J Therm Anal Calorim (2016) 124:729–741
DOI 10.1007/s10973-015-5198-4
The research for crumb rubber/waste plastic compound modified
asphalt
Feng Zhang1 • Changbin Hu1
Received: 10 August 2015 / Accepted: 6 December 2015 / Published online: 22 December 2015
Ó Akadémiai Kiadó, Budapest, Hungary 2015
Abstract Crumb rubber (CR)/waste plastic compound
modified asphalts were prepared by the addition of CR and
waste plastic including waste polypropylene, low-density
polyethylene, linear low-density polyethylene (LLDPE).
The physical properties of each modified asphalt were
studied and compared, and LLDPE was confirmed as the
right modifier in enhancing the high-temperature perfor-
mance. Meanwhile, dioctyl phthalate (DP) as a plasticizer
was used further in improving low-temperature properties.
On the basis of the optimal proportion of CR/LLDPE/DP
modified asphalt, rheological tests were used to study the
high- and low-temperature properties and structural char-
acteristics of modified binder. Fourier transform infrared
spectroscopy was used to investigate the modification
mechanism of each modifier. Morphology observation was
used to study the effect of modifier and ageing on the
morphological characteristics of asphalt. Thermal analysis
was adopted to study the thermodynamic characteristics
and constituents of each modified binder.
Keywords Asphalt
CR
LLDPE
DP
Introduction
Asphalt as the binder of aggregate has been widely used in
road pavement. Unfortunately high-temperature rutting and
low-temperature cracking of asphalt cement or coating
layer due to the severe temperature susceptibility limit its
& Feng Zhang
wucifanying@163.com
1
Department of Civil Engineering, Fu Zhou University,
Fu Zhou 350108, People’s Republic of China
further application. Therefore, it is necessary to modify
asphalt. Among the modifiers of asphalt, CR and waste
plastics are widely used in road pavement [1].
CR as a waste is widely used in asphalt modification.
The research and application for CR modified (CRM)
asphalt can be dated back to several decades ago in the
USA, Canada and other countries [2–4]. The past research
and application showed that CRM asphalt had some good
characteristics such as higher softening point, reduced
fatigue/reflection cracking, improved durability and lower
pavement maintenance costs [5–7]. In recent years, with
the rapid development of automobile industry, the volume
of scrap tires also increased quickly, and the use of CR is
very significant in environmental protection and waste
recycle [8].
Waste polyethylene (PE) is also used in asphalt modi-
fication for a long period of time. Generally, the waste PE
used in asphalt modification includes LDPE and LLDPE,
and it has been found that the use of waste PE improved the
high-temperature performances of asphalt and declined the
temperature susceptibility greatly [9–12]. Nevertheless, the
low-temperature performance and compatibility of PE
modified asphalt were still not good, which blocked the
application to some extent [13, 14].
The compound modification of PE and CR for asphalt is
reported in some publications. Fang et al. [15] studied the
proportion and properties of PE/CR modified asphalt;
however, both the kinds of modifiers and research extent
are very limited. Yan et al. [16] investigated the effect of
PE or CR content on the physical and rheological proper-
ties of asphalt; however, the research is not detailed and no
structural research is concerned. Wang and Ouyang sug-
gested the compound use of graft LLDPE, CR, high-den-
sity polyethylene (HDPE) in asphalt and implied that the
compatibility between polymer and asphalt was improved
123
730
further by graft reaction [17]. Nevertheless, the graft PE is
difficult to be prepared in the large production of polymer
modified asphalt (PMA). Moreover, the improvement for
the low-temperature properties of CR/PE modified asphalt
is not concerned and the poor low-temperature perfor-
mance as the major lack hinders the application to some
extent. Besides, the used PE in these studies is a product
not waste, and actually the study and recycle for waste PE
are more significant. With the development of plastics
industry in China, the recycle for waste PE is being paid
more attention.
In this paper, we made a systemic study for CR/waste
plastic modified asphalt. CR with different meshes and
waste plastics such as LDPE, LLDPE and PP were used in
the preparation of modified binders, and the detailed study
for the physical properties was made. Finally, the propor-
tion for CR/waste plastic modified asphalt was optimized,
and the improvement for the low-temperature property was
made further. On the basis of the optimized proportion,
different analysis ways including rheological test, mor-
phology observation, FTIR and thermal analysis were used
to investigate and compare the structural characteristics of
modified binder before and after ageing.
1. Rheological testing was used to investigate the effect
of modifier and ageing on the rheological behaviour
and structural characteristics of asphalt by comparing
master curves.
2. Morphology observation was used to study the mor-
phological characteristics of binder and the compati-
bility between polymer and asphalt after ageing or
modification.
3. FTIR test was used to investigate the effect of modifier
and ageing on the distribution of the major functional
groups of modified asphalt.
4. Thermal analysis was used to evaluate the thermal
stability of each binder. The effect of modifier and
ageing on the structural characteristics of binder was
studied further by comparing the thermodynamic
parameters and enthalpy curves.
Materials and measurements
Materials
Hulian-70 paving asphalt was obtained from the Fuzhou
Petroleum Asphalt Factory, China. The general CR
(80 mesh) was tyre crumb rubber from Haihong Rubber
Factory, China, and the physical properties and chemical
compositions are listed in Table 1. The basic properties of
waste plastic including LLDPE, LDPE and PP are listed in
123
F. Zhang, C. Hu
Table 2. Plasticizers are DP and furfural extract oil (FEO).
DP is chemically pure reagent and was produced by
Puyang Petrochemical Co., Ltd., China. FEO is technically
pure reagent, and the major constituent is arene.
Preparation of samples
The modified asphalts were prepared using a high shear
mixer (made by Qishuang Machine Co., Ltd., China).
Firstly, asphalt (300 g) was heated until it became fluid in
an iron container; then, upon reaching about 180 °C, CR
powder (80 mesh, based on 100 parts asphalt) was added.
The shearing time was 1 h, and then, the modifiers (based
on 100 parts asphalt) were added, heated until reaching
about 180 °C and sheared 1 h at the shearing speed of
4500 r min-1; subsequently, the blend was stirred by a
mechanical stirrer at 180 °C for 2 h to make sure the fully
swelling of the modifiers in the asphalt. After that, the
preparation has been finished. The proportion for each
modified binder is listed in Table 3.
The ageing of modified asphalt
The ageing of modified polymer asphalt was performed
using the thin-film oven test (TFOT, ASTM D 2872) and
simulates the changes in the properties of asphalt during
the hot mixing and the lay down process.
Physical properties test
The physical properties of asphalts, including softening
point, penetration, toughness and tenacity, ductility and
flexibility and elastic recovery, were tested in accordance
with ASTM D 36, D 5, D 5801-95, D113 and D 6084-97,
respectively.
Storage stability test
The storage stability of modified asphalts was measured as
follows. The sample was poured into an aluminium
toothpaste tube (32 mm in diameter and 160 mm in
height). The tube was sealed and stored vertically in an
oven at 163 °C for 48 h, then taken out, cooled to room
temperature and cut horizontally into three equal sections.
The samples taken from the top and bottom sections were
used to evaluate the storage stability of a polymer modified
asphalt (PMA) by measuring their softening points. If the
difference of the softening points between the top and the
bottom sections was less than 2.5 °C, the sample was
considered to have good high-temperature storage stability.
If the softening points differed by more than 2.5 °C, the
PMA was considered unstable.
The research for crumb rubber/waste plastic compound modified asphalt 731

Table 1 Physical properties and chemical compositions of crumb In each test, about 1.0 g of sample was applied to the
rubber bottom plate, covering the entire surface, and the plate was
Physical properties Density ratio/g cm-3 1.13 then mounted in the rheometer. After heating to the soft-
Moisture content mass/% 0.55 ening point of the binder, the top plate was brought into
Break strength/MPa 9.0 contact with the sample, and the sample was trimmed. The
Elongation at Break/% 460.0 actual strain was measured to calculate various viscoelastic
Chemical Ash content mass/% 3.8 parameters such as complex modulus (G*) and phase angle
compositions Acetone extract mass/% 12.1 (d). All tests were performed within the linear viscoelastic
Carbon black content mass/% 29.7 range of the sample.
Rubber hydrocarbon content mass/ 59.6
% Morphology observation

The sample morphology was observed using an optical

Table 2 Basic properties of waste plastic microscope made by Nikon Co., Japan. Squashed slides of
Softening point/ Density/ Tensile strength/ modified binders were prepared using very small amounts
°C g cm-3 MPa of the heated sample and viewed under the microscope at a
magnification of 400.
LLDPE 101 0.92 46
LDPE 85 0.92 8.96
Fourier transform infrared (FTIR) spectroscopy
PP 79 0.9 32

A FTIR spectrometer, infinity 60 AR (Mattson, resolution

Rheological characterization
A strain-controlled dynamic shear rheometer (DSR, Anton
Paar, MCR 102, Germany) with parallel plate geometry (25
or 8 mm in diameter) was used to determine the rheolog-
ical behaviour of asphalts.
Temperature sweeps (high-temperature range 30–140 °C,
25-mm parallel plate, 1-mm gap; low-temperature range
-15 to 30 °C, 8-mm parallel plate, 2-mm gap) with 2 °C
increments were applied at a fixed frequency of 10 rad s-1
and variable strain.
0.125 cm-1), was used to determine the functional char-
acteristics of modified binders before and after ageing in
wavenumbers ranging from 400 to 4000 cm-1. Binders
were dissolved in chloroform with 10 mass/% concentra-
tion, then dropped onto KBr table and dried for the FTIR
analysis.
Thermal analysis
Thermal analysis was performed using a TA Instrument,
model SDT 2960, under argon atmosphere, sample mass
around 7–10 mg, with a constant heating rate of

Table 3 Proportion for CR/waste plastic modified asphalt

AH-70 CRM CRPM CRLM CRLLM CRLLM2 CRLLDM CRLLFM

CR mass/% 0 15 13 13 13 13 13 13
PP mass/% 0 0 2 0 0 0 0 0
LDPE mass/% 0 0 0 2 0 0 0 0
LLDPE mass/% 0 0 0 0 2 4 2 2
FEO mass/% 0 0 0 0 0 0 0 0.5
DP mass/% 0 0 0 0 0 0 0.5 0
AH-70: Fuzhou 70# base asphalt
CRM: CR modified asphalt
CRPM: CR/waste PP modified asphalt
CRLM: CR/waste LDPE modified asphalt
CRLLM and CRLLM2: CR/waste LLDPE modified asphalt
CRLLDM: CR/waste LLDPE/DP modified asphalt
CRLLFM: CR/waste LLDPE/FEO modified asphalt
FEO: Furfural extract oil
CR: 80 mesh crumb rubber

123
732 F. Zhang, C. Hu

Table 4 Physical properties of base and CRM asphalts

AH-70 CRM/40 CRM/80 CRM/120

Softening point/°C 49.1 58 56.4 53

Penetration/25 °C/0.1 mm 61.0 36.5 38.7 40.5
Viscosity/135 °C/Pa s 0.77 5.6 4.2 3.8
/177 °C/Pa s – 1.12 0.99 0.85
Ductility/5 °C/cm 0 5.3 9.9 10.3
Flexibility/5 °C/cm/N 0 0.09 0.14 0.2
Toughness/25 °C/N m 5.1 16.1 15.2 14.9
Tenacity/25 °C/N m 0 4.2 5.1 5.4
Elasticity/25 °C/%/3 min 10 60 42 38
/25 °C/%/1 h 18.5 92 83 75
Softening point difference/°C – -7.1 -2.4 -1.2
After TFOT ageing
Softening point/°C 54.3 67.8 62.6 57.9
Penetration/25 °C/0.1 mm 34 30.7 36.3 41
Ductility/5 °C/cm 0 6.2 7.9 8.3
Flexibility/5 °C/cm/N 0 0.053 0.076 0.087
Toughness/25 °C/N m 8.9 17.3 14 14.5
Tenacity/25 °C/N m 0 3.1 4.6 4.3
Elasticity/25 °C/%/5 min 7 62 62 41
/25 °C/%/1 h 28 80 77 65

Table 5 Physical properties of CR/waste plastic modified asphalts

CRPM CRLM CRLLM CRLLM2

Softening point/ °C 55.2 56.3 60.3 62.9

Penetration/25 °C/0.1 mm 47.2 45.1 35.5 32.3
Viscosity/135 °C/Pa s 3.9 4.1 4.3 6.8
/177 °C/Pa s 0.69 0.93 0.96 1.8
Ductility/5 °C/cm 6.5 8.9 6.4 4
Flexibility/5 °C/cm/N 0.12 0.14 0.08 0.045
Toughness/25 °C/N m 15.1 11.8 12.2 10.4
Tenacity/25 °C/N m 6.3 3.9 3.2 3.5
Elasticity/25 °C/%/3 min 48 63 51.7 43
/25 °C/%/1 h 63 71 70 61
Softening point difference/°C -4.6 -2.1 -1.5 39.1
After TFOT ageing
Softening point/°C 56.5 58.4 63.3 62.2
Penetration/25 °C/0.1 mm 38.7 39.3 33.5 27.3
Ductility/5 °C/cm 6 7.9 6.6 2.1
Flexibility/5 °C/cm/N 0.072 0.086 0.067 0.03
Toughness/25 °C/N m 9.4 10.1 12.9 10.3
Tenacity/25 °C/N m 3.9 3.7 3.6 4.2
Elasticity/25 °C/%/5 min 54 54.5 54 46
/25 °C/%/1 h 68 71.5 72 65

123
The research for crumb rubber/waste plastic compound modified asphalt 733

10 °C min-1 heated from room temperature to 900 °C. The
argon flow during the experiments was 120 mL min-1.
The thermogravimetry (TG) curve, derivative thermo-
gravimetric (DTG) curve and differential scanning
calorimetry (DSC) curve were used to evaluate the thermal
behaviour of binders. All experiments were performed
three times for reproducibility.
Results and discussion
Physical properties
The physical properties of base asphalt and CRM asphalts
with different rubber meshes (40, 80, 120 mesh) are given
in Table 4. It can be seen that the major physical properties
of base asphalt including softening point, elastic recovery,
ductility, toughness and tenacity were improved greatly by
the addition of CR. Compared with base asphalt, CRM
asphalts own better high- and low-temperature properties,
adhesion and elasticity. In the preparation of CRM asphalt,
CR particles were sheared into smaller parts and swelled
fully in asphalt. Light asphalt components such as aro-
matics and saturates were absorbed by CR particles, and
CR was swelled to a great extent in asphalt, leading to the
improved softening point and toughness. The swelled CR
particles made asphalt more elastic and flexible, so the
elasticity and ductility of binder were also improved.
The properties of CRM asphalt depend on the rubber
mesh to a great extent. It can be seen that the high-tem-
perature properties and elasticity of modified binder
increased and low-temperature performances declined with
increasing the mesh. The binder with 40 mesh owns higher
softening point and elasticity, and the binder with
120 mesh owns better ductility and flexibility. Compared
with the CRM asphalt with 80 mesh, the CRM asphalt with
40 mesh is unstable, the softening point difference in sta-
bility test is more than 2.5 °C; for the CRM asphalt with
120 mesh, the softening point and elasticity are lower.
Considering the major properties including high- and low-
temperature properties, storage stability, elasticity and the
CRM asphalt with 80 mesh CR can be selected for the
further modification.
To improve the high-temperature property of CRM
asphalt (80 mesh CR) further, we used different kinds of
waste plastic including PP, LDPE and LLDPE in the
sample preparation, and the physical properties are listed in
Table 5. It can be seen that CR/LLDPE modified
(CRLLM) asphalt owns higher softening point than that of
CR/LDPE modified (CRLM) and CR/PP modified (CRPM)

Table 6 Physical properties of CRLLM asphalt with different meshes

CRLLM/40 CRLLM CRLLM/120

Softening point/ °C 61.7 60.3 59.5

Penetration/25 °C/0.1 mm 35.5 35.5 41
Viscosity/135 °C/Pa s 6 4.3 4.8
/177 °C/Pa s 1.2 0.96 1
Ductility/5 °C/cm 5.5 6.4 7.1
Flexibility/5 °C/cm/N 0.08 0.08 0.08
Toughness/25 °C/N m 12.8 12.2 13.4
Tenacity/25 °C/N m 3.9 3.2 4.3
Elasticity/25 °C/%/3 min 64.5 51.7 50
/25 °C/%/1 h 75 71 68
Softening point difference/°C -8 -1.5 -0.5
After TFOT ageing
Softening point/°C 60.2 63.3 61.2
Penetration/25 °C/0.1 mm 34.3 33.5 32.5
Ductility/5 °C/cm 5.5 6.6 4.6
Flexibility/5 °C/cm/N 0.064 0.067 0.063
Toughness/25 °C/N m 10 12.9 11.9
Tenacity/25 °C/N m 3.8 3.6 3.7
Elasticity/25 °C/%/5 min 56 54 59
/25 °C/%/1 h 72 72 76.5
CRLLM/40: CRLLM asphalt with 40 mesh CR
CRLLM/120: CRLLM asphalt with 120 mesh CR
CR content: 13 mass/%; LLDPE content: 2 mass/%

123
734 F. Zhang, C. Hu

Table 7 Effect of plasticizer on physical properties of CRLLM ageing. Considering the further improvement for the high-
asphalt temperature performance of CRM asphalt, LLDPE was
CRLLM CRLLFM CRLLDM selected as the candidate and used in the compound mod-
ification for CRM asphalt. The physical properties of
Softening point/°C 60.3 57.9 58.2
CRLLM2 asphalt with 4 mass/% LLDPE are also given in
Penetration/25 °C/0.1 mm 35.5 41.4 45.2 Table 5. It can be seen that the softening point increased
Viscosity/135 °C/Pa s 4.3 4.9 4.6 further; however, the lower penetration and higher vis-
/177 °C/Pa s 0.96 1.1 1.04 cosity show the further addition of 2 mass/% LLDPE made
Ductility/5 °C/cm 6.4 7.6 7.9 asphalt more rigidity. The excessive thickness caused by
Flexibility/5 °C/cm/N 0.08 0.09 0.11 4 mass/% LLDPE declined the major physical properties
Toughness/25 °C/N m 12.2 12.1 13.5 including ductility, flexibility, elasticity and toughness
Tenacity/25 °C/N m 3.2 4 4.3 before and after ageing. Besides, the great difference in
Elasticity/25 °C/%/3 min 51.7 47 63 softening point after storage test shows the serious phase
/25 °C/%/1 h 70 64 78 separation. Considering the major properties before and
Softening point difference/°C -1.6 -2 -2.2 after ageing roundly, the right content of LLDPE in CRM
After TFOT ageing asphalt should be 2 mass/%.
Softening point/°C 63.3 61.7 60.6 To investigate the effect of CR mesh on the properties of
Penetration/25 °C/0.1 mm 33.5 34.2 37.1 modified binder based on the proportion of CRLLM
Ductility/5 °C/cm 6.6 5.1 5.2 asphalt, the binders with 40 and 120 mesh CR were pre-
Flexibility/5 °C/cm/N 0.067 0.05 0.085 pared and the physical properties are listed in Table 6.
Toughness/25 °C/N m 12.9 11.8 10.7 Generally, larger CR particles made the binder predomi-
Tenacity/25 °C/N m 3.6 3.6 3.8 nant in high-temperature properties and elasticity [18]. It
Elasticity/25 °C/%/5 min 54 53 52 can be seen that the modified binder with larger CR mesh
/25 °C/%/1 h 72 71 70 also owns higher softening point, elasticity and lower
ductility. However, after ageing, the softening point of the
40 mesh binder declined a little and is lower than that of
the two others; this can be attributed to the obvious
asphalts; this can be attributed to the more concentrated degradation of larger CR. Though the increased hard
molecule weight of LLDPE, which led to the higher asphalt compositions improved the high-temperature per-
melting point and density compared to those of PP and formances of binder in a way, the polymer degradation still
LDPE. The low-temperature ductility and flexibility of played an obvious role. For the other binders, the increased
CRPM and CRLLM asphalts are lower than those of softening point shows an opposite effect and the 80 mesh
CRLM asphalt; this is because the density and molecule binder owns better low-temperature ductility and flexibil-
weight of LLDPE and PP still are higher than those of ity. Considering the physical properties before and after
LDPE, and there are more branches in the molecule chain ageing, the proportion of the binder with 80 mesh was still
of PP, which hindered the stretching of polymer molecule confirmed.
to a great extent in ductility test. This point also can be To improve the low-temperature properties of CRLLM
confirmed further by the result of elastic recovery test; it asphalt further, CR/LLDPE/FEO modified (CRLLFM) and
can be seen that the elastic recovery rate of CRLM binder CR/LLDPE/DP modified (CRLLDM) asphalts were pre-
is higher than that of CRPM and CRLLM binders, showing pared by the addition of two kinds of plasticizers: FEO and
that LDPE with lower density and rigidity is more elastic. DP, respectively, and the physical properties are listed in
Toughness and tenacity of CRPM binder are much higher Table 7. Obviously, the physical properties of CRLLDM
than those of CRLM and CRLLM binders; this is because asphalt including ductility and flexibility, elasticity,
PP owns higher intensity and stiffness, which caused larger toughness and tenacity are better than those of CRLLFM
tension in toughness test. After ageing, owing to the effect asphalt, which can be attributed to the better plasticization
of the increased hard asphalt compositions, the softening of DP. With the better swelling of DP, both CR and
point of the three binders increased and the penetration LLDPE became more flexible in asphalt, leading to an
decreased correspondingly. The great loss of low-temper- obvious improvement in the low-temperature properties
ature flexibility shows the serious polymer degradation to and elasticity. After ageing, CRLLDM binder still owns
some extent, which also can be confirmed further by the better low-temperature ductility and flexibility, and there is
declined toughness and tenacity of CRPM binder. no evident difference in the other physical properties
Compared with CRM, CRPM, CRLM asphalts, CRLLM between the two binders. In the consideration of improving
asphalt owns higher softening point before and after the high- and low-temperature properties of binder roundly,

123
The research for crumb rubber/waste plastic compound modified asphalt 735

(a) (b)
1000000 80
81 1000000
78
78 76
100000 75 74
100000
88 °C 72 72
69 70
10000 10000 68
G∗/Pa

G∗/Pa
66

δ /°

δ /°
66
63
1000 64
60 1000
62
CRM 57 60
100 CRLLDM 54 100 CRM 58
CRLLM CRLLM 56
51
CRLLDM 54
10 48 10 52
30 40 50 60 70 80 90 100 110 120 130 140 30 40 50 60 70 80 90 100 110 120 130 140
Temperature/°C Temperature/°C

Fig. 1 a The isochronal plots of G* and phase angle versus temperature before ageing. b The isochronal plots of G* and phase angle versus
temperature after ageing (temperature sweep, 30–140 °C, 10 rad/s)

(a) 65 (b) 65
60 60
1E8
55 1E8 55
50 50
45 45
G∗/Pa

G∗/Pa
δ /°

δ /°
40 40
1E7
1E7
35 35

30 30
CRM CRM 25
25
CRLLM CRLLM
1000000 CRLLDM 20
CRLLDM 20 1000000
15
15
–15 –10 –5 0 5 10 15 20 25 30 –15 –10 –5 0 5 10 15 20 25 30
Temperature/°C Temperature/°C

Fig. 2 a The isochronal plots of G* and phase angle versus temperature before ageing. b The isochronal plots of G* and phase angle versus
temperature after ageing (temperature sweep, -15–30 °C, 10 rad/s)

the proportion of CRLLDM asphalt is perfect and consid-
ered as the optimal one.
Rheological properties
To investigate the effect of LLDPE and plasticizer on the
rheological properties of CRM asphalt in the high-tem-
perature range (from 30 to 138 °C), the rheological beha-
viour of CRM, CRLLM and CRLLDM asphalts before and
after ageing was tested and is shown in Fig. 1a, b. It can be
seen that the addition of LLDPE improved the high-tem-
perature performance of CRM asphalt to a little extent, as
shown by the higher G* of CRLLM asphalt at elevated
temperature in Fig. 1a; however, the higher phase angle of
CRLLM asphalt compared to CRM asphalt before 88 °C
shows a viscous behaviour, which can be attributed to the
replace of LLDPE for some elastic CR. The elevated phase
angle curve of CRLLDM asphalt in the whole temperature
range indicates a more viscous behaviour accused by the
dilution of plasticizer and the G* of modified binder also
decreased. After ageing, the effect of LLDPE and plasti-
cizer still exists, as shown by the similar change in phase
angle and G* in Fig. 1b. Both LLDPE and plasticizer
increased the viscous behaviour of CRM asphalt and have
opposite effects on the high-temperature performance of
CRLLDM asphalt.
The rheological behaviour of modified asphalts in the
low-temperature range (-15 to 30 °C) before and after
ageing was tested and is shown in Fig. 2a, b. Before age-
ing, as shown in Fig. 2a, the lower G* and higher phase
angle of CRLLDM asphalt show an obvious viscous
behaviour, which made the binder flexible and improved
the low-temperature performances greatly. At lower tem-
peratures, the asphalt binder becomes more hard and brittle

123
736
and the use of LLDPE made binder more tough, which is
illustrated by the higher G* and lower phase angle of
CRLLM asphalt. After ageing, the difference in G* and
phase angle between CRLLDM and CRM asphalts was
decreased to a little extent, as shown in Fig. 2b, and the
higher phase angle of CRLLDM binder compared to
CRLLM binder still shows an obvious viscous behaviour or
the improved flexibility.
Morphology
The morphology of the CRM, CRLLM and CRLLDM
asphalts before and after ageing is shown in Fig. 3a–f. For
CRM asphalt, as shown in Fig. 3a, it can be seen that lots
of coarse CR particles are dispersed in asphalt, showing the
poor compatibility between CR particles and asphalt. Many
CR particles still did not desulfurate and decompose into
smaller particles in the sample preparation process. The
morphology of CRLLM asphalt is shown in Fig. 3b; the
tiny luminous yellow plastic particles are dispersed in
asphalt and interlaced with the black CR particles, leading
to the formation of a more dense polymer network in
asphalt. In the morphology of CRLLDM asphalt, as shown
in Fig. 3c, the filamentous LLDPE was interlaced with the
black CR particles together in asphalt, which means
LLDPE was swelled further by the addition of plasticizer.
After ageing, the morphology of each binder is shown in
Fig. 3d–f. For CRM binder, as shown in Fig. 3d, the
smaller size of CR particles than before ageing shows
ageing prompted the decomposition of CR and improved
Fig. 3 Morphology of modified asphalts (optical microscopy) at a
magnification of 400 before and after ageing. a CRM asphalt,
b CRLLM asphalt, c CRLLDM asphalt, d CRM asphalt after ageing,
e CRLLM asphalt after ageing, f CRLLDM asphalt after ageing
123
F. Zhang, C. Hu
90
AH-70
80
CR
Transmittance/%
CRM
70
60
50
40
400 800 1200 1600 2000 2400 2800 3200 3600 4000
Wavenumber/cm–1
Fig. 4 FTIR spectra of base, CR, CRM asphalts (400–4000 cm-1)
the compatibility between asphalt and CR. For CRLLM
and CRLLDM binders, most polymer particles declined
obviously and no obvious filamentous LLDPE appears in
the morphology, showing a serious polymer degradation.
FTIR analysis
The FTIR spectrum of base, CRM asphalts and CR is given
in Fig. 4. For base asphalt, the strong peaks within
2853–2915 cm-1 region were typical C–H stretching
vibrations in aliphatic chains. The peak at 1636 cm-1 was
attributed to C=C stretching vibrations in aromatics. The
C–H asymmetric deforming in CH2 and CH3 and the C–H
symmetric deforming in CH3 vibrations were observed at
1454.1 and 1375.2 cm-1, respectively. The peak at
1219.3 cm-1 corresponded to the frame vibration of
(CH3)3C–R. The peak at 1030 cm-1 was ascribed to
S=O stretching vibrations. The small peaks within
671.2–871.2 cm-1 region were typical C–H vibrations of
benzene ring [19]. For CR, the board peak at 3456 cm-1 is
the stretching vibration of O–H, the peak at 2917.4 and
2849.3 cm-1 is the vibration absorbing of –CH2–,
1636.9 cm-1 is attributed to the framework vibration of C=C
of benzene ring, 1449.5 cm-1 is the stretching vibration of
-CH2- and the antisymmetry stretching vibration of -CH3.
The weak peaks within 438.8–1087.8 cm-1 region were typ-
ical C–H vibrations of benzene ring [20]. For CRM asphalt, it
can be seen that the major peaks of CRM asphalt are still
similar to those of base asphalt and no new peak appears.
Because of the absorption of CR to asphalt, the peak intensity
of CRM asphalt is much lower than that of base asphalt.
The spectrum of DP is shown in Fig. 5a; 2853 and
2915 cm-1 are still the typical C–H stretching vibrations in
aliphatic chains of Essien ester. 1732.8 cm-1 is the
stretching vibration of C=O, 1583 cm-1 is the frame
The research for crumb rubber/waste plastic compound modified asphalt 737

(a) of CR, LLDPE and DP was belong to the physical modifi-

100 cation, and there was no obvious chemical reaction taken
place. After ageing, the FTIR spectrum of each modified
80 653.4 asphalt is similar to that before ageing and there is still no
Transmittance/%

1583 new peaks appeared.

60

40 743.1 Thermal analysis

20 1073
1122.7
1456.8 The thermal stability of modified asphalt is an important
1276.2
1732.8
2853
2915
property to be considered in the analysis for the structural
0
characteristics of asphalt binder [22]. In this article, the
500 1000 1500 2000 2500 3000 3500 4000
thermal behaviour of base asphalt, CRM, CRLLM and
Wavenumber/cm–1
CRLLDM asphalts before and after ageing was studied by
thermogravimetry at the heating rate: 10 °C min-1. The
(b) TG/DSC/DTG curves for each binder before and after
90 ageing are shown in Fig. 6 and 7, respectively, and the TG/
80 DTG properties are listed in Table 8. The TG curves show
70 that all binders undergo the major mass loss stage
350–550 °C, and the mass loss is mainly due to the
Transmittance/%

60
50
40
30 LLDPE
CRLLM
20 CRLLDM
10
0
500 1000 1500 2000 2500
Wavenumber/cm–1
Fig. 5 a FTIR spectra of DP (400–4000 cm-1), b FTIR spectra of
LLDPE, CRLLM, CRLLDM asphalts (400–4000 cm-1)
stretching vibration of C=C, 1456.8 cm-1 is the C–H
asymmetric deforming in CH2, 1276.2 and 1122.7 cm-1
are the stretching vibrations of C–O. The peak at
1073 cm-1 and small peaks within 653.4–743.1 cm-1
region were typical C–H vibrations of benzene ring [21].
The FTIR spectrum of LLDPE, CRLLM, and CRLLDM
asphalts is shown in Fig. 5b. For LLDPE, the board peak at
3445 cm-1 is still the stretching vibration of O–H,
2915 cm-1 is the asymmetrical stretching vibration of
–CH2– and 2853 cm-1 is the symmetrical stretching
vibration of –CH2–, 1628.4 cm-1 is the frame vibration of
C=C, 1470.7 cm-1 is the stretching vibration of –CH2– and
the antisymmetrical stretching vibration of –CH3, 712.1 cm-1
is the typical C–H vibrations of benzene ring. In the spectrum
of CRLLM asphalt, no new peak appears by the addition of
LLDPE and most peaks of LLDPE are overlapped by those of
asphalt. A similar phenomenon also can be found for
CRLLDM asphalt; all peaks still can be attributed to those of
asphalt, which indicates that the modification by the addition
volatilization of the light asphalt components such as sat-
urates and aromatics and the decomposition of polymer and
large asphalt molecule [23, 24]. This is the major mass loss
stage, as demonstrated by the dramatic event in the DTG
and DSC curves. The DSC curves show that the thermo-
mechanical behaviour of each binder can be described by
the endothermic peak in the major mass loss stage, and the
3000 3500 4000 area of each endothermic peak can be calculated by the
using tangent [18, 25]. The calculated peak areas of all
binders before and after ageing are listed in Table 9. By
comparing the area of endothermic peak, we can evaluate
the molecule weight distribution and constituents of mod-
ified asphalt further [25, 26].
To investigate the effect of LLDPE and CR on the
thermal behaviours of asphalt, the TG/DSC/DTG curves of
CR (80 mesh) and waste LLDPE are also shown in Fig. 8.
In Fig. 8a, it can be seen that the mass loss process of CR is
distributed between 325 and 476 °C. After 325 °C, the
mass loss of CR increases with increasing the temperature
and the mass loss rate arrives at the maximum, as shown by
the DTG curve, the abroad endothermic peak after 325 °C
shows the molecule weight distribution was not concen-
trated and the volatilized components were various [25].
The TG/DSC/DTG curves of LLDPE are shown in Fig. 8b;
it can be seen that there are three endothermic peaks at the
DSC curve with increasing the temperature. Also, the two
peaks 2 and 3 which appear in the DTG curve within the
two temperature ranges: 400–500 °C and 600–700 °C
correspond to the peaks 2 and 3 of DSC curve, respec-
tively, even the peak 3 is not obvious. The major mass loss
is concentrated between 400 and 500 °C, which is con-
firmed by the poignant peak of DTG and DSC curves.

123
738 F. Zhang, C. Hu

(a) 110 16 (b) 110 14

TG 0.8 TG
100 14 100 2.5
12
0.7
90 12 90

Derivative mass/% min–1

10 2.0

Derivative mass/% min–1

0.6
80 10 80

End
0.5 8

End
70 70 1.5
Mass/%

Mass/%
8
60 0.4
60 6

Heat flow/mW
6 1.0

Heat flow/mW
DSC 0.3
50 50
4 4
40 0.2 40 0.5
2 2
30 DTG 0.1 30 DSC
0 0.0
20 0.0 0
20 DTG
–2
10 –0.1 10 –2 –0.5
0 100 200 300 400 500 600 700 800 900 0 100 200 300 400 500 600 700 800 900 1000
Temperature/°C Temperature/°C

(c) 110 14 5.0 (d) 110 1.0

TG 4.5 TG 12
100 12 100 Peak 3
4.0 0.8
90 90 10

Derivative mass/% min–1

10 3.5
Derivative mass/% min–1

80 80 0.6
3.0 8

End
End
8
70 70
Mass/%

2.5 Mass/% Peak 2 6 0.4

60 6 2.0 60

Heat flow/mW
Heat flow/mW

50 1.5 50 4
4 0.2
1.0
40 40 Peak 1
2 0.5 DSC 2
30 0.0
30
DTG 0.0
0 0
20 –0.5 20 DTG –0.2
DSC
10 –2 –1.0 10 –2
0 100 200 300 400 500 600 700 800 900 1000 0 100 200 300 400 500 600 700 800 900 1000
Temperature/°C Temperature/°C

Fig. 6 a TG/DSC/DTG curves of base asphalt, b TG/DSC/DTG curves of CRM asphalt, c TG/DSC/DTG curves of CRLLM asphalt, d TG/DSC/
DTG curves of CRLLDM asphalt

In the TG/DSC/DTG curves of CRLLM asphalt, as LLDPE. The use of DP declined the thermal stability
shown in Fig. 6c, it can be seen that the peaks 1 and 3 of again, as shown by the lower T0 and TDTG of CRLLDM
LLDPE in Fig. 8b do not appear. However, in Fig. 6d, the asphalt. As a light component, DP was volatilized more
characteristic peaks of LLDPE appear obviously, espe- easily at elevated temperature. After TFOT ageing, the
cially for the peak 3, which means the LLDPE swelled by T0 and TDTG of modified binders declined to a little
DP became more energy consumption, leading to the extent due to the polymer degradation. The similar
appearance of the characteristic peaks. After TFOT ageing, consequence of T0 and TDTG among binders than before
the characteristic peaks of LLDPE still appear in the DSC/ ageing still shows the same effect of each modifier on
DTG curves of CRLLDM binder, as shown in Fig. 7d, thermal behaviour.
which means that the swelled LLDPE still existed and In Table 9, the similar peak area of CRM asphalt
played a role on the thermal behaviour of CRLLDM compared to base asphalt indicates less heat absorption in
binder. the major mass loss process, which means less asphalt
In Table 8, the lower T0 and TDTG of CRM asphalt components or materials were volatilized or decomposed
compared to those of base asphalt indicate the suscepti- due to the absorption of CR and the inertia of CR. The
bility of CR to heating degradation. With increasing the obviously declined area of CRLLM asphalt shows the
temperature, some parts of CR begin to degrade. For replace of LLDPE for some CR particles changed the
CRLLM asphalt, the replace of LLDPE for 2 mass/% molecule weight distribution of modified binder to some
CR declined the susceptibility a little, as shown by the extent and less molecules or components were degraded or
higher T0 and TDTG, which is attributed to the more volatilized, resulting in the lower energy consumption. The
concentrated molecule weight and higher density of use of plasticizer led to an opposite effect, as shown by the

123
The research for crumb rubber/waste plastic compound modified asphalt 739

110 14 14 4.0
(a) (b) 110
TG 1.2 TG
100 100 3.5
12 DTG 12
90 1.0 90 3.0
DTG 10 10

Derivative mass/% min–1

80 80 2.5

Derivative mass/% min–1

Heat flow/mW End

Heat flow/mW End

8 0.8 8
70 70 2.0
Mass/%

Mass/%
60 6 0.6 60 6 1.5

50 50 1.0
4 0.4 4
40 40 0.5
2 2
30 DSC 0.2 30 DSC 0.0
0 0 –0.5
20 20
0.0
10 –2 10 –1.0 –2
0 100 200 300 400 500 600 700 800 900 0 100 200 300 400 500 600 700 800 900 1000
Temperature/°C Temperature/°C

5.0
(c) 110 14 (d) 110 14 1.4
TG 4.5 TG
100 DTG 100
12 DTG Peak 3 12 1.2
4.0
90 90
3.5 1.0
10 10
80

Heat flow/mW End

3.0 80
Derivative mass/% min–1

Derivative mass/% min–1

Heat flow/mW End 0.8
8 8
70 2.5 70 Peak 2
Mass/%

0.6
60 6 2.0 Mass/% 60 6
1.5 0.4
50 50
DSC 4 4
1.0 0.2
40 40
2 0.5 2
DSC Peak 1 0.0
30 30
0.0
20 0 0 –0.2
–0.5 20
10 –2 –1.0 10 –0.4
–2
0 100 200 300 400 500 600 700 800 900 1000 0 100 200 300 400 500 600 700 800 900 1000
Temperature/°C Temperature/°C

Fig. 7 a TG/DSC/DTG curves of base asphalt after ageing, b TG/DSC/DTG curves of CRM asphalt after ageing, c TG/DSC/DTG curves of
CRLLM asphalt after ageing, d TG/DSC/DTG curves of CRLLDM asphalt after ageing

Table 8 TG/DTG properties of base and modified asphalts before Table 9 Area of major endothermic peak
and after ageing
AH-70 CRM CRLLM CRLLDM
T0/°C TDTG/°C Residual/%/800 °C
Before ageing 27 27.1 23.8 27.9
AH-70 423.6 464.5 17.2 After ageing 23.7 21.4 35.3 39.6
CRM 414.7 464 20.4
CRLLM 419.3 465.6 18.6
CRLLDM 417.1 464.5 21.3
After TFOT ageing because the larger CR particles were decomposed into
AH-70 429.1 466.8 18.2 smaller ones by ageing and the smaller CR particles were
CRM 405.3 462.7 21.2 easy to be decomposed in heating. For CRLLM and
CRLLM 408.9 465.1 19.8 CRLLDM binders, the obviously increased peak area than
CRLLDM 404.8 464.4 19.9 before ageing shows the constituents and molecule weight
distribution of binder became more complex. Owing to
the degradation of LLDPE by ageing, more polymer
larger peak area of CRLLDM asphalt, because DP as a fragments with different sizes or volumes appeared in
light component was easy to be volatilized in heating, asphalt matrix, resulting in the more broad molecule
leading to the further energy consumption. After ageing, weight distribution and larger endothermic peak.
the peak area of CRM binder declined than before ageing CRLLDM binder owns larger peak areas, because the

123
740 F. Zhang, C. Hu

(a) 110 7 1.0 (b) 35 2.0

TG 100
100 6 TG 30

Derivative mass/% min–1

0.5
1.5
90 Peak 1 Peak 2
5 80

Derivative mass/% min–1

25

End
0.0

End
80 4 20 1.0
DSC 60
Mass/%

Mass/%
–0.5

Heat flow/mW
70

Heat flow/mW
3 15
0.5
60 40
2 –1.0 10
DSC
50 0.0
1 20 Peak 3 5
–1.5
40 DTG DTG
0 0
–2.0 0 –0.5
30
–1 –5
0 100 200 300 400 500 600 700 800 900 1000 0 100 200 300 400 500 600 700 800 900 1000
Temperature/°C Temperature/°C

Fig. 8 a TG/DSC/DTG curves of CR, b TG/DSC/DTG curves of LLDPE

residual DP in asphalt after ageing still consumed energy
further in heating process.
Conclusions
The physical and rheological testing shows LLDPE was pre-
dominant in improving the high-temperature properties of
CRM asphalt and DP was necessary to improve the low-tem-
perature properties of CRLLM asphalt further; both LLDPE
and DP increased the viscous behaviour of CRM asphalt to
some extent. Morphology observation showed an interlaced
polymer network consisting of CR and LLDPE was formed in
asphalt and DP prompted the further swelling of polymer in
asphalt. FTIR analysis shows the effect of LLDPE and DP in
asphalt is still belong to the physical modification. Thermal
analysis showed CR and LLDPE declined the thermal sus-
ceptibility of asphalt greatly and DP led to an opposite effect.
References
1. Wang SF, Yuan CH, Deng JX. Crumb tire rubber and poly-
ethylene mutually stabilized in asphalt by screw extrusion. J Appl
Polym Sci. 2014;131:41189(1–7).
2. Daryl M, Susanna H, Ryan W, Ludo Z. Study of crumb rubber
materials as paving asphalt modifiers. Can J Civil Eng.
2007;34:1276–88.
3. Xiao FP, Amirkhanian SN, Shen J. Influences of crumb rubber
size and type on reclaimed asphalt pavement (RAP) mixtures.
Constr Build Mater. 2009;23(2):1028–34.
4. Li X, Jian C, Guo HQ. Microstructure and performance of crumb
rubber modified asphalt. Constr Build Mater. 2009;23:3586–90.
5. Miriam E. Use of coupling agents to stabilize asphalt–rubber–
gravel composite to improve its mechanical properties. J Clean
Prod. 2009;17(15):1359–62.
6. Yetkin Y. Polymer modified asphalt binders. Constr Build Mater.
2007;21:66–72.
7. Shen J, Amirkhanian S. The influence of crumb rubber modifier
(CRM) microstructures on the high temperature properties of
CRM binders. Int J Pavement Eng. 2005;6(4):265–71.
8. Cheng Y. Prospect for application of waster powder. China Synth
Rubber Ind. 2001;24:65–6 (Chinese).
9. Hu R, Yu ZP, Zhang LN, Zhou SS, Mi XH. Pavement properties
of asphalt modified with packaging-waste polyethylene. J Vinyl
Addit Technol. 2014;20(1):31–5.
10. Wang SF, Wang Q, Wu XY, Zhang Y. Asphalt modified by
thermoplastic elastomer based on recycled rubber. Constr Build
Mater. 2015;93:678–84.
11. Marı́a A, Vargasa MA, Vargasa A, Octavio M. Asphalt/poly-
ethylene blends: rheological properties, microstructure and vis-
cosity modeling. Constr Build Mater. 2013;45:243–50.
12. Giovanni P, Stefano B, Dario B, Jiri S, Ludovit Z. Asphalt
modification with different polyethylene-based polymers. Eur
Polym J. 2005;41:2831–44.
13. Wu XW. Study on preparation and properties of high density
polyethylene modified asphalt (Master Dissertation). Dongying
City: China University of Petroleum; 2012.
14. Fang CQ. Analysis of modifying asphalt by the waste-PE in
packing (Master Dissertation). Xian City: Xian University of
Technology; 2005.
15. Fang CQ, Li TH, Zhang ZP, Jing DQ. Modification of asphalt by
packaging waste-polyethylene. J Polym Compos. 2008;29(5):
500–5.
16. Yan KZ, Xu HB, You LY. Rheological properties of asphalts
modified by waste tire rubber and reclaimed low density
polyethylene. Constr Build Mater. 2015;83:143–9.
17. Ouyang CF, Gao Q, Shi YT, Shan XQ. Compatibilizer in waste
tire powder and Low-Density polyethylene blends and the blends
modified asphalt. J Appl Polym Sci. 2012;123:485–92.
18. Zhang F, Hu CB. The research for structural characteristics and
modification mechanism of crumb rubber compound modified
asphalts. Constr Build Mater. 2015;76:330–42.
19. Ouyang CF, Wang SF, Zhang Y, Zhang YX. Improving the aging
resistance of asphalt by addition of zinc dialkyldithiophosphate.
Fuel. 2006;85:1060–6.
20. Zhang WB. Study on mechanism of crumb rubber modified
asphalt (Master Dissertation). Chongqing City: Chongqing Jiao-
tong University; 2009.
21. Bellamy LJ. Infrared spectrum of complex molecules. 1st ed.
Beijing: Science Press; 1975.

123
The research for crumb rubber/waste plastic compound modified asphalt
22. Zhang F, Hu CB. The research for thermal behaviour, creep
properties and morphology of SBS-modified asphalt. J Therm
Anal Calorim. 2015;121(2):651–61.
23. Zhang F, Hu CB. Influence of aging on thermal behavior and
characterization of SBR compound-modified asphalt. J Therm
Anal Calorim. 2014;115(2):1211–8.
24. Radhakrishnan CK, Sujith A, Unnikrishnan G. Thermal beha-
viour of styrene-butadiene rubber/poly(ethylene-co-vinylacetate)
blends TG and DSC analysis. J Therm Anal Calorim. 2007;90:
191–9.
741
25. Gao JL. Analysis and evaluation of bitumen new index and
additive index (Doctor Dissertation). Nanjing City: Southeast
University; 2005.
26. Gao JL, Huang XM, Li HJ. Evaluation method of differential
scanning calorimetry for asphalt performance. J Traff Tran Eng.
2005;5:37–42.
123