Effectiveness of a Bio-based Additive to Restore Properties

of Aged Asphalt Binder

Laurent Porot1, William Grady2
1
Arizona Chemical BV, Almere, The Netherlands, [email protected]
2
Arizona Chemical LLC, Savannah, Georgia US, [email protected]

Abstract

Global asphalt paved road network is approx. 12.6 million kilometers. Continuous effort to
maintain and grow this network of roads has a strong impact not only in terms of economic costs
but also in terms of utilization of natural resources (virgin aggregate and asphalt binder).
Currently the widely accepted technologies allow an average use of 20% RA (Reclaimed
Asphalt) in asphalt mixes. This low percentage, dictated by final road performance, limits to a
minimum the economic benefits associated with a higher use of RA and puts strain on the use of
virgin materials.

This paper investigates the effect of a bio-based additive on aged RA binders through analysis of
basic properties, such as penetration, softening point and viscosity, and of rheological behavior
through Dynamic Shear Rheometer (DSR). The results show how the additive restores the aged
binder properties to meet specifications with small dosages; the consistency of the additive’s
effect across different types of aged binders; the restoration of the rheological properties to a
level similar to the virgin binder; the positive effect on the long term aging of the additive on
aged RA binders. This indicates that this technology will allow using up to 100 % RA into
asphalt mixture.

Keywords: Reclaimed Asphalt Pavement, Asphalt additive, Aging, Bituminous binder,

rejuvenation.

1 Introduction

Economic and environmental constraints are leading more and more to the valuation of products
throughout their entire life cycle. For the pavement industry, the focus is on the overall
management of the natural resources, e.g., aggregates and binder. In this context the use of
Reclaimed Asphalt, (RA) is an important challenge. Asphalt pavement is one of the most
recycled and reusable materials in the world. Today it is widely accepted to use 30 % of
Reclaimed Asphalt into new hot mix asphalt; however, for higher percentages, some specific
techniques are required and researches shown the use of bio-based product can benefit [1] [2].

The main limiting factor to the use of higher RA percentages is the aging of the binder. The
aging mechanism is complex with negative effects coming from oxidation and chemical
modification [3] [4]. Due to aging, the material becomes harder and more brittle [5]; on one
hand, the stiffness is an advantage, as the road becomes less prone to permanent deformation; on
the other hand, the material will be more brittle and thus more prone to cracking, clearly a

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significant disadvantage [6] [7]. Hence a technology that aims to use higher percentages of RA
must be able to fully restore the properties of the aged binder. In this context, a bio-based
rejuvenating agent has been evaluated with regards to its effect on bituminous binder.

The objectives of the study were to determine the capacity of the additive to restore the
properties of an aged binder based on basic properties and also a more fundamental analysis
using Dynamic Shear Rheometer, (DSR) measurements. Then the effect was evaluated towards
different RA aged binder and long-term effect was investigating through aging testing.

2 Materials and methods

2.1 Bio-based rejuvenating agent

Over aging, the major changes include loss of maltenes, which act to soften, and the increase in
asphaltenes and polar aromatics through oxidation. Historically, rejuvenators, such as petroleum
flux oils, only address the former issue by softening the aged binder through a dilution effect of
the asphaltenes. Such an approach does not serve to break the stronger intermolecular
associations built by the ever-increasing polarity of the asphaltenes. The specific bio-based
rejuvenating agent is a liquid additive that will with its specific amphipathic chemical structure
disperses the highly polar fractions limiting the agglomeration of asphaltenes. It is an engineered
additive which is proprietary protected. Table 1 presents the main properties.

Table 1. Properties of the rejuvenating agent.

Flash point Viscosity at 60 °C Density Cloud point

> 280 °C 22 Cst 0.93 < -25 °C

2.2 Bituminous binders

In the first part of the study a single source of RA binder was used to evaluate the effect of the
bio-based rejuvenator. In the second part, the effect was assessed on different RA type including
a virgin binder and artificially aged binder. In the third part, aging was investigated with RA
binder treated with a single dosage of the bio additive.

2.3 Experimental plan

Within this research different testing methods were used from basic properties to more
fundamental testing according to the different steps in the program.

The basic properties of the binders and additive blended binders were based on the European
specifications EN 12591 including penetration at 25°C (EN 1426), softening point temperature
(EN 1427) and Brookfield viscosity (EN 13302).

More in depth analysis was made using a Dynamic Shear Rheometer, DSR. For this study the
test used a 10 mm plate and was run at one frequency (10 rad/s) in a range of - 30 °C to + 90 °C.
These measurements are used to assess the performance of the binder at high, intermediate and
low temperatures, thus providing an indication of asphalt mix performances pertaining to rutting

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resistance, stiffness and cracking susceptibility, respectively. Some more additional tests
including BBR were performed but will be reported in a separate study.

For aging the Rolling Thin Film Oven Test (RTFOT) and Pressure Aging Vessel (PAV)
protocols were used which corresponds respectively to the aging during manufacture, transport
and laying and long-term pavement aging under road conditions [8]. While it is not recognized as
exactly mimicking the real aging condition it provides with indications on aging behavior.

3 Effect of the rejuvenating agent at various dosage levels

A dosage study was conducted to evaluate, how the additive affects the aged binder properties, at
different dosage levels. Aging and oxidation cause hardening of asphalt binders. In this first part
of the work the evaluation was based on the basic properties with penetration value at 25 C,
softening point and viscosities as a quick and simple way to quantify the effect. The aged binder
came from a RA source with significant hard aged properties commonly encountered.

The blend was performed by mixing the aged binder and the additive based on the method as
described in ASTM D4887. The dosage of additive varied from 1 % up to 15 % based on the
weight of the aged binder. Table 2 displays the full results of the basic properties. From this
table, the effect of additive on the aged binder is noticeable even at low dosage levels.

Table 2. Properties of Treated aged binder at different dosage.

Pen R&B Viscosity, mPa/s

Dosage 0,1 mm °C 90 °C 135 °C 150 °C 180 °C
EN 1426 EN 1427 EN 13302
0% 13 67.3 90,400 1,858 850 213
1% 16 65.3 70,080 1,625 693 195
3% 24 62.7 43,750 1,340 620 170
5% 32 58.1 32,130 1,160 545 153
10% 72 49.3 13,230 755 310 105
15% 145 39.5 5,542 435 228 75

Figure 1 displays the impact of the additive at different dosages on penetration value on the
vertical axis and the softening point temperature on the horizontal axis. The boxes are providing
the indication of pen grade specifications as per EN 12591.While the RA binder displays very
hard properties, the effect of the additive helps to restore its properties to a wide range of pen-
grade specifications even at dosages below 10%, based on the weight of aged binder. It can meet
from 20/30 to 70/100 specification with an additive dosage that varies from 3 % to 10 %. In
average, a dosage of 5 % restores the properties by 2 grades.

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Figure 1 Effect of additive dosage on pen and softening point.
Figure 2 displays the impact of the additive on Brookfield viscosity. It provides an indication at
which temperature the binder may be used during mixing and application (mainly compaction).
The horizontal line is the maximum viscosity for mixing [5]. The solid line represents the
viscosity profile of the RA binder indicating it would require high mixing temperatures in an
asphalt plant as high as 180 °C. The broken, dashed lines represent the RA binder with different
dosages. It shows how the additive helps to reduce the viscosity to reasonable values for mixing
with a temperature around 160 °C as usually encountered during asphalt mix manufacturing.

Figure 2 Effect of additive on viscosity.

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4 Effect of additive on various RA binders

RA binders vary in quality, source, history, aging etc. due to different climate conditions [9];
therefore, the effectiveness of the additive, at a constant dosage of 5 %, on various RA qualities
and sources was investigated. Four types of RA and two types of virgin binders of which one
was aged through PAV were considered. The different types of RA binders cover a wide range
of qualities representing from relatively soft RA to much harder RA. The different binders used
are listed in Table 3.

Table 3. Basic properties of the different asphalt binders.

50/70 aged PAV RA 1 RA 2 RA 3 RA 4

Penetration at 25 °C 53 24 32 21 13 7
Softening point 49.2 °C 64.8 °C 62.9 °C 65.6 °C 67.3 °C 92.6 °C

Figure 3 display the effect of the bio-based rejuvenating agent at 5 % dosage on the different
binders. It shows a significant effect on the properties of the different bituminous binders, either
as recovered from granulated RA or as neat asphalt binder aged in the laboratory. Both trends, in
terms of penetration value and softening point changes, are consistent.

Figure 3 Effect of 5% rejuvenating agent on various binders.

5 Rheological analysis

The effectiveness of the additive was further studied using rheological behavior during shear
tests (moduli and phase angle measurements). For this purpose, the same material as in the
dosage study was used at 2 dosage levels, 5 % and 10 %. In addition a control virgin bituminous
binder 35/50 pen graded was used for comparison.

Figure 4 shows │G*│ vs. temperature for the additive at the 2 dosages, 5 % and 10 %, compared
with the RA binder and control virgin binder. It provides an indication of the stiffness of the
material. At low temperature, the material is hard and the │G*│ usually reaches a plateau around
109 Pa. At high temperature, typically above the softening point, the material becomes more
viscous and starts to flow. Usually with │G*│ value below 103 Pa, the data is not reliable and
reaches the limit of accuracy of measurement.

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The additive shows a significant effect even at the 5 and 10% dosage levels. This results in
restoring the behavior of the RA aged binder. At high temperature, 70 C, the shear modulus of
the RA binder is 10 times higher than that of the virgin binder. At this higher temperature, the
additive can restore the modulus similar to the control at a dosage of 10%. At intermediate
temperatures, the RA aged binder is about 8 times harder than the control virgin binder and the
additive restores the modulus to that of the control binder at a dosage of 5%.

Figure 4 Effect of additive on │G*│ master curve.

An interesting analysis from this graph is the temperature susceptibility of the binder; this is the
ability of the material to change its behavior with temperature (or frequency). For the control
virgin binder, between 0 C to 70 C, the shear modulus varies by a factor of 105, while in the
same range of temperatures, the aged binder varies by a factor of 104. This suggests that the
stiffness of the materials will change less during daily or seasonal temperature variations. While
the additive restores the properties of the aged binder similarly to a virgin binder, it keeps the
lower temperature susceptibility leading to a decreased variation with temperature.

An optimum dosage of 5 % can meet similar behavior of the virgin binder at ambient
temperature. At high temperature, the modulus remains higher than the control virgin binder
which means better rutting resistance. And at the same time at low temperature, such as -10 °C
the shear modulus is lower than the control binder which means better for cracking susceptibility
at low temperature.

6 Effect of additive during aging

For the additive to remain useful after plant mixing and after years of use on a road, it must
maintain its effectiveness under these conditions. For this purpose, aging was addressed with
binder aging tests using the RTFOT and PAV. A total of three different asphalt binder blends
were used to compare the data:

 A control pen graded 35/50 asphalt binder,

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  A blend of the reference RA binder treated with 5% of additive which provides similar
properties to those of the 35/50 pen graded asphalt binder,
 A blend made up with RA binder treated with 5 % additive and virgin binder as a case
study for a mix using 75% of RA in a new asphalt mixture.

For each blend aged in the laboratory, mass change, penetration value at 25 C, and softening
point were measured and recorded. Table 4 displays the results. The aged RA binder is included
as reference unfortunately, the quantity was not enough to do aging on RA binder.

Table 4. Effectiveness of additive through binder aging.

Unit 35/50 PEN RA + 5% RA + 35/50

RA graded additive + additive
Fresh
PEN 1/10 mm 21 47 42 41
SP °C 66 52 56 56
After RTFOT
PEN 1/10 mm na 35 36 35
SP °C na 57 59 58
Mass change % na -0.36 -0.62 -0.55
Retained PEN % na 76 86 84
Delta SP °C na 6 2 2
After RTFOT + PAV
PEN 1/10 mm na 28 29 29
SP °C na 64 64 64
Retained PEN % na 60 71 71
Delta SP °C na 12 7 8

The mass change after RTFOT was recorded. All blends are in the same range between 0.4 %
and 0.6 %. Considering the repeatability of the test (in the range of 0.15 %) these values are all
comparable and within the specification. This shows that the rejuvenating agent remains with the
binder and does not evaporate or decompose.

The Figure 5 displays the effect on the penetration values. The retained penetration is determined
as the decrease of the penetration value in percentage. It shows that the retained penetration is
greater for RA treated binders compared to the virgin binder, meaning there is less change in
hardness after RTFOT and PAV. The additive has no deleterious effects while allowing
increased RA usage leading to greater retained penetration and less change in pavement
properties over time.

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Figure 5 Effectiveness on penetration over aging.
Figure 6 displays the effect on the softening point temperature. A similar effect is seen, the
change in softening point is less for binder containing RA and the additive and thus less change
in pavement properties.

Figure 6 Effectiveness on softening point over aging.

To summarize this aging study, blends with RA aged binder and additive alone or in combination
with virgin binder have lower changes in properties compared to a virgin asphalt binder,
meaning they are less prone to age over time. Had the additive evaporated during aging, it would
have been seen on mass loss and if it had degraded, the properties after aging would have been
higher than the initial RA. The effectiveness of the additive remains sustainable over time to
restore and keep the properties of aged binder.

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7 Conclusion

For several years the asphalt industry investigated potential solutions to increase the
reuse/recyclability of asphalt mix, but without a sustainable answer in the long term. This paper
investigated the effect of a bio-based rejuvenating agent that enables to meet this need.

The study was based on a binder laboratory evaluation, through an overall approach as follow:

 How effective is the additive and can restore the properties of a RA binder with low
dosages (from 3 to 10% based on the amount of aged binder)?
 Is this effect consistent and reproducible with various types of aged binder still
maintaining constant the additive level (5%)?
 A more in depth analysis of the rheological behavior based on DSR measurements
 What is the long term effect of the additive through a binder aging evaluation (based on
RTFOT and PAV)?

The main conclusions of the above studies are summarized below:

It is possible to restore the properties of any standard aged binder to virgin binder levels with
small dosage (5 %) of additive, making it possible to design a fit for purpose asphalt mix
whatever the amount of RA. And this effect is consistent across different types of aged RA
binders, including hard aged binder. A 5 % dosage restores by two grades binders

Different blends of aged binders and additive are less prone to age over time compared to
standard virgin asphalt binder. The additive does not evaporate or decompose during process or
in use and is safe to handle and of consistent quality.

References

[1] M. Zaumanis, R. Mallick and R. Frank, “Evaluation of rejuvenator’s effectiveness with

conventional mix testing for 100% RAP mixtures,” 92nd TRB meeting, 13-1447, 2013.
[2] Porot L. and Nigen-Chaidron S., “Laboratory investigation of recycled binder performance,”
in 6th LJMU International conference on Sustainable Construction Materials, 2007.
[3] J. C. Petersen, “A review of the fundamentals of asphalt oxidation,” Transportation Research
Circular E-C140, October 2009.
[4] J. C. Petersen and R. Glaser, “Asphalt Oxidation Mechanisms and the Role of Oxidation
Products on Age Hardening Revisited,” Road Materials and Pavement Design, pp. Vol. 12,
No. 4 pp. 795-819, 2011.
[5] J. Read and W. David, The Shell Bitumen Handbook, fifth edition, Shell UK Oil Products
Limited, 2003.
[6] R. Karlsson and U. Isacsson, “Material-Related Aspects of Asphalt Recycling—State-of-the-
Art,” Journal of Material and Civil Engineering, pp. 18(1), pp 81–92, 2006.
[7] A. Molenaar, E. Hagos and M. Van de Ven, “Effects of Aging on the Mechanical

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 Characteristics of Bituminous Binders in PAC,” Journal of Materials in Civil Engineering,
pp. Vol. 22, No. 8, pp. 779-787, 2010.
[8] C. A. Bell and D. Sosnovske, “Aging: Binder Validation. SHRP-A-384,” Strategic Highway
Research Program, National Research Council, Washington, 1994.
[9] R. F. Coons and P. H. Wright, “An Investigation of the Hardening of Asphalts Recovered
from Pavements of Various Ages,” Journal of Association of Asphalt Paving Technologists,
pp. Vol. 37, pp. 510-528, 1968.

Disclaimer

The authors believe the information set forth above to be true and accurate, but any findings,
recommendations or suggestions that may be made in the foregoing text are without any
warranty or guarantee whatsoever, and shall establish no legal duty or responsibility on the part
of the authors or any Kraton Polymers entity. Furthermore, nothing set forth above shall be
construed as a recommendation to use any product in conflict with any existing patent rights. All
Kraton Polymers entities expressly disclaim any and all liability for any damages or injuries
arising out of any activities relating in any way to this publication or the information set forth
herein.

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