Journal of Hazardous Materials 233234 (2012) 254258

Contents lists available at SciVerse ScienceDirect

Journal of Hazardous Materials
j our nal homepage: www. el sevi er . com/ l ocat e/ j hazmat
Short communication
Investigation of the possibility of using waste cooking oil as a rejuvenating agent
for aged bitumen
Majid Zargar

, Esmaeil Ahmadinia, Hallizza Asli, Mohamed Rehan Karim

Centre for Transportation Research, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
h i g h l i g h t s
An environmental friendly use of waste cooking oil (WCO) is introduced.
Novelty is applied in the rejuvenating of aged bitumen by WCO.
Rheological properties of aged, rejuvenated and virgin bitumen are compared.
a r t i c l e i n f o
Article history:
Received 17 November 2011
Received in revised form16 May 2012
Accepted 11 June 2012
Available online 19 June 2012
Keywords:
Rejuvenating agent
Waste cooking oil
Aged bitumen
Rheological characteristics
a b s t r a c t
The ageing of the bitumen during storage, mixing, transport and laying on the road, as well as in service
life, are the most important problems presented by the use of bitumen in pavements. This paper inves-
tigates the possibility of using waste cooking oil (WCO), which is a waste material that pollutes landlls
and rivers, as an alternative natural rejuvenating agent for aged bitumen to a condition that resembles
the original bitumen. With this target, the physical and chemical properties of the original bitumen, aged
bitumen and rejuvenated bitumen were measured and compared by the bitumen binder tests softening
point, penetration, Brookeld viscosity, dynamic shear rheometer and Fourier transform infrared spec-
troscopy. In addition, the behaviour of the WCO rejuvenated bitumen is investigated and compared with
virgin bitumen after using the rolling thin lm oven ageing process. In general, the results showed that
using 34% of WCO the aged bitumen group 40/50 was rejuvenated to a condition that closely resembled
the physical, rheological properties of the original bitumen (80/100), however, there was a difference in
the tendency to ageing between the WCO rejuvenated bitumen and the virgin bitumen during mixing,
transport and laying on the road.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Bitumen is a useful and expensive material with high thermal
sensitivity. Despite the limited resources, it has been applied in
abundance (110milliontonnes annually in the world) in the high-
way industry [1]. The ageing of the bitumen during storage, mixing,
transport and laying on the road, as well as in service life [2], are
the most important problems presented by the use of bitumen in
pavements. The main ageing mechanism of bitumen is the loss of
volatiles and oxidation, which leads to having higher viscosity and
a bitumen that is stiffer than fresh bitumen [2,3].
The ageing problemof bitumen leads to pavement failure, such
as surface ravelling and cracking, especially reective cracking
[3]. These problems increase the expense of renovation and

Corresponding author. Tel.: +60 379675339; fax: +60 379552182.

E-mail addresses: majidzargar2009@gmail.com(M. Zargar),
halli izza@yahoo.com(H. Asli).
the preservation of bituminous pavements. Therefore, highway
agencies, due to high demand, high expense, lowlife cycle, ageing,
and lack of sufcient natural resources of bituminous material,
have introduced the application of recycled asphalt pavement
(RAP) material in hot mix asphalt (HMA) as an economic and
environmentally sound solution [4,5].
The investigations illustrated that even though the life cycle
of HMA has reached the end, the binder and aggregate from the
old HMA are still valuable [6]. The only problem that has limited
the application of the RAP (only 15%) is the ageing of bitumen. An
increase in the application of a higher percentage of the RAP (till
80%) in the pavement is possible using a rejuvenator [7]. Rejuvena-
tors, which are categorised into rejuvenating agents and softening
agents [1], restore the original ratio of asphaltenes to maltenes in
oxidised (aged) bitumen binders [8] in order to soften the aged
binder and create a broad-spectrumrejuvenation that replenishes
the volatiles and dispersing oils while promoting adhesion [3].
In recent years, the use of rejuvenation in RAP materials (for
application in HMA mixtures) [5], chip seals, and as rejuvenation
0304-3894/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2012.06.021
M. Zargar et al. / Journal of Hazardous Materials 233234 (2012) 254258 255
Table 1
Characteristics of bitumen pen-grade 80/100.
Bitumen test Standard test methods 80/100
Penetration (0.1mm) at 25

C ASTMD5 85
Softening point (

C) ASTMD36 46
Penetration index (PI) 0.968
Ductility (mm) at 25

C ASTMD113 >100
Viscosity (mPa s) at 135

C ASTMD4402 306.5
Complex shear modulus at 76

C ASTMD-4 Proposal P 246 215.5

Phase angle, (

) at 76

C ASTMD-4 Proposal P 246 90

seals [3] (this methodextends theservicelifeof roads) torejuvenate
the aged bitumen has increased remarkably. In addition, recently,
because of the high demand for rejuvenators, the application of
waste products as a rejuvenating agent, such as recycled motor oil
(RO), have been investigated. Romera et al. [9], in Spain, applied RO
and other rejuvenators in recycled HMA mixture. The results of the
investigationindicate that by employing ROas a rejuvenating agent
the permanent deformation was postponed compared to a sample
of the original bitumen. Furthermore, they reported that a mixture
of 80% aged bitumen with 20% recycled motor oil as a rejuvenator,
obtained exclusively fromwaste materials, can compete with new
60/70 bitumen in terms of quality [9].
The successful application of motor recycling oil (RO), powered
the theory of the application of waste oil, such as WCO, as a reju-
venating agent in bitumen. The novelty of this paper is using the
waste cooking oil (WCO) as a rejuvenator in aged bitumen using
the bitumen test methods including penetration, softening point,
Brookeld viscosity, dynamic shear rheometer and Fourier trans-
form infrared (FTIR) spectroscopy test. The aim of this research is
to determine the potential of using waste cooking oil as a reju-
venating agent for aged bitumen binder in order to reduce WCO
environmental pollution [10] and the expense of highway renova-
tion.
2. Material and experimental procedure
2.1. Material
The applied bitumen (80/100 grad) was tested and the
properties are illustrated in Table 1. Furthermore, the chemi-
cal compound in waste cooking oil was measured by the gas
chromatographymass spectrometry (GCMS) test provided by the
Combinatorial & Catalysis Research Centre (COMBICAT), as illus-
trated in Table 2.
2.2. Experimental procedure
Thepropeller mixer was manipulatedas a simulationof thenon-
standard method to hasten the ageing process of the bitumen in
the laboratory. This test was signicant for measuring the effects
Table 2
Chemical properties of used cooking oil in this study.
Fatty acid Waste cooking oil (%)
Lauric acid (C12:0) 0.34
Myristic acid (C14:0) 1.03
Palmitic acid (C16:0) 38.35
Stearic acid (C18:0) 4.33
Oleic acid (C18:2n9c) 43.67
Linoleic acid (C18:2n6c) 11.39
-Linolenic acid (C18:3n6) 0.37
Linolenic acid (C18:3n3) 0.29
cis-11-Eicosenoic acid (C20:1) 0.16
Heneicosanoic acid (C21:0) 0.08
Total 100
Fig. 1. Penetration value versus different rejuvenated WCO bitumens (AB: aged
bitumen).
of heat and air on a moving semi-solid bitumen lm. To prepare
aged bitumen, the original 80/100 bitumen was heated in the oven
at a constant temperature of 160

C for about one and a half hours

to 2h until it was uid enough to pour. Thereafter, approximately
900g of the bitumen was poured into several 5l cylindrical con-
tainers after it had melted completely. Then, the melted bitumen
was placed on the hot plate and mixed using the propeller mixer.
The ageing process was continued for 7h at a speed of 350rpm
to produce aged bitumen 40/50 penetration group. After the age-
ing process was completed, the aged bitumen was tested using the
penetrationtest todetermine the groupof agedbitumen. The 40/50
aged bitumen was then blended with 1%, 2%, 3%, 4%and 5%of waste
cooking oil using the propeller mixer for 30min at 160

C with a
constant speed of 200rpm.
Additionally, the rolling thin lmoven (RTFOT) method (ASTM
D2872) is also applied, to simulate manufacturing and place-
ment ageing (short term), for comparing the normal bitumen and
WCO rejuvenated bitumen after the ageing process. Subsequently,
the total outcomes also underwent the bitumen tests including
penetration (ASTM D5), softening point (ASTM D36), Brookeld
rotational viscometer (ASTM D4402) and dynamic shear rheome-
ter (ASTMD-4 Proposal P246). Furthermore, to assess the chemical
changes, the Fourier transform infrared (FTIR) spectroscopy and
asphaltenes content (ASTMD 4124) was applied. A FTIR Spectrom-
eter, PerkinElmer model SpectrumOne, was used for investigating
the functional characteristics of bitumen binders.
3. Results and discussion
3.1. Penetration value
The consistency of penetration grade or oxidised bitumen was
measured by the penetration test [11]. The 40/50 aged bitumen
was rejuvenated with WCO at 1%, 2%, 3%, 4% and 5% by weight of
bitumen. The effects of mixing waste cooking oil into aged bitu-
men on the penetration value are illustrated clearly in Fig. 1. It
was observed that the penetration value increased linearly as the
amount of waste cooking oil in the aged bitumen increased. The
increase in penetration value is caused by the reduction in the ratio
of asphaltenes to maltenes [12,13], as illustrated in Table 3. How-
ever, when it reached an optimumpercentage of waste cooking oil,
the lower penetration value resembled the original bitumen. The
Table 3
Chemical components of virgin bitumen and WCO rejuvenated bitumen.
Asphaltenes
(wt.%)
Maltenes
(wt.%)
Asphaltenes/
maltenes (%)
Original bitumen 9.23 90.77 10.17
Aged bitumen 10.98 89.02 12.34
Rejuvenate bitumen 9.69 90.31 10.73
256 M. Zargar et al. / Journal of Hazardous Materials 233234 (2012) 254258
Fig. 2. Softening point value versus different rejuvenated WCO bitumens (AB: aged
bitumen).
penetration value of the original bitumen (specic value) was 85
(
0
=85). As displayed in Fig. 1, approximately 3% of added waste
cooking oil rejuvenates the aged bitumen of the 40/50 penetration
group to a similar condition to the original bitumen.
3.2. Softening point value
The relationshipbetweensoftening point value and40/50group
aged bitumen prepared by the propeller mixer are presented
in Fig. 2. As illustrated in the graph, the softening point value
decreased with the addition of waste cooking oil content into the
agedbitumen. Intheagedbitumen, theincreaseof asphaltenes con-
tent with high molecular weight can produce harder bitumen with
lower temperature susceptibility and an increase in the softening
point [14], while the mixture of waste cooking oil can rejuvenate
the aged bitumen. As can be seen in Fig. 2, when approximately 3%
of waste cooking oil is added into aged bitumen penetration group
40/50, it resembles the original bitumen value.
3.3. Penetration index (PI)
The temperature susceptibility of the diverse group of bitumen
has been calculated in terms of penetration index (PI) using the
results obtained from the penetration and softening point tests
according to the proposed equation of the Shell Bitumen Handbook
[1].
PI =
1952 500(Pen
25
) 20SP
50 log(Pen
25
) SP 120
Temperature susceptibility is dened as the change in the consis-
tency parameter as a function of temperature [15]. As illustrated in
Fig. 3, the PI value of virgin bitumen reduces after ageing. In con-
trast the value of PI increased with the addition of waste cooking
oil content into the aged bitumen especially for bitumen with 4% of
WCO. The higher PI value indicates less temperature susceptibility
Fig. 3. Penetration index versus different rejuvenated WCO bitumens (AB: aged
bitumen; VB: virgin bitumen).
Fig. 4. Viscosity versus different rejuvenated WCO bitumens 135

C (AB: aged bitu-

men).
and more rubbery elastic behaviour [16]. However it is noted that
although WCO could modify the temperature susceptibility of aged
bitumen it does not resemble the original bitumen value.
3.4. Viscosity
The viscosity from the rotational viscometer (ASTM D4402) is
the measurement of internal friction of the asphalt [17]. The vis-
cosity for high temperature at 135

C is usually applied to measure

workability, according to the Superpave specication [11], there-
fore the elevated temperature of 135

C was used in this research

for testing. Fig. 4 displays the viscosity of the 40/50 aged bitumen
penetration group with various percentages of waste cooking oil,
which is compared to the original bitumen pen-grade 80/100. As
the graph shows, the age bitumen has a highest viscosity value,
while the addition of 4% waste cooking oil into the aged bitumen
penetration group of 40/50 achieves almost the same viscosity as
the original bitumen. Therefore the same workability is expected
fromrejuvenated bitumen.
3.5. Dynamic shear rheometer test
3.5.1. Complex shear modulus
The rheological diagraminthis researchis focusedonisochronal
plots. Fig. 5 shows the relationship between the complex
Fig. 5. Complex shear modulus versus temperature for different rejuvenated WCO
bitumens (VB: virgin bitumen; AB: aged bitumen).
M. Zargar et al. / Journal of Hazardous Materials 233234 (2012) 254258 257
Fig. 6. Phase angle versus temperature for different rejuvenated WCO bitumens
(VB: virgin bitumen; AB: aged bitumen).
shear modulus (ASTM D-4 Proposal P246) against a range of
temperatures for original bitumen and aged bitumen group 40/50
with the addition of several waste cooking oil contents. From the
illustrated diagram below, it can be summarised that rejuvenated
bitumen is attained when a certain percentage of waste cooking
oil is well blended, thus, the line for the original bitumen and that
of the rejuvenated bitumen line almost overlap. As the tempera-
tures are increased from30

C to 80

C, the complex shear modulus

decreases steadily. As canbe seenfromthe graph, the original value
of bitumen achieved when approximately 3% of waste cooking oil
is added into the aged bitumen group of 40/50.
3.5.2. Phase angle
The relationship between the phase angle (ASTM D-4 Proposal
P246) for original bitumen and aged bitumen group of 40/50 over a
wide range of test temperatures (i.e., 3080

C) with various quan-

tities of waste cooking oil is shown in Fig. 6. Fromthis gure, it can
be seen that aged bitumen have lower phase angle than virgin one.
It implies that ageing leads to a greater increase in storage modu-
lus (G

) than in loss modulus (G

) accordingly leads to have a more

elastic behaviour [18]. The phase angle clearly increases with the
additionof wastecookingoil as theoverall temperatureis increased
correspondingly. From a comparison with the phase angle of the
original bitumen, the phase angle curve of rejuvenated bitumen
is accomplished when 4% waste cooking oil is added. At tempera-
tures of above 65

C, the phase angle value of 90

is attained, thus,
the binder can be considered purely viscous in nature.
3.6. The chemical tests
To assess the chemical changes, the Fourier transform infrared
(FTIR) spectroscopy was applied for virgin, aged and rejuvenated
bitumen and also WCO (Fig. 7). In addition, the asphaltenes and
maltenes content changes (ASTMD 4124) were measured, as illus-
tratedinTable3. Themainchemical reactionthat takes placeduring
ageing is the formation of oxidation products coming from the
asphalt. The bands at 1700 and 1300cm
1
correspond to C O car-
bonyl and S O sulphoxide compounds modes of vibration, respec-
tively. As Fig. 7 illustrates, the increase in intensity of the band from
the C O and S O for aged bitumen correlates with an increase in
content of the most polar components that constitute of higher
molecular size (asphaltenes) [19]. The comparing of asphaltenes
content fromthe fraction of virgin and aged bitumen (Table 3) also
Fig. 7. FTIR analysis of virgin aged and rejuvenated bitumen (VB: virgin bitumen;
AB: aged bitumen; RB: rejuvenated bitumen).
showed the same results [20]. The asphaltenes content increased
from9.23 for virgin bitumen to 10.98 for the aged bitumen.
Moreover, fromcomparingtheFTIRspectrumof therejuvenated
bitumen containing WCO and virgin bitumen it can be seen that
the newabsorption peaks, which appeared at 1744 and 1160cm
1
,
respectively, belong to the ester carbonyl functional groupandC O
stretching. In Comparing with the virgin bitumen, these peaks can
also be found in the FTIR spectra of WCO. In addition, the oxy-
genated function (S Oand C O) peak area intensity of rejuvenated
bitumenshows aslight decreaseincarbonyl peakcomparedtoaged
bitumen. Correlating to the S O intensity, the peak is the same
as aged bitumen. The comparing of asphaltenes content from the
fraction of rejuvenated and aged bitumen (Table 3) also shows the
same reduction of asphaltenes for rejuvenated bitumen. It is clear
that adding WCO can reduce the ratio of asphaltenes to maltenes
but cannot restore this ratio.
3.7. The assessing of virgin and WCO rejuvenated bitumen after
ageing
The susceptibility of virgin bitumen and WCO rejuvenated bitu-
men were evaluated by means of an ageing index, which is dened
as the ratio of a chemical or physical parameter of binder after the
RTFOTageing process, as showninTable 4. It was observedfromthe
penetration, viscosity andG* ratioresults that rejuvenatedbitumen
has less tendency to ageing compared to original bitumen.
In addition, the rejuvenated and virgin bitumen correlated
to chemical changes measured by the asphaltenes and asphalt
volatility ratio. The results illustrated that the changes in the
asphaltenes is higher in virgin bitumen compared to the rejuve-
nated bitumen, after short-term ageing. The same behaviour was
Table 4
Comparing the effect of short-term ageing on related properties of aged and reju-
venated bitumen.
Test properties Aged bitumen Rejuvenated
bitumen
Viscosity (mPa s) 400 432.4
Viscosity ageing index (%) 1.31 1.03
Penetration (0.1mm) 60 67
Softening point (

C) 48.3 48
Loss in penetration 25 14
Complex shear modulus at 64

C 357.25 292.5
Complex shear modulus changes 1.56 1.08
Asphaltenes index 1.030 1.018
Asphalt volatility 0.275 0.174
258 M. Zargar et al. / Journal of Hazardous Materials 233234 (2012) 254258
observed regarding asphalt volatility, in which virgin bitumen has
tendency to evaporate. This can be related to the lower volatility
susceptibility of bio oil [21] that is related to high percentage of
saturated hydrocarbons on chemical component of bio oils.
4. Conclusion
As mentioned earlier, the main purpose was to investigate the
possibility and the effects of waste cooking oil as the rejuvenat-
ing agent for aged bituminous pavement by assessing the physical
properties of bitumen binders. Fromthese preliminary results, the
following conclusions fromthe ndings can be drawn:
1. In this study, waste cooking oil behaved as an antioxidant or
rejuvenator on age-hardened bitumen.
2. By observation of an unconventional ageing method (MIXER), it
canbeconcludedthat 34%wastecookingoil content canrejuve-
natetheagedbitumenof group40/50tomeet all thephysical and
rheological tests to a level that is comparable with the original
80/100 bitumen.
3. Therejuvenatedbitumenhas less tendencytoshort-termageing,
correlated to physical, rheological and chemical ratio, compare
with virgin bitumen.
4. The successful application of WCO as a rejuvenating agent for
aged bitumen will introduces an environmental and economical
solution for reuse of this waste material.
5. Recommendation
This study has shown clearly that the WCO can rejuvenate the
prepared aged bitumen in laboratory but for using the WCO as a
RAP material rejuvenator more investigation on original aged bitu-
minous mixture, extracted fromroads, is needed.
References
[1] . Garcaa, E. Schlangen, M. Ven, G. Sierra-Beltrna., Preparation of capsules
containing rejuvenators for their use in asphalt concrete, J. Hazard. Mater. 184
(2010) 603611.
[2] X. Lu, U. Isacsson, Chemical and rheological evaluation of ageing properties of
SBS polymer modied bitumens, Fuel 77 (1998) 961972.
[3] G. Holleran, T. Wieringa, J. Tailby, Rejuvenation Treatments for Aged Pave-
ments, Transport Research Board, ITRD E215026, 2006.
[4] I. Widyatmoko, Mechanistic-empirical mixture design for hot mix asphalt
pavement recycling, Constr. Build. Mater. 22 (2008) 7787.
[5] J. Shen, S.N. Amirkhanian, B. Tang, Effects of rejuvenator on performance-based
properties of rejuvenated asphalt binder and mixtures, Constr. Build. Mater. 21
(2007) 958964.
[6] F. Xiao, S.N. Amirkhanian, J. Shen, B. Putman, Inuences of crumb rubber size
and the type on reclaimed asphalt pavement (RAP) mixtures, Constr. Build.
Mater. 23 (2009) 10281034.
[7] J. Shen, S. Amirkhanian, J.A. Miller, Effects of rejuvenating agents on superpave
mixtures containing reclaimed asphalt pavement, J. Mater. Civil Eng. 19 (2007)
376384.
[8] . Garcaa, E. Schlangen, M. Ven, Properties of capsules containing rejuvenators
for their use in asphalt concrete, Fuel 90 (2011) 583591.
[9] R. Romera, A. Santamaria, J.J. Pena, M.E. Munoz, M. Barral, E. Garcia, V. Janez,
Rheological aspects of the rejuvenation of aged bitumen, Rheol. Acta 45 (2006)
474478.
[10] L. Talens Peiro, L. Lombardi, G. Villalba, Mndez, I. Gabarrell, X. Durany,
Life cycle assessment (LCA) and exergetic life cycle assessment (ELCA) of
the production of biodiesel from used cooking oil (UCO), Energy 35 (2010)
889893.
[11] Y.R. Kim, Modeling of Asphalt Concrete, ASCE Press United State of America,
2009.
[12] M. Le Guern, E. Chailleux, F. Farcas, S. Dreesen, I. Maibille, Physico-chemical
analysis of ve hard bitumens: identication of chemical species and
molecular organization before and after articial aging, Fuel 89 (2010)
33303339.
[13] J. Shen, S. Amirkhanian, J.A. Miller, Effects of rejuvenating agents on superpave
mixtures containing reclaimed asphalt pavement, J. Mater. Civil Eng. 19 (2007)
376.
[14] C. Ouyang, S. Wang, Y. Zhang, Improving the aging resistance of
styrenebutadienestyrene tri-block copolymer modied asphalt by addition
of antioxidants, Polym. Degrad. Stab. 91 (2006) 795804.
[15] B. Sengoz, G. Isikyakar, Evaluation of the properties and microstructure of
SBS and EVA polymer modied bitumen, Constr. Build. Mater. 22 (2008)
18971905.
[16] N. Dehouche, M. Kaci, K.A. Mokhtar, Inuence of thermo-oxidative aging on
chemical composition and physical properties of polymer modied bitumens,
Constr. Build. Mater. (2011).
[17] J. Read, D. Whiteoak, The Shell Bitumen Handbook, Thomas Telford Services
Ltd., 2003.
[18] X. Lu, U. Isacsson, Effect of ageing on bitumen chemistry and rheology, Constr.
Build. Mater. 16 (2009) 1522.
[19] C. Ouyang, S. Wang, Y. Zhang, Y. Zhang, Improving the ageing resis-
tance of asphalt by addition of zinc dialkyldithiophosphate, Fuel 85 (2006)
10601066.
[20] Z. Feng, Y. Jianying, W. Shaopeng, Effect of ageing on rheological prop-
erties of storage-stable SBS/sulfur-modied, J. Hazard. Mater. 182 (2010)
507517.
[21] I. Gawrilow, Palmoil usage in lubricants, in: 3rd Global Oils and Fats Business
ForumUSA, 2003.