged

Bitumens.” PhD Thesis, School of Civil Engineering, University of Nottingham,

UK.

Airey, G.D. and Brown, S.F. (1998). “Rheological Performance of Aged Polymer

Modified Bitumens.” Journal of the Association of Asphalt Paving

Technologists, 67, 66-100.

Blow, C.M. (1971). “Rubber Technology and Manufacture.” Institution of the Rubber

Industry, London, UK.

 24

Brule, B., Brion, Y. and Tanguy, A. (1988). “Paving Asphalt Polymer Blends:

Relationship between Composition, Structure and Properties.” Proceedings of

Association of Asphalt Paving Technologists, 57, 41-64.

Cotte, C. and Such, C. (1996). “Influence of RTFOT Ageing on the Rheological

Behaviour of Polymer Modified Bitumen and Their Associated Phases.”

Proceedings of the Eurasphalt & Eurobitume Congress, Session 5: Binders –

Functional Properties and Performance Testing, E&E.5.105, Strasbourg.

Ferry, J.D. (1971). “Viscoelastic Properties of Polymers.” New York: John Wiley and

Sons.

Goodrich, J.L. (1988). “Asphalt and Polymer Modified Asphalt Properties Related to

the Performance of Asphaltic Concrete Mixes.” Proceedings of the Association

of Asphalt Paving Technologist, 57, 116-175.

Green, E.L. and Tolonen, W.J. (1977). “The Chemical and Physical Properties of

Asphalt-Rubber Mixtures.” Report ADOT-RS-14 (162), Arizona Department of

Transport.

Heitzman, M. (1992). “Design and Construction of Asphalt Paving Materials with

Crumb Rubber Modifier.” Transport Research Record 1339, Transport

Research Board, Washington, D.C.

Isacsson, U. and Lu. X. (1995). “Testing and Appraisal of Polymer Modified Road

Bitumens – State of the Art.” Materials and Structures, 28, 139-159.

Kuppens, E.A.M. (1995). “Ageing Resistance of Bitumen.” Proceedings of the

Rheology of Bituminous Binders European Workshop, Eurobitume, Paper No.

49, Brussels.

Labout, J.W.A. (1950). “Constitution of Asphaltic Bitumen.” The Properties of

Asphaltic Bitumen, J.P. Pfeiffer, Ed. Elsevier, New York, 13-48.

 25

Linde, S. and Johansson, U. (1992). “Thermo-oxidative Degradation of Polymer

Modified Bitumen.” Polymer Modified Asphalt Binders, Editors K.R. Wardlaw

and S. Shuler, ASTM, STP 1108.

Manual of Contract Documents for Highway Works. (1992). Clause 939, Highways

Agency, UK.

Singleton, T.M., Airey, G.D., Widyatmoko, I. and Collop, A.C. (2000a). “Residual

Bitumen Characteristics following Dry Process Rubber-Bitumen Interaction.”

Proceedings of the Asphalt Rubber 2000 Conference, Vilamoura, Portugal.

Singleton, T.M., Airey, G.D. and Collop, A.C. (2000b). “Effect of Rubber-Bitumen

Interaction on the Mechanical Durability of Impact Absorbing Asphalt.”

Proceedings of the 2nd Eurasphalt and Eurobitume Congress, Session 4,

Barcelona, 1053-1060.

Takallou, H.B. (1988). “Development of Improved Mix and Construction Guidelines

for Rubber Modified Asphalt Pavements.” Transport Research Record 1171,

Transport Research Board, Washington, D.C.

Treloar, L.R.G. (1975). “The Physics of Rubber Elasticity.” 3rd Edition, Oxford, UK.

Vonk, W.C. and Bull, A.L. (1989). “Phase Phenomena and Concentration Effects in

Blends of Bitumen and Cariflex TR.”, Proceedings of the VII International

Roofing Congress, Munich, Germany.

Whiteoak, C.D. (1995). “The Shell Bitumen Industrial Handbook.” Shell Bitumen,

Surrey, UK.
 26

List of Figures

FIG. 1. Increase in mass of rubber cured in different concentrations of SBS

modified bitumen at 155C

FIG. 2. Absorption of SBS modified bitumen in different concentrations of crumb

rubber at 155C

FIG. 3. Relationship between the increase in mass of rubber cured in different

concentrations of SBS PMB and the percentage absorption of the binder

FIG. 4. SARA analysis on the SBS PMB base bitumen cured with and without

rubber

FIG. 5. Schematic of the Dynamic Shear Rheometer (DSR) testing configuration

FIG. 6. Master curve of complex modolus at a reference temperature of 35C for

SBS modified bitumen cured without rubber for 1 and 24 hours at 155C

FIG. 7. Master curve of phase angle at a reference temperature of 35C for SBS

modified bitumen cured without rubber for 1 and 24 hours at 155C

FIG. 8. Master curve of complex modulus at a reference temperature of 35C for

SBS modified bitumen cured with 50% rubber for 1, 6 and 24 hours at

155C

FIG. 9. Master curve of phase angle at a reference temperature of 35C for SBS

modified bitumen cured with 50% rubber for 1, 6 and 24 hours at 155C

FIG. 10. Schematic of the Vialit Pendulum Cohesion Test

FIG. 11. Vialit Pendulum Cohesion curves for SBS modified bitumen cured for

different periods of time with and without rubber

FIG. 12. Schematic of the abrasive wear test

FIG. 13. Percentage mass loss of Impact Absorbing Asphalt

 27

FIG. 1. Increase in mass of rubber cured in different concentrations of SBS

modified bitumen at 155C
 28

FIG. 2. Absorption of SBS modified bitumen in different concentrations of

crumb rubber at 155C
 29

FIG. 3. Relationship between the increase in mass of rubber cured in different

concentrations of SBS PMB and the percentage absorption of the binder
 30

Percentage m/m
0% 20% 40% 60% 80% 100%

1 hour without rubber 5.9 65.5 20.6 8

6 hours without rubber 6.2 63 22.1 8.7

Saturates
24 hours without rubber 6.3 59.6 25.5 8.6
Aromatics
Resins
Asphaltenes
1 hour with rubber 5.7 63.9 21.6 8.8

6 hours with rubber 5.7 62.3 23 9

24 hours with rubber 5.2 56.9 26.5 11.4

FIG. 4. SARA analysis on the SBS PMB base bitumen cured with and without
rubber
 31

Water bath

Oscillating
disc Bitumen

Fixed
disc

FIG. 5. Schematic of the Dynamic Shear

Rheometer (DSR) testing configuration
 32

FIG. 6. Master curve of complex modulus at a reference temperature of 35C for

SBS modified bitumen cured without rubber for 1 and 24 hours at 155C
 33

FIG. 7. Master curve of phase angle at a reference temperature of 35C for SBS
modified bitumen cured without rubber for 1 and 24 hours at 155C
 34

FIG. 8. Master curve of complex modulus at a reference temperature of 35C for

SBS modified bitumen cured with 50% rubber for 1, 6 and 24 hours at 155C
 35

FIG. 9. Master curve of phase angle at a reference temperature of 35C for SBS
modified bitumen cured with 50% rubber for 1, 6 and 24 hours at 155C
 36

Limit of swing Initial Position

after impact

Movement of
arm

Swept angle
after impact ()

Impact with steel

cube

FIG. 10. Schematic of the Vialit Pendulum

Cohesion Test
 37

2.40
Aged without rubber for 1 hour Aged without rubber for 24 Hours
2.20 Maximum Cohesion : 2.10 J/cm2 Maximum Cohesion : 2.10 J/cm2
o o
Temp at Max Cohesion :32 C Temp at Max Cohesion : 34 C
2.00

Aged in rubber for 24 Hours

1.80
Maximum Cohesion : 1.75 J/cm2
o
Temp at Max Cohesion : 34 C
1.60
Cohesion (J/cm )
2

1.40

1.20

1.00

0.80

0.60

0.40

0.20

0.00
0 10 20 30 40 50 60 70 80
o
Temperature ( C)

FIG. 11. Vialit Pendulum Cohesion curves for SBS modified bitumen cured for
different periods of time with and without rubber
 38

SIDE Normal Load PLAN VIEW

VIEW
Cyclic Loading
Load Cell
Abrasive
Loading Ram
Tool
Support Clamp

Abrasive Tool

Sample

FIG. 12. Schematic of the abrasive wear test

 39

FIG. 13. Percentage mass loss of Impact

Absorbing Asphalt

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