AP-T166/10

AUSTROADS TECHNICAL REPORT

Measurement of Changes in PMBs during

Transport and Storage: A Pilot Study

Measurement of Changes in PMBs during Transport

and Storage: A Pilot Study

Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

Published August 2010

Austroads Ltd. 2010

This work is copyright. Apart from any use as permitted under the Copyright Act 1968,
no part may be reproduced by any process without the prior written permission of Austroads.

Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

ISBN 978-1-921709-36-4

Austroads Project No. TT1354

Austroads Publication No. APT166/10

Project Manager
David Hubner
Prepared by
Dr John Oliver and Khar Yean Khoo

Published by Austroads Ltd.

Level 9, Robell House
287 Elizabeth Street
Sydney NSW 2000 Australia
Phone: +61 2 9264 7088
Fax: +61 2 9264 1657
Email: austroads@austroads.com.au
www.austroads.com.au

Austroads believes this publication to be correct at the time of printing and does not accept
responsibility for any consequences arising from the use of information herein. Readers should
rely on their own skill and judgement to apply information to particular issues.

Measurement of Changes in PMBs during Transport

and Storage: A Pilot Study

Sydney 2010

Austroads profile
Austroads purpose is to contribute to improved Australian and New Zealand transport outcomes
by:

providing expert advice to SCOT and ATC on road and road transport issues

facilitating collaboration between road agencies

promoting harmonisation, consistency and uniformity in road and related operations

undertaking strategic research on behalf of road agencies and communicating outcomes

promoting improved and consistent practice by road agencies.

Austroads membership
Austroads membership comprises the six state and two territory road transport and traffic
authorities, the Commonwealth Department of Infrastructure, Transport, Regional Development
and Local Government, the Australian Local Government Association, and New Zealand Transport
Agency. Austroads is governed by a Board consisting of the chief executive officer (or an
alternative senior executive officer) of each of its 11 member organisations:

Roads and Traffic Authority New South Wales

Roads Corporation Victoria
Department of Transport and Main Roads Queensland
Main Roads Western Australia
Department for Transport, Energy and Infrastructure South Australia
Department of Infrastructure, Energy and Resources Tasmania
Department of Lands and Planning Northern Territory
Department of Territory and Municipal Services Australian Capital Territory
Department of Infrastructure, Transport, Regional Development and Local Government
Australian Local Government Association
New Zealand Transport Agency.

The success of Austroads is derived from the collaboration of member organisations and others in
the road industry. It aims to be the Australasian leader in providing high quality information, advice
and fostering research in the road sector.

Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

CONTENTS
1

INTRODUCTION ......................................................................................................................1

1.1 Background...............................................................................................................................1
1.2 Aims of the Study......................................................................................................................2
2

EXPERIMENTAL......................................................................................................................3

2.1 Materials ...................................................................................................................................3

2.2 Treatments................................................................................................................................3
2.2.1 Thermal Stability ........................................................................................................ 3
2.2.2 Oxidation.................................................................................................................... 4
2.2.3 Segregation ............................................................................................................... 5
2.3 Binder Tests..............................................................................................................................7
2.3.1 Elastometer ................................................................................................................ 7
2.3.2 Dynamic Shear Rheometer ..................................................................................... 10
2.3.3 Softening Point ........................................................................................................ 10
3

RESULTS ...............................................................................................................................11

DISCUSSION .........................................................................................................................13

4.1
4.2
4.3
4.4
4.5

Introduction .............................................................................................................................13
Thermal Stability .....................................................................................................................13
Oxidation.................................................................................................................................15
Segregation ............................................................................................................................16
Viscosity..................................................................................................................................18
4.5.1 Relationship between Underlying Viscosity (20/40) and G .................................... 18
4.5.2 Relationship between Underlying Viscosity (20/40) and Consistency at 5%
Strain ....................................................................................................................... 19
4.6 General ...................................................................................................................................20
4.6.1 Segregation ............................................................................................................. 20
4.6.2 Thermal Stability ...................................................................................................... 20
4.6.3 Oxidation.................................................................................................................. 21
5

CONCLUSIONS .....................................................................................................................22

REFERENCES ................................................................................................................................23

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

TABLES
Table 2.1:
Table 3.1:
Table 3.2:
Table 3.3:
Table 3.4:
Table 3.5:
Table 3.6:

Binders used in the pilot study ....................................................................................3

Underlying Viscosity (20/40 method) ........................................................................11
Consistency at 100% strain ......................................................................................11
Consistency at 5% strain ..........................................................................................11
Complex modulus from DSR testing .........................................................................12
Phase angle from DSR testing .................................................................................12
Ring and ball softening point ....................................................................................12

FIGURES
Figure 2.1:
Figure 2.2:
Figure 2.3:
Figure 2.4:
Figure 2.5:
Figure 2.6:
Figure 2.7:
Figure 4.1:

Figure 4.2:
Figure 4.3:
Figure 4.4:
Figure 4.5:

Figure 4.6:

Thermal stability equipment (cap for inert gas purge not shown) ...............................4
Metal RTFO bottle with metal rollers ..........................................................................4
Segregation apparatus with sampling points marked .................................................6
Typical elastometer output ..........................................................................................7
Example of consistency measurement .......................................................................8
Examples of Underlying Viscosity measurement ........................................................9
Consistency calculated at 5% and 100% strain ........................................................10
Underlying Viscosity (20/40) results before and after thermal stability
exposure ...................................................................................................................14
Phase angle results before and after thermal stability exposure ..............................15
Underlying Viscosity (20/40) results before and after oxidation treatment................15
Phase angle results before and after oxidation treatment ........................................16
Underlying Viscosity results for top and bottom aliquots after segregation
treatment ...................................................................................................................17
Phase angle results for top and bottom aliquots after segregation
treatment ...................................................................................................................18

Figure 4.7: Relationship between Underlying Viscosity (20/40) and G .....................................19

Figure 4.8: Relationship between Underlying Viscosity (20/40) and consistency at
5% strain ...................................................................................................................20

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

SUMMARY
Polymer modified binders (PMBs) can provide improved service performance over normal
bitumens in demanding situations. However, a number of field problems have been experienced
with PMBs and some of these have been attributed to property changes which can occur during
storage and transport of a binder to the work site.
The pilot study was undertaken to obtain information on the changes likely to occur in different
PMB grades. Such information would be useful in developing guidelines for the handling, storage
and use specific to each grade or type of PMB. It could also be used to adjust specification limits
or develop supplementary specification tests.
The main mechanisms by which property change can occur are segregation, oxidation and thermal
degradation. Three laboratory treatments which simulated these mechanisms were used in the
study. Two bitumens and four PMBs were chosen as representative of the different grades and
polymer types available. These were subjected to each of the three treatments.
Untreated and treated binders were tested using an Elastometer, a dynamic shear rheometer and
a softening point apparatus. The Elastometer test results were used to calculate Consistency at
100% strain and 5% strain, and Underlying Viscosity at 20 to 40% strain. Consistency at 5% strain
produces values similar to Underlying Viscosity at 20 to 40% strain.
The response of PMBs subjected to oxidation and thermal stability treatments is complex and this
made interpretation of the results provided by the different test procedures (Softening Point,
Consistency, etc.) difficult. Instead, analysis of the results focused on Underlying Viscosity and
phase angle which provide information on the viscoelastic behaviour of a sample.
The results showed severe segregation in one of the four PMB samples. Segregation can have a
major effect on the field performance of seals and asphalts. It was recommended that purchasers
should consider a stricter approach than used at present with respect to application of the
segregation requirement in the Austroads framework specification. The Austroads segregation test
and ease of remixing test should be reviewed to determine whether they are suitable, and whether
the specified limits are appropriate.
While changes in binder properties were observed during thermal stability treatment, these can be
picked up more easily in the oxidation treatment. It was recommended that the thermal stability
treatment be used instead to check whether severe change occurs in PMBs if they are
inadvertently heated to higher temperatures or localised hot spots occur during heating. The
results would be used to update advice on handling different types of PMBs.
It was also recommended that the Modified Rolling Thin Film Oven Test be used to evaluate a
wide range of PMBs with a view to providing advice on the property changes which could be
expected in different transport and storage scenarios, or as a specification measure.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

INTRODUCTION

1.1

Background

Polymer modified binders (PMBs) can provide improved service performance, compared to
bitumen. They are used in both surfacings and bases but probably their main use is in thin asphalt
and sprayed seal surfacings. Different formulations have been developed to provide, among other
things, improved rutting resistance and longer fatigue life in asphalt; and improved aggregate
retention under stress, strain alleviating membranes to retard cracking and to enable long-life seals
in sprayed seals.
The improved performance of PMBs in demanding situations is considered to more than justify
their increased cost over unmodified bitumen. However, PMBs require more care in transport and
handling, and significant failures of sprayed seals have been attributed to PMB problems (Neaylon
& Busuttil 2007).
Probably the most demanding PMB type is that based on styrene butadiene styrene (SBS) double
ended block copolymer. This has the advantage that, at high temperatures, the polymer molecules
can move freely and the PMB can be relatively easily sprayed or mixed with aggregate in an
asphalt plant. At low (service) temperatures the SBS molecules can associate to form a network
structure that provides improved performance.
In order to achieve this desirable outcome, the chemical properties of the particular SBS
composition used must be matched to the bitumen with which it is blended. To assist in this
process, suitable oils may be added to the blend or the SBS molecules grafted (cross-linked) to
bitumen molecules by a process similar to vulcanisation.
The behaviour of SBS blends is complex and their properties can depend on the degree of
degradation of the polymer, due to high temperature exposure or oxidation, and the phase
morphology of the blend (the form in which the polymer is distributed throughout the binder and
interacts with the bitumen). This, in turn, depends on the chemistry of the components, their
degree of mixing and the thermal history of the binder since manufacture.
The main field problems reported in Australia have been associated with segregation of PMBs into
polymer rich and bitumen rich fractions, and with degradation of PMBs. This latter problem can
sometimes take the unusual form of a PMB being blended with a higher than required
concentration of polymer to take into account, for example, the degradation expected during a
lengthy transport operation. Where such degradation does not occur, the higher than expected
polymer concentration can cause problems to seals in particular through an inability of the binder
to wet the surface of aggregate particles and adhere to them.
Efforts to control such problems have been hampered through difficulties in relating the
manufactured properties of PMBs with properties measured during placement (i.e. after storage
and transport to the construction site) (Neaylon & Busuttil 2007). Since control by testing PMBs
during placement is impractical at present, satisfactory placement properties must be ensured by
relying on test results carried out at an earlier stage of the process (e.g. shortly after manufacture).
This can only be done if change in the properties of PMBs during transport and storage is
minimised through adherence to appropriate handling protocols such as those recommended by
Australian Asphalt Pavement Association (2005). If property change cannot be prevented for a
particular PMB type then the magnitude of the likely change should be estimated so that the
placement properties can be accurately predicted.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

1.2

Aims of the Study

In order to obtain such information, the pilot study reported here was undertaken. The overall aim
of the investigation was:

to improve the performance of PMBs used in road construction by refining guidelines for
handling, transport and storage and use appropriate to each specific type of PMB.

The main mechanisms causing changes in PMB properties during transport and storage are
believed to be:

segregation

thermal degradation

oxidation.

This report describes candidate tests to assess the effect of each of these mechanisms. The tests
were trialled on a small range of PMBs.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

EXPERIMENTAL

2.1

Materials

Four commercially produced PMBs, intended to cover the range of polymer concentrations used in
the road industry, were obtained (Table 2.1). The sample names used are those of the PMB grade
(Austroads 2006a) to which the sample was manufactured. Two bitumen grades were also
included for comparison purposes.
Although not all the PMB samples conformed to the current Austroads specification (Austroads
2006a) they were nonetheless representative of the different grades and polymer types available.
S15E which was specified in earlier Austroads documents (Austroads 1997, Austroads 2000) is
used by some road authorities and was chosen so as to include a low concentration SBS level in
this sample set. Three of the PMBs (A10E, S20E, and S15E) are normally manufactured using an
SBS polymer, while the fourth (S35E) is normally manufactured using a polybutadiene (PBD)
polymer. Ethylene vinyl acetate (EVA) and ethyl methacrylate (EMA) based polymers have been
used in the past in Australia but were not currently available when samples were obtained for this
study.
Table 2.1: Binders used in the pilot study
Sample

Typical application

C170

Sealing grade bitumen

C320

Asphalt grade bitumen

A10E

Specialty asphalt binder for severe conditions (normally SBS)

S20E

High Stress Seals (HSS); Strain Alleviating Membrane (SAM) (normally SBS)

S15E

Specialty binder for less severe seal conditions (normally SBS)

S35E

High Stress Seals (normally PBD)

2.2

Treatments

2.2.1

Thermal Stability

A simple treatment apparatus was developed and consists of a 500 mL (disposable) can which is
heated in a temperature controlled aluminium block (Figure 2.1). Approximately 400 mL of sample
is used and the headspace is filled with carbon dioxide. The sample is gently stirred during
treatment to prevent segregation.
Treatment conditions are the same as for the segregation experiment (24 h at 180 C) except that
the thermal stability sample is stirred while the segregation sample is not.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

Pt100 temperature sensor

positioned in base of aluminium

180.0
Temperature Controller

Hot Plate

Figure 2.1: Thermal stability equipment (cap for inert gas purge not shown)

2.2.2

Oxidation

An existing procedure was used to assess oxidation susceptibility. This procedure is the Modified
Rolling Thin Film Oven (MRTFO) test. It is based on a conventional Rolling Thin Film Oven Test
which has been developed further to incorporate rollers in the bottle (Figure 2.2) to ensure a similar
thickness of binder film is deposited on the bottle walls by PMBs with different flow characteristics.
The procedure is described in Appendix A2 of Austroads test method AG:PT/T103 (Austroads
2006c).
The treatment time and temperature used in this study was that specified in AG:PT/T103 (1 h
at163 C).

Roller - shown as transparent so

attachment of end pieces is visible

Figure 2.2: Metal RTFO bottle with metal rollers

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

2.2.3

Segregation

An existing Austroads test method covers segregation of PMBs (Austroads 2006d) but this test
was not considered to be sensitive enough to provide the information required in the pilot study.
The Austroads test is similar to a cigar tube test employed in the U.S. but uses a soft drink can
rather than a cigar tube.
A specific piece of equipment was designed by ARRB which consisted of a tall cylinder, equipped
with sample tapping points (Figure 2.3). The charged cylinder is stored in an oven at elevated
temperature for segregation to occur. The apparatus was designed to meet the following
requirements:

incorporate an arrangement to minimise oxidation (i.e. an inert gas atmosphere in the

headspace). CO2 is purged at 2 L/min through a Teflon tubing, which is connected to the lid
of the metal cylinder column, throughout the segregation treatment. This setup is to expel
any air through the partially open upper sampling point and establish a CO2 blanket.

be tall, to maximise separation of the polymer from the base bitumen

include facilities to remove top and bottom samples after treatment with no disturbance of the
sample in the cylinder which might cause remixing (i.e. gravity feed valves)

permit a minimum of 100 mL samples to be drawn from two tapping points (top and bottom)

have a total sample size no greater than 1 L in order to minimise the volume of material
required.

Two units were manufactured, together with a stand to assist with handling, and to hold the
segregation cylinders vertically in the oven during treatment. Figure 2.3 shows a unit with the
sampling points marked. The volume of sample required is 800 mL.
The correct starting volume is obtained before oven treatment by draining the column to the upper
sampling point. Following oven treatment, the normal arrangement is to withdraw 100 mL of
sample from the top by draining to the second sampling point, followed by 100 mL by beaker
volume from the lower tap. A treatment time of 24 h (with a CO2 blanket) in an oven at 180 C was
used.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

Carbon Dioxide connection to

minimise oxidation and, if necessary,
help expel binder
Screw cap
Upper sampling point to establish
start level prior to treatment

Second sampling point 100 mL below

start surface

Lower sampling point to remove

100 mL of sample from the bottom
of the column.

Figure 2.3: Segregation apparatus with sampling points marked

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

2.3

Binder Tests

2.3.1

Elastometer

The Elastometer procedure is described in Austroads test method AG:PT/T121 (Austroads 2006a).
The instrument operates by shearing an annular sample of material between two concentric
cylinders at a controlled strain rate (perpendicularly to the circular plane of the cylinders), and to a
desired preset strain level (loading phase). The load is then removed and the amount of strain
recovery is measured with time (recovery phase). During the loading / unloading phases, both
displacement and force are measured (Figure 2.4).
100

10

90

Force (stress)
or Strain
Y

80

strain of
1.0

Strain

70

strain recovery
60

50

Force

40

30

20

10

residual strain

1
0

Time under Stress (s)

20
40
60
10
12
14
16
Unloading time (s)

80
18

100
20

Figure 2.4: Typical elastometer output

Source: AG:PT/T121 (2006).

For the high service temperature parameter, Consistency (at 100% strain) has been provisionally
adopted for the Austroads PMB specification framework (Austroads 2006a). Consistency is
derived from the peak force at the maximum strain (i.e. 100%) and defined as peak stress (max) /
strain rate (). An example is shown in Figure 2.5.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

1.6
1.4

Force (N)

1.2
1.0

Consistency is derived
from the peak force
recorded at the end of
the loading phase
(strain 100%)

0.8
0.6
0.4
0.2
0.0
0

10

Time (sec)

Figure 2.5: Example of consistency measurement

Underlying Viscosity is one of a number of methods that can be used to approximate the viscous
component of a PMB. During the loading phase where a constant strain rate ( = 0.1 s-1) is
applied, the viscous response provides a rapid force increase at the very beginning of the loading
phase. Since Consistency (at 100% strain) is derived from the peak force at the end of the loading
phase, it is unable to measure the viscous behaviour (particularly if the material is mainly elastic).
More discussion on this topic can be found in a report by Choi (Austroads 2010a forthcoming).
Two different UV extrapolation methods (Figure 2.6) are currently under review by an Austroads
technical committee, namely:

50/100 method UV is derived from the line (intercept to Y-axis) fitted on the curve within the
range of 50 100% strain (Figure 2.6 (a), referred to as UV in this report). This 50/100
method was proposed for research proposes (Tredrea 2003).

20/40 method UV is derived from the line (intercept to Y-axis) fitted on the curve within the
range of 20 40% strain (Figure 2.6 (b), referred to as UV 20/40 in this report).

The 50/100 method is a method that has been used for some time. However, the 20/40 method
was recently suggested (as an alternative UV measurement method) due to some data
interpretation problems encountered when the 50/100 method was used.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

1.6
1.4
UV is derived from the line
fitted on the curve within the
range of 50 100% strain

Force (N )

1.2

Strain 100%

1.0
0.8
Strain 50%

0.6
0.4
0.2
0.0
0

10

10

Time (sec)
(a) UV measured using the 50/100 method

1.6
1.4
UV 20/40 is derived from the
line fitted on the curve within the
range of 20 40% strain

Force (N)

1.2
1.0
0.8
0.6

Strain 40%

0.4

Strain 20%

0.2
0.0
0

Time (sec)
(b) UV measured using the 20/40 method
Figure 2.6: Examples of Underlying Viscosity measurement

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

In this report, Underlying Viscosity is calculated using the 20/40 method since a study by Choi
(Austroads 2010a forthcoming) showed that this gave a better correlation with rutting, as indicated
by wheel tracking, than the 50/100 method for the samples studied. This study also showed that
Consistency measured at 5% strain (Figure 2.7) produced values similar to Underlying Viscosity
calculated using the 20/40 method. The correlation with wheel tracking results was similar for both
parameters.

1.6
1.4

Force (N)

1.2
Consistency at
5% strain

1.0

Consistency at
100% strain

0.8
0.6
0.4
0.2
0.0
0

10

Time (s)
Figure 2.7: Consistency calculated at 5% and 100% strain

2.3.2

Dynamic Shear Rheometer

A TA Instruments Dynamic Shear Rheometer (DSR) was used to obtain modulus and phase angle
data. Parallel plate geometry was employed, and cylindrical specimens were prepared with a
diameter of 25 mm and height of 1 mm. These were subjected to a series of sinusoidal oscillation
frequency sweeps at a temperature of 60 C. The test specimen was surrounded by a temperature
controlled water bath. The results reported were complex modulus (G*) and phase angle ()
measured at 1 rad/s.
2.3.3

Softening Point

The Ring and Ball Softening Point of treated and untreated samples was determined according to
Austroads test method AG:PT/T131 (Austroads 2006f). Whilst this test is difficult to interpret in
terms of fundamental properties such as elasticity and viscosity, the apparatus is widely available
and the test is commonly used for control purposes.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

RESULTS

Results are presented in Table 3.1 to Table 3.6, and are discussed in Section 4.
Table 3.1: Underlying Viscosity (20/40 method)
Underlying Viscosity (Pa.s) at 60 C, 0.1 strain rate using Mould B
Sample

No treatment

Thermal
degradation

MRTFO#

Segregation top

Segregation
bottom

C170

167

224

282

N/A

N/A

C320

399*

463

682

N/A

N/A

A10E

810

1053

1023

4190

623

S20E

736

636

945

1014

910

S15E

330

287

439

190

191

S35E

536

761

1026

636

629

# Modified rolling thin film oven test.

Measured using capillary viscometer.
* Value is beyond the maximum value of 380 Pa.s, as specified in AS2008.

Table 3.2: Consistency at 100% strain

Consistency (Pa.s) at 60 C, 0.1 strain rate using Mould B
Sample

No treatment

Thermal
degradation

MRTFO#

Segregation top

Segregation
bottom

A10E

6 621

6 017

7 324

45 873

2 017

S20E

5 895

1 997

5 657

8 773

8 818

S15E

2 905

340

2 573

281

299

S35E

644

950

1 349

779

773

# Modified rolling thin film oven test.

Table 3.3: Consistency at 5% strain

Consistency (Pa.s) at 60 C, 0.1 strain rate using Mould B
Sample

No treatment

Thermal
degradation

MRTFO#

Segregation top

Segregation
bottom

A10E

1033

1154

1178

4663

630

S20E

880

619

1051

1163

1111

S15E

444

260

500

193

200

S35E

505

699

908

576

575

# Modified rolling thin film oven test.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

Table 3.4: Complex modulus from DSR testing

Complex modulus G* (Pa) at 60 C and 1 rad/s
Sample

No treatment

Thermal
degradation

MRTFO#

Segregation top

Segregation
bottom

C170

156

210

253

N/A

N/A

C320

302

413

536

N/A

N/A

A10E

728

931

1198

5519

508

S20E

739

629

761

821

699

S15E

272

310

344

388

363

S35E

441

632

855

486

525

# Modified rolling thin film oven test.

Table 3.5: Phase angle from DSR testing

Phase angle () measured at 60 C and 1 rad/s
Sample

No treatment

Thermal
degradation

MRTFO#

Segregation top

Segregation
bottom

C170

90

89

89

N/A

N/A

C320

89

89

88

N/A

N/A

A10E

74

51

65

11

71

S20E

45

61

59

39

48

S15E

48

53

58

39

45

S35E

78

76

75

78

78

# Modified rolling thin film oven test.

Table 3.6: Ring and ball softening point

Softening Point (C)
Sample

No treatment

Thermal
degradation

MRTFO#

Segregation top

Segregation
bottom

C170

46.6

48.1

49.6

N/A

N/A

C320

52.7

52.0

54.5

N/A

N/A

A10E

69.9

91.0

88.5

130.0

56.9

S20E

90.6

94.5

84.3

99.0

88.3

S15E

70.9

58.8

67.6

67.3

64.7

S35E

53.8

56.7

58.4

54.3

55.1

# Modified rolling thin film oven test.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

DISCUSSION

4.1

Introduction

The response of PMBs subjected to the various treatments used in this study is complex. A
number of processes may occur, some in parallel. These include:

hardening of the base bitumen due to oxidation

increase in asphaltene content of the base bitumen due to oxidation

segregation which is influenced by initial bitumen/polymer compatibility, any additives used

and the method of mixing polymer and bitumen

structural changes in the polymer due to oxidation or thermal degradation

decreased compatibility between polymer and bitumen due to asphaltene increase

improved compatibility between polymer and bitumen due to polymer changes caused by
oxidation or thermal degradation

change in segregation propensity due to compatibility changes caused by oxidation or

thermal degradation

changes in phase morphology which depends on the compatibility of the polymer and
bitumen used, the effectiveness of initial and subsequent mixing, and the thermal history of
the blend.

A particular test procedure (such as Softening Point or Consistency) may emphasise the effect of
one or more of the above changes in a different way to another test procedure. This makes
interpretation of the results in Section 3 difficult.
It was, therefore, decided to focus in this discussion on those test properties which either indicated
basic behaviour of the sample (such as phase angle) or which had been correlated with
performance (such as Underlying Viscosity). A report by Choi (Austroads 2010a forthcoming)
showed that Underlying Viscosity was correlated with rutting performance of asphalt (as indicated
by wheel tracking performed on a range of PMBs) and that Consistency, measured at 5% strain,
gave a similar numerical value and further information is given in Section 4.5.2. Only Underlying
Viscosity is discussed in this report but the remarks apply equally to Consistency at 5% strain.

4.2

Thermal Stability

The thermal stability treatment, as detailed in Section 2.2.1, involved exposure of samples for 24 h
at 180 C with low shear mixing under a carbon dioxide blanket. The Underlying Viscosity values
shown in Figure 4.1 for the two bitumens (C170 and C320) are actually capillary viscosity values
(equivalent to UV for an ideal Newtonian fluid, but not identical). The two bitumens have hardened
during exposure in spite of the carbon dioxide blanket. The most likely cause is oxidation due to
dissolved oxygen, or oxygen entrained by the mixing process because the carbon dioxide blanket
was not completely effective.
While the A10E and S35E binders have also hardened, the opposite has occurred in the case of
S20E and S15E. The most likely cause is degradation of the polymer through chain scission. This
would reduce elastic behaviour and such a reduction is shown by an increase in phase angle
(Figure 4.2).

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

It is perhaps surprising that the third SBS-based PMB (A10E) showed a different behaviour. A
possible explanation is that the phase morphology of the A10E sample changed significantly during
thermal stability exposure. Phase morphology of PMBs is the subject of a separate study. Stirring
of sample the A10E during the 24 h treatment appeared to change the sample morphology from a
continuous bitumen phase with dispersed polymer to a continuous polymer phase with bitumen
inclusions. However, sample A10E was very prone to segregation and this may have contributed
to the result.
The thermal stability treatment temperature of 180 C was chosen as representative of transport
and storage conditions. However, some polymers are particularly susceptible to thermal
degradation at higher temperatures which may be reached accidentally during handling or in local
hot spots during heating. It may be advisable to assess PMBs for their susceptibility to property
change at high temperature, on a non-routine basis, so that advice can be given on whether it is
essential to avoid extreme temperature conditions for particular PMBs.
Thermal stability - Underlying Viscosity (20/40)

Underling Viscosity (Pa.s)

1,200
Original

1,000

Treated

800
600
400
200
0
C170

C320

A10E

S20E

S15E

S35E

Figure 4.1: Underlying Viscosity (20/40) results before and after thermal stability exposure

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Thermal stability - Phase Angle

Phase angle (degrees)

100
90

Original

80

Treated

70
60
50
40
30
20
10
0
C170

C320

A10E

S20E

S15E

S35E

Figure 4.2: Phase angle results before and after thermal stability exposure

4.3

Oxidation

The oxidation treatment used is described in Section 2.2.2, and involved exposure of samples for
1 h at 163 C in a rotating metal bottle containing a roller. This has resulted in an increase in the
viscosity of the base bitumens, due to oxidation, and increases in the Underlying Viscosities of the
PMBs (Figure 4.3). Sample S35E showed a much larger increase than the other binders.
Oxidation - Underlying Viscosity (20/40)

Underlying Viscosity (Pa.s)

1,200
Original
Treated

1,000
800
600
400
200
0
C170

C320

A10E

S20E

S15E

S35E

Figure 4.3: Underlying Viscosity (20/40) results before and after oxidation treatment

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

Oxidation - Phase Angle

Phase angle (degrees)

100
90

Original

80

Treated

70
60
50
40
30
20
10
0
C170

C320

A10E

S20E

S15E

S35E

Figure 4.4: Phase angle results before and after oxidation treatment

Oxidation of the bitumens resulted in a small reduction in phase angle, and thus slightly more
elastic behaviour, as expected (Figure 4.4). The S20E and S15E binders showed an increase in
phase angle (larger viscous component), similar to that which occurred during the thermal stability
treatment, and this may be due to structural changes, such as chain scission, in the polymers.
This did not occur for the A10E sample but the tumbling action of the steel roller in the treatment
bottle may have served to improve the mixing of the polymer with the base bitumen and alter the
phase morphology of the binder. However, as indicate previously this binders strong tendency to
segregation may have contributed to the result.
The observed increase in viscosity of the two bitumens (C170 and C320) after treatment was
comparatively small (134% and 116% respectively). Average values of 188% and 185% were
obtained for Class 170 and Class 320 bitumen respectively subjected to the conventional RTFO
test (Standards Australia 1994) and reported in a study of the properties of Australian bitumens
(Austroads 2007). This suggests that oxidation conditions during the MRTFO treatment were
milder than those in the conventional RTFO treatment. This is probably due to the greater quantity
of binder used in the MRTFO treatment (50 g compared to 35 g for the RTFO treatment) which will
result in higher film thickness and slower oxygen diffusion.

4.4

Segregation

Where there is not complete compatibility between the dispersed polymer and bitumen,
segregation can occur over a period of time, with the lighter polymer fraction floating to the
surface. A number of factors influence how rapidly segregation occurs. The main ones are degree
of compatibility and temperature at which the binder is stored.
The segregation treatment in the current study was carried out in a vertical column placed in an
oven for 24 h at 180 C with a carbon dioxide blanket and no stirring. The Underlying Viscosity
chart (Figure 4.5) shows that sample A10E had a very strong tendency to segregate. Sample
S20E showed a slight tendency to segregate under the test conditions.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

The phase angle chart (Figure 4.6) confirms the above observations. The segregated top fraction
shows more elastic behaviour, due to a higher polymer content than the bottom fraction, in both
cases.

Underlying Viscosity (Pa.s)

The very high segregation propensity exhibited by the A10E binder could very easily result in field
problems. Indeed, problems were experienced in the laboratory with splitting the sample to obtain
representative sub-samples. Some split sub-samples showed different properties in spite of
careful stirring immediately before sample splitting.

Segregation Top and Bottom - Underlying Viscosity

(20/40)
4,500
Top
4,000
Bottom

3,500
3,000
2,500
2,000
1,500
1,000
500
0
A10E

S20E

S15E

S35E

Figure 4.5: Underlying Viscosity results for top and bottom aliquots after segregation treatment

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

Segregation Top and Bottom - Phase Angle

90
Top
Bottom

Phase angle (degrees)

80
70
60
50
40
30
20
10
0
A10E

S20E

S15E

S35E

Figure 4.6: Phase angle results for top and bottom aliquots after segregation treatment

4.5

Viscosity

4.5.1

Relationship between Underlying Viscosity (20/40) and G

Work to develop the Austroads PMB and Multigrade specification framework has, up to now,
concentrated laboratory investigations on identifying the binder properties which control asphalt
rutting. Rutting was chosen as the first field property to be studied since it could be simulated
reasonably well in the laboratory with a wheel tracking test.
It appears that rutting is mainly influenced by the viscosity of a bitumen or the viscous component
of the behaviour of a PMB. The above discussion has, therefore, focused on Underlying Viscosity
as a field performance indicator since it can be calculated from information obtained during routine
Elastometer testing.
The viscous component of the complex modulus (G) can be calculated from DSR testing using
Equation 1 (Dickinson 1984, Mezger 2006):
G* x sin

G*

the complex shear modulus (Pa)

the angular phase difference between force and

displacement in sinusoidal loading (degrees).

where

The relationship between Underlying Viscosity and G is shown in Figure 4.7 for initial results
(before sample treatment) and for samples subjected to oxidation and thermal stability treatment.
The square symbol indicates an outlier that was excluded when calculating the trend line. This
point may be in error since some samples of A10E may have differed from others due to
segregation during sample splitting.
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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

The graph indicates a high degree of correlation between G measured using a dynamic shear
rheometer and Underlying Viscosity measured using an Elastometer.

Underlying Viscosity (20/40) at 60C (Pa.s)

1,200

1,000
R2 = 0.9456

A10E
outlier

800

600

400

200

0
0

200

400

600

800

1000

1200

Viscous com ponent (G") of the com plex m odulus at 60C & 1 rad/s (Pa)

Figure 4.7: Relationship between Underlying Viscosity (20/40) and G

While the emphasis in this report has been on viscosity since that property has been related to
rutting performance, other parameters may be better related to fatigue and crack resistance in
asphalt and to the performance of sprayed seals.
4.5.2

Relationship between Underlying Viscosity (20/40) and Consistency at 5% Strain

As discussed earlier, Choi (Austroads 2010a forthcoming) showed that Consistency measured at
5% strain (Figure 2.7 ) produced values that were comparable to Underlying Viscosity calculated
using the 20/40 method. Chois data was for a range of PMBs tested for rutting resistance. A
relationship is shown in Figure 4.8 for the PMBs used in this pilot study, both before and after
treatment for thermal stability, oxidation and segregation.
Since both parameters are based on the same Elastometer curve, the effect of sample variability is
eliminated from the correlation. A high degree of correlation R2 = 0.99 was observed for the
current data.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

Underlying viscosity (20/40) at 60 o C (Pa.s)

1,400

1,200

1,000
R2 = 0.9906

800

600

400

200

0
0

200

400

600

800

1,000

1,200

1,400

Consistency at 5% strain at 60o C (Pa.s)

Figure 4.8: Relationship between Underlying Viscosity (20/40) and consistency at 5% strain

4.6

General

4.6.1

Segregation

This limited study has looked at the usefulness of three treatments in indicating the changes which
can occur during the transport and storage of PMBs. The largest and potentially most damaging
change was that caused by segregation, and it is recommended that a segregation test result be
declared for each batch of PMB.
There is a requirement in the Specification Framework for Polymer Modified Binders and
Multigrade Bitumens (Austroads 2006a) for a segregation test to be performed, and for an ease of
remixing test (Austroads 2006b) to be performed if the segregation value exceeds 8%. The
results for sample A10E indicated that it was very prone to segregation and it is unlikely that the
material would have met the specification requirement. Purchasers should consider a stricter
approach to ensure that a product does not segregate after manufacture. It may be worthwhile to
review the Austroads segregation and ease of remixing tests since there appears to be little data
on their operation.
4.6.2

Thermal Stability

The thermal stability treatment was performed at 180 C since this was considered representative
of typical storage and transport conditions. It is recommended that the treatment be used instead
to check whether severe change occurs in PMBs if they are inadvertently heated to higher
temperatures or localised hot spots occur during heating. However, the effectiveness of the CO2
blanket arrangement should be checked first.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

The results would be used to update advice on handling different types of PMBs. It is not
recommended that the treatment be used routinely or in a specification.
4.6.3

Oxidation

The oxidation treatment indicated that significant property changes can occur under comparatively
mild conditions. It is recommended that the test be pursued further, either to provide advice on
likely property changes which could occur in different transport and storage scenarios, or as a
specification measure.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

CONCLUSIONS

Potentially damaging segregation can occur in commercially produced PMBs, and

purchasers should consider a stricter approach than applied at present to ensure that a
product does not segregate after manufacture.

The Austroads segregation and ease of remixing tests should be reviewed to determine
whether they are suitable, and whether the specified limits are appropriate.

The thermal stability test described in this report should be used to determine the effect of
inadvertent periods of high temperature on the performance of PMBs.

The Modified Rolling Thin Film Oven Test should be used to evaluate a wide range of PMBs
with a view to providing advice on the property changes which could be expected in different
transport and storage scenarios, or as a specification measure.

The focus in the analysis of results was on viscosity since it has been shown to be related to
an asphalt rutting. However, other parameters may be more appropriate for indicating the
contribution of the binder to asphalt fatigue and crack performance, and to sprayed seal
performance.

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Measurement of Changes in PMBs during Transport and Storage: A Pilot Study

REFERENCES
Australian Asphalt Pavement Association 2005, Guide to the heating of binders for storage and asphalt
manufacture, Advisory note 7, AAPA, Kew, Vic.
Austroads 1997, Austroads specification framework for polymer modified binders, APRG report no. 19,
Austroads, Sydney, NSW.
Austroads 2000, Austroads specification framework for polymer modified binders, AP-T04/00, Austroads,
Sydney, NSW.
Austroads 2006a, Consistency, stiffness, elastic recovery and tensile modulus of polymer modified binders
(ARRB elastometer), AG:PT/T121, Austroads, Sydney, NSW.
Austroads 2006b, Ease of remixing of polymer modified binders, AG:PT/T109, Austroads, Sydney, NSW.
Austroads 2006c, Pre-treatment and loss on heating of bitumen, multigrade and polymer modified binders
(rolling thin film oven (RTFO) test), AG:PT/T103, Austroads, Sydney, NSW.
Austroads 2006d, Segregation of polymer modified binders, AG:PT/T108, Austroads, Sydney, NSW.
Austroads 2006e, Softening point of polymer modified binders, AG:PT/T131, Austroads, Sydney, NSW.
Austroads 2006f, Specification framework for polymer modified binders and multigrade bitumens, by P
Tredrea, AP-T41/06, Austroads, Sydney, NSW.
Austroads 2007, The physical properties of Australian bitumens 1956-2004, by JWH Oliver & E Woodall,
report AP-T74/07, Austroads, Sydney, NSW.
Austroads 2010a forthcoming, Laboratory study on relationship between binder properties and asphalt
rutting, by Y Choi, Austroads, Sydney, NSW.
Dickinson, EJ 1984, Bituminous roads in Australia, Australian Road Research Board, Vermont South, Vic.
Mezger, TG 2006, The rheology handbook: for users of rotational and oscillatory rheometers, 2nd edn,
Vincentz Network, Hanover, Germany.
Neaylon, KL & Busuttil, R 2007. A study of polymer modified binder properties before spraying. AAPA
pavements industry conference, 2007, Sydney, New South Wales, Australian Asphalt Pavement
Association, Kew, Vic, 9 pp.
Standards Australia 1994, Methods of testing bitumens and related roadmaking products: method 10:
determination of the effect of heat and air on a moving film of bitumen rolling thin film oven RTFO test,
AS/NZ 2341.10:1994, SA, North Sydney, NSW.
Tredrea, P 2003, Viscosity in high performance binders and its contribution to asphalt deformation control,
ARRB Transport Research conference, 21st , & Road Engineering Association of Asia and Australasia
(REAAA) conference, 11th, Cairns, Queensland, ARRB Transport Research, Vermont South, Vic, 5 pp.

Austroads 2010
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INFORMATION RETRIEVAL

Austroads, 2010, Measurement of Changes in PMBs during Transport and

Storage: A Pilot Study, Sydney, A4, 31pp, AP-T166/10

Keywords:
Polymer modified binder, PMB, segregation, oxidation, Underlying Viscosity,
consistency, transport, storage, test method.
Abstract:
Three laboratory procedures were used to simulate the changes which occur
during transport and storage of polymer modified binders (PMBs). The
procedures were thermal stability, oxidation and segregation. Four
commercially manufactured PMBs and two bitumens were used in the study.
Following treatment, samples were tested using an Elastometer, dynamic
shear rheometer and softening point apparatus. Severe segregation, which
could have detrimental field consequences, occurred with one of the PMBs.
Oxidation and thermal stability treatment caused a smaller change in properties
of the other PMBs.