Construction

and Building

Construction and Building Materials 21 (2007) 1899–1908

MATERIALS
www.elsevier.com/locate/conbuildmat

Rheological effects of commercial waxes and polyphosphoric acid

in bitumen 160/220 – high and medium temperature performance
a,*
Y. Edwards , Y. Tasdemir b, U. Isacsson c

a
Division of Highway Engineering, Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden
b
Yozgat Faculty of Engineering and Architecture, Erciyes University, Yozgat, Turkey
c
Division of Highway Engineering, Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden

Revised 17 June 2006; accepted 3 July 2006

Available online 20 September 2006

Abstract

The effects of adding three commercial waxes and a polyphosphoric acid to three bitumens of 160/220 penetration grade were studied
using different types of laboratory equipment, such as Dynamic Shear Rheometer (DSR), Differential Scanning Calorimeter (DSC),
Force Ductilometer (FD) as well as equipment for determining conventional parameters like penetration, softening point and Fraass
breaking point. The paper deals with effects at medium and high in-service temperatures likely to affect the rutting performance of an
asphalt concrete pavement. The results show that magnitude and type of effect on bitumen rheology depend on the bitumen as well as
type and amount of additive used. Bitumen composition was found to be of decisive importance. Adding polyethylene wax or polyph-
osphoric acid especially to a non-waxy bitumen, showed considerable positive effects on the rheological behaviour at medium and higher
temperatures.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Bitumen rheology; Wax; Polyphosphoric acid; Dynamic shear rheometer; Differential scanning calorimeter

1. Introduction aromatic and alicyclic components or heteroatoms show

Natural wax is part of practically all bitumens and may
in different ways affect bitumen properties. Sometimes
commercial wax is added to bitumen (with or without nat-
ural wax) in order to achieve certain properties. This paper
deals with the addition of such commercial waxes to bitu-
men and especially the effects on high and medium temper-
ature performance. Low temperature performance and
effects are dealt with in a separate paper [1].
Often, waxes in bitumen are divided into three general
categories: macrocrystalline, microcrystalline and/or amor-
phous (non-crystalline) wax. Macrocrystalline waxes typi-
cally have about 30 carbon atoms and crystallize in large
crystals. At 40 or higher numbers of carbon atoms, smaller
crystals are formed. Wax with branched carbon chains,
difficulties in crystallizing and are considered as amor-
phous, ductile or elastic [2]. The presence of large crystals
(macrocrystalline wax) in bitumen is considered to be most
problematic. However, bitumen wax generally is micro-
crystalline and/or amorphous, and different bitumens
may contain larger or smaller amounts of wax without
showing any negative effects on the bitumen properties.
In some cases, wax may even show a positive effect on
the bitumen. The parameters controlling the effect of wax
on bitumen are as follows:
 origin, chemical composition and rheological properties
of the bitumen;
 wax content in the bitumen;
 chemical composition and crystalline structure of the
wax.

*
Corresponding author. Tel.: +46 8 7908707; fax: +46 8 4118432. The amount of heteroatoms, alicyclic and aromatic
E-mail address: ylva.edwards@byv.kth.se (Y. Edwards). components in waxes, as well as molecular distribution

0950-0618/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2006.07.012
1900 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908
and carbon chain branching, greatly influence the wax
properties. This is true for natural as well as commercial
waxes. Furthermore, of crucial importance regarding the
effect of wax on bitumen is the temperature range used
and, not least, the definition of wax in the bitumen chosen.
As a rule of thumb, it has been stated that the natural wax
content in bitumen should not be higher than 3% [3].
Crystallizing wax in bitumen may change bitumen prop-
erties in a negative way and give rise to increased sensitivity
to plastic deformation or cracking in asphalt concrete
pavements.
Some waxes crystallize on cooling. The crystallizing
fractions in bitumen may start to form around +80 C
and then precipitate gradually as the temperature
decreases, causing more or less effect on the physical prop-
erties. The crystallization depends on factors like carbon
chain length, temperature, bitumen viscosity and steric
effects [4].
The crystalline parts belonging to the microcrystalline
and macrocrystalline waxes, respectively, show different
melting areas. The branched alkane chains in the micro-
crystalline waxes do not allow any undisturbed formation
of crystal lattice, resulting in lower crystallization and
lower melting temperature. Macrocrystalline waxes
(mainly composed of n-alkanes), the molecule chains of
which are able to line up parallel, can build up a crystal lat-
tice within a higher melting temperature area. In this con-
nection, it should be mentioned that also microcrystalline
waxes with very high melting point area exist, meaning
waxes which on account of symmetric structure can form
a dense packing and high melting crystals [5]. The melting
point of isolated macrocrystalline wax normally lies in the
area of 50–70 C, but drops with 20–30 C when added to
bitumen as a result of mixing effects [6].
Commercial wax is sometimes used as flow improver
(viscosity depressant) in asphalt concrete and mastic
asphalt (Gussasphalt in German). Wax as flow improver
shows a softening effect on the binder and asphalt mix at
higher temperature (above approximately 80 C). The main
purpose of such an addition is to reduce the mixing temper-
ature of the asphalt in order to reduce energy consumption
and emissions (of bitumen smoke and aerosol). Further-
more, lower void content due to improved compaction
should make the pavement more durable. Below the laying
and compaction temperatures, there may be an increase in
viscosity due to wax crystallization, which in turn could
increase the asphalt pavement resistance to plastic defor-
mation. Other asphalt pavement properties such as suscep-
tibility to low temperature cracking, resistance to fatigue
Table 1
Bitumens used in this study
Bitumen Penetration (dmm) Softening point (C)
Non-waxy Venezuelan, NV 173 39
Middle East, ME 170 38
Waxy bitumen, WB 208 38
and adhesion properties may be affected in a negative
way. However, people in favour of this technique are of
the opinion that crack susceptibility at low temperatures,
fatigue resistance and adhesion properties are hardly
affected in any negative way by the flow improver [7,8].
2. Experimental
2.1. Materials
2.1.1. Bitumen
Three different bitumens of the same penetration grade
160/220 were used for the study, one non-waxy and the
other two containing approximately 3.8 and 2.0 wt% natu-
ral bitumen wax, respectively, according to DSC measure-
ments. Characteristics of the bitumens are given in Table 1.
Two of the bitumens are believed to be the same as those
used in an earlier published study by Edwards et al. [9].
2.1.2. Additives
The commercial additives used and their characteristics
are presented in Table 2. They are called S (Sasobit), MW
(Montan Wax), PW (Polyethylene Wax) and PPA (PolyPh-
osphoric Acid) in this paper. Obviously PPA is not a wax.
The reason for using this additive in the study was that the
effect of PPA on binder properties was expected to be sim-
ilar to those of S, MW and PW [10].
S and MW are typical so-called bitumen flow improvers
(viscosity depressants), which are used for asphalt pave-
ments and mastic asphalt to reduce the mixing temperature
and thereby energy consumption and emissions.
Sasobit is an FT-paraffin, which is produced in a so-
called Fischer Tropsch synthesis, where carbon monoxide
is converted into higher hydrocarbons in catalytic hydroge-
nation followed by a distillation process. The end product
consists of mainly hydrocarbon chains with 40–100 carbon
atoms. Addition of Sasobit to bitumen increases the soften-
ing point and the plasticity span of the bitumen consider-
ably according to product information and certain
performed studies [6–8]. The penetration decreases to some
extent. The effect on softening point and penetration
decreases with increasing hardness of the bitumen. Sasobit
melts at about 100 C and with that noticeably reduces the
viscosity of the bitumen, which is considered to be an
advantage, particularly for hard and/or polymer modified
bitumen. Sasobit is completely soluble in bitumen at tem-
peratures above 140 C and is admixed at about 150 C.
Addition of 4% is considered optimal. However, with the
addition of P4% Sasobit, the low temperature properties
PI Wax (wt%) obtained using DSC
1.58 0.0
1.24 3.8
0.68 2.0
 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908 1901

Table 2
Information regarding additives used in this study obtained from product data sheets
Additive Characteristics Value
Sasobit (FT paraffin wax) Congealing point (ASTM D 938) 100 C
Penetration at 25 C (ASTM D 1321) <1 dmm
Penetration at 65 C (ASTM 1321) 7 dmm
Romonta Asphaltan B (Montan wax) Solidification point (Romonta test method W 1.1) 95–105 C
Dropping point (Romonta test method W 1.3) 110–120 C
Viscosity at 120 C (Romonta test method W 7.1.1) 20–200 mPas
Luwax A (Polyethylene wax) Melting point (microscope or DSC) 98–108 C
Congealing point (ASTM D 938) 92–100 C
Penetrometer value at 23 C (ASTM D 1321) 1–2 dmm
Viscosity at 120 C (ASTM D 2126) 950–1550 mm2/s
Density at 23 C (ASTM D 792) 0.91–0.93 g/cm3
Innovalt N200 (Polyphosphoric acid) Specific gravity (25 C) 1.92
Melting point 16–30 C
Viscosity at 25 C 840 cP
Viscosity at 100 C 35 cP

of the bitumen may be affected in a negative way (higher
breaking point according to Fraass) [6].
Montan wax is a fossil ester wax and as such has a more
complicated structure than FT-paraffin. Montan waxes
have been specially modified to make the softening point
of bitumen increase by the addition, but also for the pur-
pose of improving asphalt concrete adhesion properties
[11]. Montan wax, as flow improver for bitumen, is mar-
keted under different names. Asphaltan B, with congealing
point of about 100 C is used for asphalt concrete. Other
MWs are used for mastic asphalt (with higher mixing and
laying temperatures than asphalt concrete).
The polyethylene wax (PW) used in this study is nor-
mally not used as flow improver or modifier in asphalt
mixes. Areas where it has been used are for instance in plas-
tics and polishes, as thickener for lubricating oils and pet-
rolatum and as paraffin wax improver/upgrader.
Finally, polyphosphoric acid (PPA) is a bitumen mod-
ifier used for improving both high and low temperature
performance. The product has been used in the US since
the early 1970s and is supposed to act as a deflocculant of
the asphaltene bitumen fraction (prevent asphaltene asso-
ciation) due to neutralization of polar groups, either by
acid/base neutralization or by esterification [10]. PPA
has been used as a modifier alone or in combination with
polymers. The intention of adding PPA to polymer mod-
ified bitumen is to reduce the polymer content leading to
improved processing conditions, high temperature viscos-
ity and storage stability. However, the mechanism of
chemical modification of bitumen with PPA depends on
the base bitumen and is to a great extent still unknown
[12].
2.2. Preparation of samples
Samples were prepared by adding calculated amount of
additive to approximately 250 g of bitumen, after which the
sample was heated 30 minutes at 155 C. (Prior to this sam-
ple preparation, the original binders were heated in larger
buckets for about 3 h at the same temperature and subdi-
vided.) The samples were then placed in preheated blocks
and homogenized by shaking 90 s. The same treatment
was applied to the base bitumens. Levels of 3 and 6 wt%
wax were used. For polyphosphoric acid the levels were
0.4 and 1 wt%.
Samples were aged using the RTFO (Rolling Thin Film
Oven) test followed by PAV (Pressure Ageing Vessel)
according to SHRP specifications. Ageing in PAV was per-
formed at 90 C.
2.3. Methods of analysis
2.3.1. Dynamic mechanical analysis, DMA
Rheological measurements were performed with temper-
ature sweeps using a rheometer (Rheometrics, RDA II).
Experiments were carried out in the total temperature
range of 30 C to +100 C. For the temperature range
30 to +80 C, parallel plates with 8 mm diameter and
gap of 1.5 mm were used, while for the range 10 to
100 C, the plate diameter was 25 mm and the gap 1 mm.
The temperature sweeps started at the lower temperature
and the temperature was increased by 2 C /min. A sinusoi-
dal strain was applied and the actual strain and torque
were measured. Dynamic shear modulus jG*j, phase angle
d and jG*j/sind were calculated. The frequencies used were
10 rad/s for the temperature range of 30 to +80 C and 1
and 0.1 rad/s for the temperature range +10 to +100 C.
Henceforth in this paper, the dynamic shear modulus jG*j
is called complex modulus G*.
Testing was performed on original samples and after
ageing in RTFO and PAV (at 90 C).
2.3.2. Differential scanning calorimetry, DSC
In DSC-analysis, a small sample is exposed to cooling
and heating cycles, and thermal effects are registered. Such
effects are due to glass transition, melting, dissolution,
1902 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908
crystallization/ precipitation, re-crystallization and other
changes of state.
DSC analysis in this study was performed using a Met-
tler TA3000 system. Approximately 15 mg of bitumen sam-
ple or wax was weighed in an open pan and placed in the
DSC cell under nitrogen blanket. The sample was heated
to +110 C and then cooled at 10 C /min to 110 C, fol-
lowed by heating to +110 C at the same rate. For samples
containing wax S, wax MW or wax PW the heating temper-
ature 160 C had to be chosen for the dissolution to be
completed. The method was used for determining the
DSC wax content of the prepared bitumen/wax samples.
Both cooling and heating cycles were used for calculation
of the amount of crystallizing material (crystallizing mate-
rial in the cooling cycle plus re-crystallizing material in the
heating cycle). Other parameters registered in the analysis
were the starting temperature of crystallization, the wax
melting out temperature, the temperature at exothermic
and endothermic peak heat flow, respectively.
For the calculation of amount of wax, a value of
DH = 121.3 J/g was used. This figure is an estimated aver-
age value developed by Nynäs in the 1980’s for natural wax
in bitumen [13]. However, different types of wax and sam-
ples have different melting enthalpies. The enthalpy value
of a certain wax in bitumen is dependent on bitumen and
differs from the value of the pure wax. For instance, the
enthalpy value of pure n-alkanes in bitumen is higher than
for waxy bitumen in general. The wax additives used in this
study differ in molecular weight distribution and by that
most certainly have different enthalpy values, why the
amounts of crystallized fractions measured with DSC
may differ somewhat from ‘‘expected’’ values. Only original
binder mixes were analyzed.
2.3.3. Empirical binder tests
Empirical binder tests were used as well. These were
softening point (EN 1427), penetration at 25 C (EN
1426) and ductility (EN 13589). Force ductility testing
was performed at +5 C. Test specimens were stretched
up to break or until constant registered zero force. Maxi-
mum load was registered.
Penetration was measured only for original samples.
Other tests were performed for original as well as aged
samples. Penetration Index (PI) was calculated using the
equation developed by Pfeiffer and Van Doormal [14]:
1952  500 log Pen25  C  20SP
PI ¼ ð1Þ
50 log Pen25  C  SP  120
where SP is softening point and Pen25 C penetration at
25 C.
2.3.4. Chemical characterization
Chemical characterization of binder mixes and waxes
were performed using Fourier Transform Infrared (FTIR)
spectroscopy. An FTIR spectrometer, Infinity 60AR
(Mattson resolution 0.125 cm1), was used in characteriz-
ing the mixes before and after ageing. The solutions of
5 wt% binder samples were prepared in carbon disulfide.
Scans were performed using circular sealed cells (ZnSe
windows and 1 mm thickness). All spectra were obtained
by 32 scans with 5% iris and 4 cm1 resolution in wave
numbers from 4000 to 500 cm1. The peaks within the
IR region from 750 to 680 cm1 were used as an indica-
tion of amorphous and/or crystalline structures in the bin-
der, and peak areas were correlated to the determined
amount of crystallizing fraction according to DSC. The
peaks at 1705 and 1030 cm1 were used as an indication
of ageing.
3. Results and discussions
Adding wax additive (S, MW or PW) showed noticeable
stiffening effect at temperatures from about +100 C down
to at least +5 C for all the bitumens studied. This stiffen-
ing effect was demonstrated by DMA temperature sweeps,
decrease in penetration (at +25 C), increase in softening
point and penetration index, as well as force ductility
results (at +5 C).
3.1. Empirical measurements
Adding S showed the highest stiffening effect expressed
in terms of penetration, softening point and force ductility
for the NV and ME bitumens followed by MW and PW.
Adding PPA also made these bitumens stiffer within the
temperature range mentioned, but to a smaller extent.
The effects on empirical measurements of adding S, MW,
PW or PPA to the NV, ME and WB bitumens are reported
in Table 3.
Concerning force ductility maximum load at +5 C,
the highest value was shown for bitumen WB and ME
containing wax S (about 200 and 150 N, respectively,
for the 6 wt% mixtures compared to about 30–40 for
the base bitumens). Also adding wax MW to bitumen
ME showed a large effect, while adding PW or PPA
showed marginal effects. Bitumen NV was somewhat less
affected than bitumen ME or WB. The effects on force
ductility at +5 C are not further discussed in this paper
as the intention is to focus mainly on effects at higher
temperatures.
3.2. DMA measurements
DMA temperature sweeps were performed for bitumen/
additive mixtures over a wide range of temperatures (30
to +80 C) at a frequency of 10 rad/s. The three bitumens,
NV, ME and WB, with 0, 3 and 6 wt% wax S, wax MW or
wax PW were used. Polyphosphoric acid (PPA) was added
to the bitumens NV and ME but in lower levels. In the case
of bitumen WB only 0, 3 and 6 wt% wax S were used (and
for some tests also 6 wt% PW). The results obtained at low
temperatures (65 C) are described in [1].
Rheological behaviour at medium and high tempera-
tures was further studied using temperature sweeps from
 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908 1903

Table 3
Results obtained from conventional test methods
Binder Penetration (dmm) Softening pointa (C) Force ductilitya max. load (N) Force ductility def. energy (J) PI
ME 170 38.9/48.1 32/87 1.1 1.24
ME + 3% S 92 77.5/83.3 73/156 1.7 5.84
ME + 6% S 74 88.3/91.5 148/223 1.9 6.52
ME + 3% PW 129 52.3/54.3 39/95 1.3 2.24
ME + 6% PW 120 54.1/59.2 40/113 1.5 2.42
ME + 3% MW 114 69.8/72.0 86/160 1.4 5.43
ME + 6% MW 87 87.8/84.5 125/– 1.6 6.98
ME + 0.4% PPA 153 40.9/50.7 33/82 1.2 0.81
ME + 1% PPA 131 43.1/53.9 33/80 1.2 0.55
NV 173 38.0/47.5 24/73 1.0 1.58
NV + 3% S 97 81.8/80.5 64/140 1.6 6.61
NV + 6% S 68 95.5/97.3 111/212 1.7 7.06
NV + 3% PW 130 45.9/54.8 34/84 1.2 0.38
NV + 6% PW 104 51.5/64.8 37/109 1.3 1.22
NV + 3% MW 118 69.8/71.3 60/123 1.3 5.57
NV + 6% MW 88 85.0/84.5 84/189 1.3 6.68
NV + 0.4% PPA 147 39.8/50.4 28/78 1.1 1.41
NV + 1% PPA 116 43.3/57.5 26/79 1.2 0.90
WB 208 38.2/45.8 39/109 1.1 0.68
WB + 3% S 111 83.3/87.0 106/201 1.9 7.29
WB + 6% S 67 96.0/99.3 201/209 2.1 7.07
WB + 6% PW 119 61.0/- – – 3.96
a
Performed on non-aged/aged samples (RTFO and PAV).

+10 up to +100 C at a lower frequency (1 rad/s). In some 3.3. DSC measurements

cases also the frequency 0.1 rad/s was used.
Within the temperature range of 30 to +80 C three
different processes may occur; glass transition, wax crys-
tallization and/or gel formation and melting, respectively.
In Fig. 1 the results using bitumen NV with 0 and 6 wt%
of each wax additive and 1.0 wt% of PPA are illustrated
for temperatures P5 C. However, the whole melting area
of wax S and wax MW in bitumen, respectively, is not
covered in the temperature sweeps as the melting temper-
ature for some part of the waxes may exceed 100 C (cf.
Table 2).
1.E+09
Non-waxy Venezuelan
aged
1.E+08
1.E+07
The effects due to wax content in bitumen shown in
DMA temperature sweeps may be well related to the corre-
sponding effects shown in DSC thermograms [9]. However,
DSC curves from bitumens are rather complicated, since
there may be several overlapping phenomena to consider.
The glass transition of bitumen occurs over a large temper-
ature range due to the complex mixture of different mole-
cules. Starting at a lower temperature range of the heat
flow diagram, the glass transition shows as a shift in spe-
cific heat versus temperature. Diagrams showing the heat
flow for bitumen NV containing 6 wt% of wax S, MW
and PW, respectively, are given in Fig. 2.
90
80
Non-waxy Venezuelan
70
60
Phase Angle, Deg

1.E+06 50
G*, Pa

Heat Flow

1.E+05 40
NV
G*
NV+6%S 30
1.E+04
NV+6%PW 20
NV
1.E+03 NV+6%MW
10
NV+6%S
NV+1%PPA
1.E+02 0 NV+6%PW
5 15 25 35 45 55 65 75
NV+6%MW
Temperature, οC

-70 -50 -30 -10 10 30 50 70 90 110 130

Fig. 1. Effect on complex modulus and phase angle (frequency 10 rad/s) of ο
Temperature, C
non-waxy bitumen NV due to addition of 6 wt% commercial wax or
1.0 wt% polyphosphoric acid. The bitumen mixes were aged in RTFO and Fig. 2. Heat flow by DSC, showing the melting process of bitumen NV
PAV. containing 6 wt% wax S, MW and PW, respectively.
1904 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908

The glass transition may be followed by a weak exother-
mic effect caused by the cold crystallization of wax, which
could not crystallize through the cooling cycle due to lim-
ited mobility. This effect did not occur for the bitumen
NV/wax mixes in Fig. 2, but for all bitumen ME/wax mixes
(as well as for the WB/wax S mixture) in this study. Con-
sequently, all three commercial waxes crystallized through
the cooling cycle and did not show any ‘‘additional’’ exo-
thermic effect in the heating cycle due to re-crystallization.
However, the amount of re-crystallizing material in the ME
mixes containing wax PW were somewhat smaller than in
the ME mixes containing wax S or wax MW, indicating
a certain effect on the re-crystallizing part of the natural
wax due to the addition of wax PW. The mixtures contain-
ing PPA did not show any additional thermal effects due to
the presence of this additive.
A broad endothermic effect may also be observed in the
DSC heat flow diagram due to the melting of crystallizing
fractions or other phenomena. At around 60–90 C, natu-
ral bitumen wax is normally completely melted out. How-
ever, for the commercial waxes used in this study the
melting out temperatures of the bitumen/wax mixes were
higher (between approximately 100 and 130 C). Results
obtained from the DSC diagrams and calculations are
shown in Table 4. Based on the results presented in Table
4, the following comments can be given:
The determined crystallizing fraction (CF) by DSC was
higher than ‘‘expected’’ (natural wax content by
DSC + added amount of wax) for all mixtures containing
wax S, which could mainly be explained by the fact that
the same enthalpy value was used for all samples. For
instance, adding 6 wt% wax S to the non-waxy bitumen
NV gave a CF value of 10.5. Mixtures containing wax
PW, on the other hand, showed lower values and mixtures
containing wax MW approximately ‘‘expected’’ values. As
mentioned earlier, the mixtures containing PPA did not
show any additional thermal effects due to the presence
of this additive.
Depending on molecular weight distribution, the wax
melting temperature range differed between different mixes
and was much broader for wax MW and wax S than for
wax PW. This is clear from Fig. 2 and Table 4.
3.4. Possible relationships between DSC and empirical
testing
Possible relationships between DSC and empirical test-
ing results obtained for the binder mixes in this study were
investigated. The best correlation was found between tem-
perature at exothermic peak heat flow and penetration
index PI (R2 = 0.92) or softening point (R2 = 0.86). Deter-
mined amount of crystallizing fraction by DSC could best
be correlated to force ductility maximum load at +5 C
(R2 = 0.72). The samples showing no thermal effects by
DSC were deleted.
The penetration index is frequently used to give an
approximation of the expected temperature susceptibility
for bitumen. The value of PI for base penetration bitumens
normally ranges from about 3 (for highly temperature
susceptible bitumens) to about +7 for highly blown (low-
temperature susceptible) bitumens [14]. In this study the
highest values (around 7) were obtained by the addition

Table 4
Results from DSC diagrams and calculations
Binder Cryst. CF at Re-cryst. fraction Melting fraction Wax melted out Temp. at Temp. at
starting exotherm. at endotherm. at endotherm. temp. (C) exotherm. peak endotherm. peak
temp. (C) region (%) region (%) region (%) heat flow (C) heat flow (C)
ME 41 3.4 0.5 3.8 86 25 14
+3% S 80 7.6 0.5 8.2 116 67 102
+6% S 87 11.7 0.6 12.3 117 77 104
+3% PW 69 4.1 0.2 4.3 107 44 90
+6% PW 79 7.1 0.2 7.3 108 57 90
+3% MW 83 5.9 0.3 6.2 125 74 90
+6% MW 91 9.7 0.4 10.1 126 81 111
+0.4% PPA 41 3.4 0.5 3.9 86 26 27
+1% PPA 43 3.2 0.5 3.7 88 26 38
NV nd 0.0 0.0 0.0 nd nd nd
+3% S 80 4.0 0.0 4.0 110 66 100
+6% S 86 10.5 0.0 10.5 114 77 102
+3% PW 46 2.2 0.0 2.3 104 38 87
+6% PW 74 5.3 0.0 5.2 109 53 87
+3% MW 83 2.6 0.0 2.7 123 74 107
+6% MW 89 5.9 0.0 6.1 122 81 109
+0.4% PPA nd 0.0 0.0 0.0 nd nd nd
+1% PPA nd 0.0 0.0 0.0 nd nd nd
WB 44 1.4 0.7 2.0 82 32 21
+3% S 81 6.3 0.5 6.8 115 68 101
+6% S 87 10.7 0.5 11.3 119 77 104
nd = Not detectable.
 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908 1905

of wax S and wax MW. However, the PI system uses the containing 1% PPA. Carbonyl absorbance was decreased
change in bitumen properties over a relatively small tem- for bitumen ME due to the addition of wax or PPA,
perature range, in this study from +25 up to +100 C. Also but increased for bitumen NV. Comparing ratios of car-
the registered temperatures at exothermic peak heat flow bonyl absorbance of the aged to original binder mix,
by DSC were within this range. NV showed higher resistance to ageing than bitumen
ME originally. All NV mixes showed lower IR absor-
3.5. Possible relationships between DSC and chemical bance ratio of aged to unaged binder than the original
characterization by FTIR NV bitumen, indicating inhibited formation of bitumen
carbonyl compounds.
Comparing CF by DSC to peak area within the FTIR
region from 750 to 680 cm1 gave a correlation value of 3.6. Rheological effects at medium and higher temperatures
R2 = 0.66 if all determined CF results were included. How-
ever, if comparing the results of one base bitumen at a time, The DMA results and calculations in this study show
the correlation improved (R2 P 0.90). The reason for using that bitumen containing natural wax (ME and WB) both
this wavelength range was that methylene groups directly showed lower value for the rutting resistance parameter
bonded to each other (straight chains) absorb there. Peaks G*/sind at for instance 60 C according to SHRP specifi-
at 720 cm1 and 730 cm1 are typical of long straight meth- cations than the non-waxy bitumen NV. This means that
ylene chains and branched methylene chains may absorb at the latter may be less sensitive to rutting, originally. Add-
735 cm1 [15]. ing wax S to ME or WB increased the value of this
As earlier mentioned, binder mixes were characterized parameter, although more for ME than for WB. Adding
before and after ageing using FTIR. Values of IR absor- wax PW to ME showed approximately the same positive
bance (peak area) at wave number 1705 (from 1720 to effect as wax S, while adding wax MW showed marginal
1660 cm1) and 1030 (from 1060 to 1000) were determined. effect. In the case of bitumen NV, adding wax PW made
Peaks at these wave numbers represent bitumen carbonyl quite a difference for the rutting resistance parameter
compounds and sulfoxides, respectively, and are often used (increase from 877 to 2439 Pa), while adding wax MW
to characterize bitumens and bitumen ageing. Determined even showed negative effects in this sense. This is easily
values are shown in Table 5. understood when comparing melting effects of NV/wax
Adding wax or PPA did not increase the sulfoxide mixes according to Fig. 2 and Table 4. At 60 C, melting
absorbance (formation) for any of the aged mixes tested. of wax PW in the NV/PW mix hardly started, while for
The lowest (most favourable) ratios of absorbance of the wax MW in the NV/MW mix melting started already
aged to original binder mix were observed for the mixes below +30 C. Also adding PPA showed a positive effect
on the rutting resistance parameter for bitumen ME and
NV. Consequently, the upper limit temperature (at which
Table 5 G*/sind = 1 kPa) was improved accordingly, meaning that
IR absorbance of carbonyl compounds and sulfoxides the highest upper limit temperature was achieved by add-
Binder 1705 cm1 1030 cm1 ing wax PW or PPA to the non waxy bitumen NV. Effects
Original Aged Original Aged on G*/sind and upper limit temperature are shown in
ME 0.86 2.25 0.96 2.65 Table 6.
ME + 3% S 0.64 2.05 0.82 2.52 G* and d are used in two ways in the SHRP specifica-
ME + 6% S 0.63 1.91 0.76 2.29 tions. Permanent deformation is controlled by limiting
ME + 3% PW 0.65 2.03 0.90 2.45 G*/sind to at least 1.0 kPa before ageing in RTFO and
ME + 6% PW 0.63 2.02 0.87 2.49
PAV and at least 2.2 kPa after ageing. A better indicator
ME + 3% MW 0.78 2.11 0.95 2.48
ME + 6% MW 0.77 2.16 0.88 2.50 for rutting could be the zero shear viscosity (ZSV), or
ME + 0.4% PPA 0.58 1.90 0.80 2.12 rather low shear viscosity, defined as the limiting value of
ME + 1% PPA 0.55 1.74 1.15 1.94 the viscosity function for ‘‘infinitely low’’ shear rates [16].
NV 4.01 6.48 0.85 1.66 The correlation between ZSV and asphalt rutting has been
NV + 3% S 4.13 6.37 0.77 1.53 shown for penetration grades and modified bitumens
NV + 6% S 4.57 6.15 0.90 1.42 [17,18]. However, measuring difficulties may occur for
NV + 3% PW 5.07 6.63 0.83 1.62 highly modified and/or waxy bitumens [19], and ZSV was
NV + 6% PW 4.91 6.99 0.82 1.63
NV + 3% MW 4.31 6.61 0.81 1.53
therefore not used in this study.
NV + 6% MW 4.41 6.76 0.81 1.54 Yet another suggested factor for rutting sensitivity is the
NV + 0.4% PPA 4.17 6.08 0.69 1.66 slope of the logarithmic function of the complex modulus
NV + 1% PPA 4.24 5.60 0.91 1.45 between +25 C and +60 C [9]. Such slope values for the
WB nd 2.81 0.79 2.19 complex modulus between these two temperatures based
WB + 3% S nd 2.20 0.78 1.94 on the DMA temperature sweeps at 10 rad/s and 1 rad/s
WB + 6% S nd 2.05 0.87 1.79 for original samples were performed in the study. The
nd = Not detectable. slopeT1T2 is given as
1906 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908

Table 6
Effects on rutting factors by DMA
Binder G*/sind at 60 C (Pa) Upper limit temp., G*/sind = 1 kPa (C)
10 rad/s 1 rad/s 10 rad/s 1 rad/s
Orig. Aged Orig. Aged Orig. Aged Orig. Aged
ME 670 2125 79.6 249.2 57.2 65.6 43.4 51.2
ME + 3% S 1245 2546 117.4 317.3 61.5 66.8 46.4 52.6
ME + 6% S 1188 3054 184.8 511.3 61.6 67.9 49.4 55.8
ME + 3% PW 1083 2987 146.8 461.8 60.6 68.9 46.2 54.4
ME + 6% PW 1475 4891 436.2 1104.2 63.1 72.7 51.0 60.8
ME + 3% MW 812 1979 91.1 258.8 58.5 64.9 44.9 51.6
ME + 6% MW 892 2372 111.5 287.0 59.2 65.9 46.4 52.7
ME + 0.4% PPA 961 3173 118.4 419.9 59.7 68.9 46.2 54.4
ME + 1% PPA 1311 5253 174.8 822.8 61.9 73.8 48.6 58.5
NV 877 3074 100.6 369.4 59.1 68.6 44.7 53.6
NV + 3% S 1078 3942 131.6 408.2 60.6 69.4 46.5 54.3
NV + 6% S 1821 4344 173.7 549.6 64.1 70.0 48.6 56.2
NV + 3% PW 1615 4949 252.9 733.1 64.6 73.2 48.6 57.7
NV + 6% PW 2439 8298 580.5 2054.1 68.0 77.0 53.2 67.5
NV + 3% MW 837 2837 104.5 331.1 58.8 67.5 45.4 53.1
NV + 6% MW 818 2906 120.3 427.8 58.6 67.2 46.9 54.8
NV + 0.4% PPA 989 4747 136.7 587.7 61.0 72.3 46.4 56.6
NV + 1% PPA 1791 10166 244.6 1549.4 64.5 79.9 50.6 63.2
WB 383 1187 49.5 136.8 54.0 61.2 40.5 47.7
WB + 3% S 548 1276 69.2 164.5 55.4 61.7 42.9 48.8
WB + 6% S 657 1475 98.7 223.0 57.0 62.7 45.0 50.7
WB + 6% PW 1292 – 855.1 – 61.7 – 57.7 –

logðG ðT 2ÞÞ  logðG ðT 1ÞÞ
ð2Þ
ðT 2  T 1Þ
where G*(T2) and G*(T1) is the complex modulus at tem-
perature T2 and T1, respectively.
The results from temperature sweeps at 10 rad/s are
given in Table 7. The negative slope2560 value was typi-
cally somewhat higher for the samples with wax S or
MW than for samples with wax PW or PPA. Adding
wax S or MW typically made the negative slope value
increase with increased wax content, indicating higher tem-
perature sensitivity, while adding PW or PPA showed the
opposite effect. Ranking and effects were the same also
for temperature sweeps at 1 rad/s and for aged samples.
The decrease in phase angle for all bitumens containing
wax or PPA indicates higher elasticity, starting already at
low temperatures (cf. Fig. 1). This indicates that the addi-
tives used may form a kind of crystal, gel or network struc-
ture in the binder. When comparing DMA analysis at a
lower frequency of 1 rad/s or 0.1 rad/s this becomes even
more evident. Particularly this is true for samples contain-
ing wax PW in this study.
The diagrams showing effects in the temperature range
from +10 C to +100 C at lower frequency (1 rad/s) are
presented in Fig. 3 for NV mixtures containing 6 wt%
wax or 1 wt% PPA. The diagrams show that the decrease
in phase angle (increased elasticity) for bitumen samples

Table 7
Effects on rutting factor slope2560 value by DMA, original mixes
Added wt% ME NV WB
wax
S2560 G* (25 C) G* (60 C) S2560 G* (25 C) G* (60 C) S2560 G* (25 C) G* (60 C)
· 102 · 105 · 102 · 102 · 105 · 102 · 102 · 105 · 102
S 0 6.92 1.8 6.8 6.77 2.1 8.8 7.32 1.4 3.8
3 7.01 3.5 12.4 6.83 2.7 10.8 7.34 2.0 5.5
6 7.18 3.9 11.9 6.58 3.7 18.2 7.36 2.5 6.6
PW 3 6.78 2.5 10.8 6.32 2.6 16.0 – – –
6 6.60 3.0 14.7 6.10 3.2 23.7 6.52 2.4 12.6
MW 3 7.34 3.0 8.1 6.87 2.1 8.4 – – –
6 7.41 3.5 8.9 6.89 2.1 8.3 – – –
PPA 0.4 6.74 2.2 9.6 6.54 2.2 11.5 – – –
1 6.52 2.5 13.0 6.23 2.7 17.7 – – –
 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908 1907

1.E+09 90 1.E+09 90

1.E+08 80 1.E+08 80
Non-waxy Venezuelan
1.E+07 70 1.E+07 70

Phase Angle [Deg]

1.E+06 60

Phase Angle [Deg]

1.E+06 60

G* [Pa]
1.E+05 50
1.E+05 50
G* [Pa]

G*
1.E+04 40
1.E+04 40
G*
1.E+03 30
1.E+03 NV 30
NV+6%S 1.E+02 20
1.E+02 NV+6%PW 20 unaged NV+6%PW
1.E+01 10
1.E+01 NV+6%MW 10 RTFOT+PAV aged NV+6%PW
NV+1%PPA 1.E+00 0
1.E+00 0 10 20 30 40 50 60 70 80 90 100
10 20 30 40 50 60 70 80 90 100 ο
Temperature [ C]
ο
Temperature [ C]
Fig. 4. Effect on complex modulus and phase angle (frequency 1 rad/s) of
Fig. 3. Effect on complex modulus and phase angle (frequency 1 rad/s) of non-waxy bitumen NV due to addition of 6 wt% commercial wax PW
non-waxy bitumen NV due to addition of 6 wt% commercial wax or before and after ageing in RTFO and PAV.
1.0 wt% polyphosphoric acid. The bitumen mixes are original mixes (not
aged in RTFO and PAV).

1.E+09 90
containing wax PW was more evident at the lower fre-
1.E+08 80
quency (cf. Fig. 1). For NV samples containing wax PW,
there was a large decrease of the phase angle prior to the 1.E+07 70

melting of the wax. This very pronounced effect appeared

Phase Angle [Deg]

1.E+06 60

between 50 and 100 C. The corresponding strong effect

G* [Pa]

1.E+05 50
was seen also at the higher frequency (10 rad/s), although 1.E+04 40
G*
not so pronounced (cf. Fig. 1), as well as at the lower fre-
1.E+03 30
quency of 0.1 rad/s. A corresponding plateau effect ME+6%PW
1.E+02 20
appeared very clearly for the complex modulus, especially NV+6%PW
1.E+01 10
at the frequency of 1 rad/s. This is a desirable phenomenon WB+6%PW

and an indication of improved elasticity possibly resulting 1.E+00

10 20 30 40 50 60 70 80 90 100
0

in an improved resistance to deformation of an asphalt ο

concrete. SBS polymer modification may show the same
kind of rheological effects [20]. Ageing (RTFOT and
PAV) showed a stiffening effect by increasing the dynamic
modulus and flattening out the plateau effect for the mod-
ulus. A corresponding decrease was registered for the phase
angle up to about 60 C. At higher temperatures than that,
the effect due to increased elasticity from adding wax PW
was markedly reduced, probably due to thermal degrada-
tion of the PW wax during ageing. This is illustrated in
Fig. 4.
ME samples containing wax PW showed similar effects
but to a lower degree. Adding wax PW to bitumen WB
showed this effect as well, but over a wider temperature
range. These results are illustrated in Fig. 5.
The reason for wax PW showing this effect on the bitu-
mens studied may partly be explained by its melting tem-
perature area (cf. Fig. 2), which for PW in bitumen is
typically much narrower than for wax S and wax MW.
From Fig. 2 it can be seen that the melting temperature
range of PW in bitumen started at about +50 C and ended
at about 100 C, while for S and MW the corresponding
ranges were much broader. Furthermore, polyethylene
could be classified as a thermoplastic polymer (together
with other thermoplastics like polypropylene, polystyrene
and ethylene vinyl acetate (EVA)). According to Shell Bitu-
men Handbook [14], non-rubber thermoplastics like poly-
Temperature [ C]
Fig. 5. Complex modulus and phase angle (frequency 1 rad/s) of unaged
bitumen mixes containing 6 wt% PW.
ethylene and EVA do not significantly increase the
elasticity of the bitumen and when heated may separate.
(EVA is the most frequently used thermoplastic in road
binders.) However, in the case of wax PW (Luwax A), in
this study binder elasticity was clearly improved.
4. Conclusions
The rheological effects at high and medium temperature
of adding commercial waxes and polyphosphoric acid (cf.
Table 2) to bitumen of penetration grade 160/220 were
studied using DMA, DSC and empirical methods. Based
on the results obtained in this study, the following conclu-
sions can be drawn:
 Magnitude and type of effect on bitumen rheology
depend on the bitumen itself as well as type and amount
of additive. Bitumen composition is of decisive
importance.
 Adding wax S to the bitumens shows the highest
stiffening effect expressed in terms of empirical param-
eters (softening point, penetration at 25 C and force
1908 Y. Edwards et al. / Construction and Building Materials 21 (2007) 1899–1908
ductility at +5 C), but not in terms of rutting factors
by DMA (such as G*/sind at 60 C and upper limit
temperature).
 Temperature sweeps show the highest stiffening effects
from adding wax PW or PPA in the temperature range
from about +25 C to +90 C. Additionally, the
slope2560 value for the logarithm of the complex mod-
ulus indicates higher temperature sensitivity for bitumen
containing wax S or wax MW than for bitumen contain-
ing wax PW or PPA. The high effect from adding wax
PW may partly be explained by its more narrow melting
temperature range in bitumen compared to bitumen
containing wax S or wax MW, as well as its ability to
form an elasticity improving crystal and/or gel network.
Comparing the results of temperature sweeps with melt-
ing effects determined by DSC gives a good indication
concerning stiffening effects of this kind. Bitumen con-
taining PPA showed no thermal effects by DSC.
 None of the additives (waxes or PPA) shows any nega-
tive sudden complex modulus lowering effect at higher
temperature, thereby possibly affecting rutting resis-
tance, as for waxes containing n-alkanes. Stiffening
effects solely occur at temperatures below +90 C. How-
ever, at temperatures higher than 90 C, wax S and wax
MW, being used as so-called flow improvers, show vis-
cosity lowering effects due to high melting temperatures
of some part of these waxes. However, such effects were
not investigated in this study.
 Adding polyethylene wax or polyphosphoric acid, espe-
cially to the non-waxy bitumen, shows considerable
positive effects (increased stiffness) on the rheological
behaviour at medium and higher temperatures. Further
studies will be performed on asphalt mixes containing
bitumen with this polyethylene wax.
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