1 3rd Conference of Transportation Research Group of India (3rd CTRG)

2 Rheological Study on Mixing Temperatures for Modified

3 Binders
4 Nikhil Sabooa and Praveen Kumarb

5 Research Scholar, Department of Civil Engineering, Indian Institute of Technology, Roorkee, India, niks.iitkgp88@gmail.com.
6 Praveen Kumar, Department of Civil Engineering, Indian Institute of Technology, Roorkee, India, pkaerfce@iitr.ac.in

7 Abstract. Study of flow behavior is crucial for viscoelastic characterization of asphalt binders. Shear thinning
8 behavior in modified bitumen requires a critical study of the viscosity at a wide range of temperatures and
9 shear rates. This will also aid in practical calculation of more appropriate mixing temperatures for asphalt
10 concrete.

11 This study focusses on appraising the flow properties of asphalt binders for a wide range of shear rates and
12 temperaturse using steady shear methods. Carreau-Yasuda (C-Y) and exponential model are pooled with the
13 concept of Rheogram for prediction of the viscosity of asphalt binder at any desired temperature and shear
14 rate. Four binders were used in the study. VG10 and VG 30 were the viscosity graded binder. VG 10 was
15 being modified with two different polymers at various percent of modification level. Steady shear viscosity
16 was evaluated for all the binders using Dynamic Shear Rheometer (DSR). Testing was done at a shear rate of
17 0-100 s-1 for a temperature range of 40-80 ˚C. High temperature viscosity was measured using Brookfield
18 viscometer.

19 It was found that C-Y model could be successfully applied to viscosity- shear rate master curves for all types
20 of asphalt binders. Exponential model produced good fit for the zero shear viscosity and the model parameters
21 were found to be binder specific. Lower mixing and compaction temperatures were acquired for modified
22 binders, which decreased with increase in shear rate. A more practical technique of finding the mixing
23 temperatures for asphalt binders is presented and discussed.

24 Keywords: Bitumen; Viscosity; Shear thinning; Polymer; Carreau-Yasuda; Rheogram

25 1. Background
26 Rheology is the study of flow of matter, in a liquid or soft-solid, which are both time and
27 temperature dependent. Over the last five decades much research has been done in studying
28 the various rheological aspects of bitumen and asphalt. Modification of bitumen is one of
29 the several techniques to improve the structural performance of bituminous mix [1–4].
30 Polymer modified binders have been successfully used to enhance the viscoelastic response
31 of bitumen. [1,5,6]. When it comes to applicability, contractors and practitioners remain
32 cynical, typically due to the high temperature requirements of mixing and compaction for
33 these binders. Additionally, increase in cost is a main concern. Conventionally, Rotational
34 Viscometer is used for assessing the mixing and compaction temperature of bitumen. The
35 viscometer applies 6.8 s-1 (20 rpm) shear rate and the resultant torque is utilized to compute
36 the viscosity of the binder at different temperatures. The log-log plot of viscosity against
37 temperature is used to find out the temperatures corresponding to 0.17±0.02 Pa.s and
38 0.28±0.03 Pa.s. These temperatures are used for mixing and compaction of bituminous mix.

39 NCHRP report 648 [7] offered new methods for assessing the mixing and compaction
40 temperatures for modified binders, which resulted in reduction of temperature requirement
41 by 20-30 ˚C, in comparison to the traditional method. In the first method named as “Phase
42 Angle Method”, the mixing and compaction temperature are determined by constructing
43 phase angle master curve at 80 ˚C. Phase angle being more sensitive to chemical changes
 3rd Conference of Transportation Research Group of India (3rd CTRG)

44 creates difficulty in construction of a smooth master curve, which results in a “wavy nature”
45 (attributable to the transition and plateau regions) [1,3–5,8,9]. Furthermore, the use of
46 frequency corresponding to 86˚ has no practical significance. In the second method, named
47 as “Steady Shear Viscosity Method”, Dynamic Shear Rheometer (DSR) is used for finding
48 the viscosity at a shear stress of 500 Pa at different temperatures. Extrapolation of the
49 viscosity data is required for forecasting the mixing and compaction temperature. Such
50 extrapolation by using straight line is misleading, as the rheology of modified binder has
51 high reliance on the molecular structure, which in turn is temperature dependent
52 [4,5,8,10,11].

53 The literature supporting the above methods lies behind the concept that modified binders
54 behave as a shear thinning fluid at practical shear rates. This concept of shear thinning and
55 the viscosity reduction is relevant only when there is high role of shear rate, classically
56 found in mixing. But compaction (as in field roller or Marshall Compactor), has very slight
57 dependence on shear rate. Rather it is the normal force and energy which has higher control.
58 So, reduction in compaction temperature with the above mentioned literature background
59 of shear thinning is again not useable. For continuous and batch mixing plants, the shear
60 rate applied at the time of mixing are approximately of the order of 6x104 to 1x105 s-1 [7].
61 The viscosity at such high shear rate will be even lower than predicted, if the role of shear
62 rate is considered, and hence even lower mixing temperatures can be suggested. But the
63 same might not be applicable to compaction temperature as there is no chief role of shear
64 rate. Many studies [7,12–14] have evaluated the change in strength and density of
65 bituminous mixes by varying the compaction temperature, but no explicit study has
66 described the effect of change of mixing temperatures. The main intention of the study is
67 to appraise the flow behaviour of unmodified and modified bitumen at different
68 temperatures and shear rates, and to define a more practical method for finding the mixing
69 temperatures.

70 2. Materials
71 Four binders were used in the study. VG10 and VG 30 were the viscosity graded (VG)
72 binder. VG 10 was being modified with Styrene Butadiene Styrene (SBS) and Ethylene
73 Vinyl Acetate (EVA) at various percent of modification level. An earlier study [1], found
74 that the interlocked phase of polymer with the base binder is obtained using 3% SBS and
75 5% EVA. Higher percentages yielded binders which were susceptible to phase separation.
76 Moreover, using lower percentages did not fully optimize the properties of the base binder,
77 which resulted in an uneconomical blend. So for comparison only 3% SBS and 5% EVA is
78 considered in the study. The conventional properties along with the high temperature grade
79 PG specification and true intermediate grade temperature for these binders are presented in
80 Table 1. In this paper the polymer modified bitumen will be represented as PMB (E) and
81 PMB (S) indicating modification with EVA and SBS. The authors also studied [1] the
82 optimum blending requirements for both the polymers. Following the study, PMB (S) was
83 modified at a temperature of 180 °C using a high shear mixture operated at 1500 rpm for
84 60 minutes. PMB (E) on the other hand was modified at 190 °C, at a shear rate of 600 rpm
85 for 30 minutes.
86
87
88
89
90
Saboo and Kumar
 3rd Conference of Transportation Research Group of India (3rd CTRG)

91 Table 1 Conventional properties of binders used in the study.

High True Grade,
Penetration Softening Penetration Storage Stability,
Binders Temperature Intermediate
, dmm Point, °C Index ΔSoft. Point, °C
PG Grade Temperature, °C
VG 10 75 47 -1.01 - PG 58- XX 25.3
VG 30 62 49 -0.95 - PG 64-XX 20.1
PMB (S) 56 60 1.31 1.5 PG 70-XX 15.7
PMB (E) 49 65 1.92 1.3 PG 76-XX 12.2
92

93 3. Experimental
94 Steady shear viscosity was evaluated for all the binders using Anton Paar Dynamic Shear
95 Rheometer (DSR). The shear rate was varied from 0-100 s-1 for a temperature range of 40-
96 80 °C. The spindle with 25 mm diameter was used and the adjusted gap was 500 µm.
97 Brookfield viscometer [2] was employed to measure the high temperature viscosity using
98 spindle no. 21 at standard rotational speed of 20 rpm. Measurements were taken at 135 °C
99 and 160 °C.

100 4. Results and Analysis

101 The variation of viscosity with shear rate have been studied at different temperatures for all
102 the binders. The Carreau-Yasuda (C-Y) equation is employed for modelling the viscosity
103 master curve obtained using the concept of rheogram. Finally, the zero shear viscosity
104 (ZSV) from the steady shear test is modelled using a suitable equation. A new technique
105 for finding out the viscosity at any desired shear rate has been proposed. This technique can
106 be successfully used for predicting the mixing temperature of bitumen.

107 4.1 Viscosity versus shear rate

108 The modified and unmodified binders were exposed to steady shear viscosity test at five
109 different temperatures. Fig. 1 (a-d) shows the viscosity variation of different binders with
110 shear rate. Due to delamination of the binder with the spindle at 80 ºC, only readings up
111 to 70 ºC are shown for VG 10. It can be seen that normal binders (VG 10 and VG 30)
112 behaves closely as Newtonian fluids at temperature above 50 °C. It was observed that
113 even at higher temperatures there was some evidence of shear thinning behavior for very
114 high shear rates. Modified binders, on the contrary, displayed shear thinning behavior at
115 all the temperatures. This characteristic was more dominant for plastomeric EVA polymer
116 modified binder (PMB). The onset of shear thinning behavior for modified binders
117 occurred at lower shear rates (critical shear rate) as compared to normal binders,
118 especially at higher temperatures. The aspect to be noted is that, for all binders the critical
119 shear rate were higher than 6.8 s-1 (shear rate used in Brookfield viscometer), and it
120 increased at higher temperatures. This viscosity hence, is the zero shear viscosity (ZSV),
121 also considered as low shear Newtonian viscosity. Two conclusion can be derived from
122 these results. First, 6.8 s-1 is not the practical shear rate the binder experiences at the time
123 of mixing an asphalt concrete. Secondly, it is due to this fact that higher mixing
124 temperatures are obtained for modified binders, displaying high shear thinning behavior.

Saboo and Kumar

 3rd Conference of Transportation Research Group of India (3rd CTRG)

a b

c d

Fig. 1 Viscosity versus Shear Rate at different temperatures

125 4.2 Construction and Modelling of Rheogram

126 Shenoy [3] suggested a method of unifying the viscosity versus shear rate data at different
127 temperature for a different grades of asphalt. He presented the concept of Rheogram,
128 through construction of temperature and asphalt grade independent master curve. The
129 master curve is a plot of  / 0 versus  0 .  .  and  0 are the corresponding viscosity and
130 zero shear viscosity of the polymer. Thus by knowing the temperature dependent ZSV, 
131 can be evaluated at any desired shear rate.
132 Shear rate dependency of shear thinning (non-Newtonian) fluids can be assessed using
133 various models [4–6]. However, Carreau Yasuda (C-Y) model [5] has been found
134 successful for polymers like bitumen [7,8]. The model can be mathematically written as
   ( n 1)/ a
 1     
a
135 (1)
0  

Saboo and Kumar

 3rd Conference of Transportation Research Group of India (3rd CTRG)

136 Where  is the viscosity of the fluid,  0 and  are the zero and infinite shear viscosity,
137  is the shear rate,  , n and a are the shape parameters. 1/  is the critical shear rate at
138 which the viscosity starts to decrease. Considering  /  0 as the desired viscosity,  d and
139 0 . 
as the desired shear rate,  d , the combination of equation 1 and the concept of
140 Rheogram would yield,

 
( n 1)/ a
 d   d  ( 0 d    d ) 1  (d . d )
a
141 (2)
142
143 All the parameters in the above equation remains same as discussed above, but will now
144 be applicable to the master curve.
145 Fig. 2 (a-d) demonstrates C-Y model fit to the master curve. It can be seen that the concept
146 of Rheogram can be successfully applied to the binders considered, although little
147 deviation for PMB (E) is observed. This is indicative of the change in polymer structure
148 within the bitumen-polymer system with change in temperature. This plot can be useful
149 in assessing the critical shear rate for bitumen at any temperature provided the ZSV is
150 accurately known at that temperature.
151

a b

c d
Fig. 2 C-Y model fit with the master curves for different binders.

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 3rd Conference of Transportation Research Group of India (3rd CTRG)

152
153 Table 2 displays the value of the parameters obtained using C-Y fit for all the binders.
154 The significant parameter is the desired critical shear rate (1/ d ). It decreases as we move
155 from normal to modified binders. The practicality of this value could be valued in the
156 calculation of the minimum shear rate that should be applied to the binder for onset of
157 shear thinning behavior. This can done by substituting the following in equation 2.

158  d ≡ / 0 ;  d ≡ 0 .  . So the desired critical shear rate (1/ d ) will be substituted by 0 . 
159 c, where  c represents the critical shear rate.

160 Table 2 C-Y Model Parameters for Different Binders

Carreau-Yasuda Model Parameters
Binder λd η0d η∞d 1/λd
n a
(s) (Pa.s) (Pa.s) (s-1)
VG 10 0.0005 0.5 1 0 4 2000
VG 30 0.0006 0.4 1 0 3 1666.667
PMB (S) 0.001 0.7 1 0 1 1000
PMB (E) 0.003 0.65 1 0 0.7 333.3333
161
162 The most paramount use of such plot and the corresponding equation can be justified as
163 follows. In equation 2 considering 0d and  d to be 1 and 0, the equation can be
164 rewritten as
( n 1)/ a
d  1   d . d  
a
165 (3)
 
( n 1)/ a
166   0 1  (d . .0 )a  (4)

167 Substituting d , n and a in the above equation, which depends on the property of binder,
168 viscosity parallel to any ZSV could be assessed. In other words it could be said that
169 knowing ZSV, at any temperature, the viscosity of the binder can be easily forecasted. In
170 turn these viscosities can then be used to determine the mixing temperatures
171 corresponding to any chosen shear rate for different asphalt binders.
172 4.3 Modelling Zero Shear Viscosity
173 The practical applicability of the above concept can be appreciated only with the accurate
174 modelling of ZSV with temperature. Various researchers [6–12] have attempted to model
175 the variation of ZSV with temperature, pressure and molecular weight. Out of various
176 models used, exponential model of Arrhenius type has shown good correlation for
177 polymers [8]. The basic equation governing the model can be written in the following
178 form

179 0  AeBT (5)

180 The model was fitted with the measured results of ZSV with respect to temperature. Fig.
181 3 (a-d) displays the model fit for all the binders considered in the study, at the measured
182 temperature range of 40 to 80 ºC. It was found that the considered model had good
183 correlation with the observed data. The steady shear viscosities measured using DSR and
Saboo and Kumar
 3rd Conference of Transportation Research Group of India (3rd CTRG)

184 Brookfield viscometer were found to be in good alignment with each other. Similar results
185 were also obtained by Cardone et.al [13]. The parameters of the model were found to be
186 binder specific, which might also vary with the source of crude oil. The ZSV calculated
187 using equation 5 was used as an input to equation 4 to forecast the viscosity at higher
188 temperatures and different shear rates. This was finally used to judge the mixing
189 temperature for different binders.

ZSV fit, VG 10 ZSV fit, VG 30

10000
10000
1000
ZSV(η0), Pa.s

ZSV(η0), Pa.s
1000
100 100 R² = 0.9831
R² = 0.985
10 10 Series1
1 Series1 1
Expon.
Expon. 0.1
0.1 (Series1)
(Series1) 0.01
0.01 0 50 100 150 200
0 50 100 150 200
Temperature, °C Temperature, °C

a b

ZSV fit, SBS ZSV fit, EVA

10000 10000
ZSV(η0), Pa.s

ZSV(η0), Pa.s

1000 1000
100 100 R² = 0.9879
R² = 0.9917
10 Series1
10 Series1
1 Expon. 1
(Series1) Expon.
0.1 0.1 (Series1)
0 50 100 150 200 0 50 100 150 200
Temperature, °C Temperature, °C

c d

Figure 3 Exponential fit for Zero Shear Viscosity (ZSV).

190 To judge the effect of shear rate on mixing temperature, the concept of rheogram and
191 exponential model were used and calculations were made to evaluate the viscosities at
192 three different temperatures (100, 130 and 160 ˚C) and three different shear rates (1000,
193 10000 and 100000 s-1). These values are good approximation of practically used shear
194 rates from laboratory to mixing plant. Plots were also made for predicting the mixing
195 temperature corresponding to viscosity of 0.17 Pa.s. Fig. 4 (a-c) and Table 3 presents the
196 mixing temperature corresponding to different shear rates. It was found that modified
197 binders are more sensitive to shear rate than the conventional binders, as can be seen in
198 Table 3. This indicates higher degree of shear thinning (non-Newtonian) behavior for
199 polymer modified bitumen. Amongst the modified binders, PMB (S) displayed lesser
200 sensitivity as compared to plastomeric PMB (E).

Saboo and Kumar

 3rd Conference of Transportation Research Group of India (3rd CTRG)

a b

Fig. 4 Mixing temperatures corresponding to 0.17 Pa.s for different bitumen at

different shear rates

201 Table 3 Mixing and Compaction Temperatures at Different Shear Rates and
202 Temperatures
Mixing temperatures for different binders, ˚C
Shear rate,s-1
VG 10 VG 30 PMB (S) PMB (E)

1000 152 154 160 165

10000 144 149 156 156

100000 108 126 148 144

203
204 The mixing temperatures for modified binder were found to be higher than conventional
205 binders with the consideration that all binders to a certain degree behaves as a shear-
206 thinning fluid. The Brookfield viscometer predicts very high mixing temperatures, as the
207 effect of practical shear rate is compounded. Increase in shear rate yielded much lower
208 mixing temperatures, even for modified binders. This will also contribute towards higher
209 energy savings and will reduce the potential degradation of binders subjected to such high
210 temperatures. The fact has to be appreciated that laboratory mixing temperatures may be
211 higher than those for field application. Compaction temperatures on the other hand will
Saboo and Kumar
 3rd Conference of Transportation Research Group of India (3rd CTRG)

212 be higher for modified binders due to diminishing role of shear rate. Obviously, a field
213 and laboratory check of the work is required in order to gain more confidence on such
214 evaluations.

215 5. Conclusions
216 Four binders including two normal and two polymer modified were used in the study.
217 The steady shear flow behavior for these binders were measured using DSR and
218 Brookfield viscometer for a wide range of temperature and shear rate. The applicability
219 of the use of Rheogram was studied. C-Y and exponential model were used to predict
220 different flow properties for the binders. Using these techniques it was attempted to
221 calculate the mixing temperatures of bitumen for different shear rates.
222 Based on the experimental results and analysis, the following conclusions can be drawn
223 - Polymer modified binders are more shear thinning as compared to normal binders
224 as shown by the viscosity-shear rate plot at different temperatures. At higher
225 temperatures, normal binders also show tendency of shear thinning, but at very
226 high shear rates. The critical shear rate for modified binders are lower than the
227 normal binders for all range of temperatures.
228 - The concept of Rheogram for plotting master curve of viscosity versus shear rate
229 is applicable to all the binders, with little deviation observed for EVA PMB. C-Y
230 model fits well with the master curve of all the binders.
231 - Steady shear viscosity measurement using DSR and Brookfield viscometer are
232 found to be in good alignment with each other. Variation in ZSV with temperature
233 can be described well with the exponential model.
234 - Mixing temperature for modified binder are found to be lower for practical shear
235 rates varying from laboratory to field. The mixing temperature requirements
236 decreases with increase in shear rate.
237

238 Recommendation
239 The prediction of mixing temperature by the above method is highly dependent on the
240 correct evaluation and modelling of ZSV. Therefore, direct values should not be taken,
241 as it may be binder specific. Laboratory and field trials with use of these reduced mixing
242 temperatures should be done as a cross check. It is also recommended that specification
243 of viscosity should be mentioned corresponding to the shear rate and blind use of any data
244 should be avoided.

245
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