1 Molecular dynamics simulation to predict virgin bitumen structural

2 properties
3

4 Khadidja Rouidi a,*,Habib Trouzinea, b, Aissa Asrouna, Abdelillah Bezzarb,c

5 a
LGCE, Civil Engineering and Environmental Laboratory, Faculty of Technology, Sidi Bel Abbes University, DZ- 22000
6 Sidi Bel Abbes, Algeria.
7 b
Civil Engineering Department, Tlemcen University, DZ- 13000 Tlemcen, Algeria.
8 c
EOLE, Faculty of Technology, Tlemcen University, DZ- 13000 Tlemcen, Algeria.
9 *
Corresponding author: rouidi-khadidja@hotmail.fr (Rouidi K.)
10
11 Abstract
12 Bitumen, which is crucial to road and asphalt construction, significantly impacts the long-term viability and
13 performance of transportation infrastructure. Understanding bitumen’s intricate molecular composition and
14 behavior is crucial to improving its properties and developing practical materials and methods. Molecular
15 dynamics simulations (MDS) have recently become popular as a powerful method of molecular-level study of
16 bitumen. The article's study describes the applications and advanced features of MD simulations regarding
17 bitumen, including the interactions between molecules, the behavior of phases, the mechanical properties of
18 bitumen, and the effects of temperature are discussed. The review's conclusion states that the potential of MDS
19 to facilitate further advances in the study of bitumen is evident; this will lead to an enhanced understanding of
20 the material and improved bitumen products and infrastructure.
21
22 Keywords: Bitumen, MDS, Mechanical properties, Young’s modulus, Temperature.
23

24 1. Introduction
25 Bitumen, also known as asphalt, remains a fundamental material in the construction industry, particularly
26 for road pavements, due to its excellent mechanical properties and cost-effectiveness [1, 2]. The mechanical
27 behavior of bitumen is crucial in determining the overall performance and durability of asphalt pavements
28 under various loading and environmental conditions [3]. Recent advancements in research have shed light on
29 understanding the intricate mechanical properties of bitumen using both experimental and computational
30 approaches [4-7].
31 Over the years, MDS has become a valuable tool in predicting the mechanical characteristics of materials
32 on a molecular scale. By employing computer algorithms and mathematical models, this approach simulates the
33 behavior of atoms and molecules, offering insights into the dynamic properties of various materials. In bitumen
34 research, MDS has demonstrated its potency in forecasting the properties of asphalt compositions [8-13].
35 In bitumen research, MDS has demonstrated its efficiency in predicting the mechanical properties of
36 different bitumen combinations [12, 14-16]. The purpose of this article is to explore the mechanical properties
37 of three kinds of bitumen material SARA fractions (Saturate, Asphaltene, Resin, and Aromatic): AAA-1, AAK-

1
2
 3

38 1, and AAM-1 [12, 17-20] at different temperatures using MDS.

39 The LAMMPS (Large-Scale Atomic/Molecular Massively Parallel Simulator) software will be used to
40 accurately simulate the behavior of bitumen molecules [21, 22]. To ensure the reliability and legitimacy of the
41 simulation results, the PCFF (Polymer Consistent Force Field) class II will be employed [23-25]. This field of
42 force is commonly utilized in the research field of bitumen [26, 27] because it accurately describes the
43 interactions between molecules and reproduces experimental results. Using the PCFF field of force, we can
44 produce accurate and legitimate predictions of the mechanical properties of bitumen.
45 In this study, we employ MDS to investigate the behavior of the Young's modulus with varying
46 temperatures (223.15 K, 248.15 K, 273.15 K, 298.15 K, 323.15 K, and 348.15 K) for three distinct bitumen
47 materials: AAA-1, AAK-1, and AAM-1.
48
49 2. Materials and methods
50 2. 1. Bitumen
51 The original asphalt samples used in this study are AAA-1, AAK-1 and AAM-1 commonly used in
52 scientific research. These special bitumen samples typically come from the following regions: Canada,
53 Venezuela, and the USA. The elemental analysis of SHRP core bitumen is shown in Table 1.
54 Bitumen samples from different geographical locations have different chemical compositions, which affects
55 their physical and rheological properties. Elemental analysis provides important insights into the fundamental
56 molecular structure and heterogeneity of these asphalt materials. Table 1 provides a comprehensive overview of
57 the elemental composition, including the relative abundance of carbon, hydrogen, nitrogen, sulfur, and other
58 trace elements in the SHRP bitumen core samples examined.
59 Table 1. Elemental analysis for the core SHRP bitumens [28]
60
AAA-1 AAK-1 AAM-1
Origin
Canada Venezuela USA

C wt.% 83.9 83.7 86.8

H wt.% 10.0 10.2 11.2
H+C wt.% 93.9 93.9 98.0
H/C Molar 1.43 1.46 1.55
O wt.% 0.6 0.8 0.5
N wt.% 0.5 0.7 0.6
S wt.% 5.5 6.4 1.2
V ppm 174 1480 58
Ni ppm 86 142 36
Mn g/mol 790 860 1300
61
62
63 By characterizing the elemental composition, researchers can establish correlations between chemical

4
 5

64 composition and observed asphalt performance characteristics. This information can serve as a basis for further
65 studies on molecular structure, aging behavior and possible modifications to improve the durability and
66 functionality of asphalt materials in various applications such as roads and road construction.
67 Table 2 described the typical values for penetration at 25°C for AAA-1, AAK-1 and AAM-1 bitumens
68 according to [28].
69 Table 2. Typical values for penetration at 25°C for AAA-1, AAK-1 and AAM-1 [28]
70
Bitumen origin Bitumen name Penetration at 25°C
Lloydminster AAA-1 155
Boscan AAK-1 65
West Texas Intermediate AAM-1 63
71
72 2. 2. Molecular model of bitumen
73 Bitumen has four distinct components: saturate, aromatic, resin and asphaltene SARA fractions. Given the
74 intricate nature of these components, selecting an appropriate molecular model is crucial to improve the
75 precision of molecular simulations. For this study, the 12-molecule bitumen model as illustrated in Fig. 1 [29]
76 was utilized to represent bitumen, thus, its three kinds were detailed as shown in Table 3 [29].

C30H62 C29H50O C30H46 C66H81N

C35H62 C36H57N C51H62S C42H54O

C40H59N C40H60S C35H44 C18H10S2

77
78 Fig. 1 - Molecular models of bitumen [29]
79
80

6
 7

81
82
83
84
85
86 Table 3. Chemical characteristics of three kinds of bitumen AAA-1 AAK-1 and AAM-1 [29]
87
SARA Number of molecules in model system
88
fractions Molecule AAA-1 AAK-1 AAM-1 Molar mass
89
90 C30H62 4 2 1 422.9
Saturate
91 C35H62 4 2 1 483.0
92 C30H46 13 10 21 406.8
Aromatic
93 C35H44 11 10 20 464.8
C29H50O 5 4 10 414.8
94
C36H57N 4 4 10 530.9
95 Resin C18H10S2 15 12 4 290.4

96 C40H60S 4 4 10 554.0
C40H59N 4 4 10 573.1
97
C66H81N 2 2 1 888.5
98 Asphaltene C51H62S 3 3 1 707.2

99 C42H54O 3 3 1 575.0

100
101 2. 3. PCFF force field parameters
102 Polymer Consistent Force Field (PCFF) has been utilized in our simulation to estimate the properties of
103 bitumen systems. In essence, PCFF is a class II force field that aims to describe non-bonded van der Waals and
104 electrostatic interactions between atoms; total potential energy comprises valence and non-bond terms, as
105 detailed in Eq. (1).

Etotal =∑ Eb + ∑ E a+ ∑ Et + ∑ Eo + ∑ E bb + ∑ E ba+ ∑ E bt + ∑ E aa + ∑ Eat + ∑ Eaa t

' ' '

106
107
Valence terms
+∑ E +∑ E
vdw elec
108
109 (1) Non-bond terms
110
111
112 Where:
113 Eb, Ea, Et, Eo are bond energy, angle energy, torsion angle energy, and out-of-plane angle energy,
114 respectively. The interconnection between them is Ebb’, Eba, Ebt, Eaa’, Eat, Eaa’t.
115 Evdw Van der Waals energy illustrated by Lennard-Jones (LJ) 9-6 potential in Eq. (2).

8
 9

116

( ) ( )
0 9 0 6
vdw r r
117 E =ɛ ij ⌊ 2 ij −3 ij ⌋ (2)
r ij r ij
118
119 Eelec Coulombic electrostatic energy illustrated Coulombic forces in Eq. (3).
120
elec qi q j
121 E = (3)
r ij
122 Where:
123 ɛ ij is the well depth.
0
124 r ij is the distance at which the LJ potential is zero.
125 r ij is the interatomic distance i and j, respectively.
126 qi, qj are partial charges.
127
128 2. 4. Young’s Modulus
129 Young’s modulus is a fundamental material property that plays a crucial role in determining the strain
130 response of a material under applied loads and the deformation behavior of a structure. Accurate determination
131 of this parameter is critical for engineers to perform reliable computer simulations and accurately predict
132 structural response. As an important input to computational models, the elastic modulus accurately predicts the
133 stress distribution, deformation and overall mechanical properties of technical systems under different loading
134 conditions [30].
135 While Young's modulus is not directly calculated in MDS, certain analytical methods can be employed to
136 estimate it. Young's modulus is a metric that gauges the rigidity of a substance and illustrates how it reacts to
137 applied stress.
138 The Stress-Strain Method involves applying strain to the system and measuring the resultant stress. The
139 slope of the stress-strain curve in the elastic region can be used to approximate the value of Young's modulus
140 Eq. (4).
stress σ
141 E= = (4)
strain ℇ
142 Where:
143 E = Young’s modulus (GPa)
144 σ = stress (GPa)
145 ɛ = strain
146 3. Molecular dynamics (MD) simulations results and discussion
147 3. 1. Construction and equilibration of bitumen model
148 For all simulations conducted in this study, the LAMMPS software was utilized. The chosen model for
149 bitumen was the classical 12- model. The proposed component model by [29] is focused on classifying bitumen

10
 11

150 into three distinct types. These types are identified as AAA-1, AAK-1, and AAM-1.
151 To create the amorphous cell module, twelve individual components were combined into a cubic shape with
152 an initial density of 0.1 g/cm3 at a temperature of 298.15 K and a cutoff of 12.5Å. The entirety of the structure
153 was relaxed through a 5000 step geometry optimization process with conjugate gradient.
154 A dynamic simulation NVT was conducted for 500 ps to stabilize the model. Afterward, a dynamic
155 simulation in NPT was executed at 298.15 K and 1 atm for duration of 500 ps, Fig. 2 illustrates equilibration of
156 AAK-1 as an example.

After equilibration

NVT, NPT

157
158 Fig. 2 - Molecular model of bitumen AAK-1 before and after equilibration
159 The ultimate densities of AAA-1, AAK-1, and AAM-1 were recorded as 0.947g/cm 3, 0.965 g/cm3, 0.936
160 g/cm3, respectively, as illustrated in Fig. 3.
1.20E+00

1.00E+00

8.00E-01
Density (gr/cm3)

6.00E-01
AAA-1
AAK-1
4.00E-01 AAM-1

2.00E-01

0.00E+00
1.5
4.5
10.5
07.5
13.5
316.5
612
19.5
915
22.5
18
25.5
21
28.5
24
31.5
27
34.5
30
37.5
33
40.5
36
43.5
39
46.5
42
49.5
45
52.5
48
55.5
51
58.5
54
61.5
57
64.5
60
67.5
63
70.5
66
73.5
69
76.5
72
79.5
75
82.5
78
85.5
81
88.5
84
91.5
87
94.5
100.5
90
97.5
103.5
93
106.5
96
102
109.5
99
105
112.5
108
115.5
111
118.5
114
121.5
117
124.5
120
127.5
123
130.5
126
133.5
129
136.5
132
139.5
135
142.5
138
145.5
141
148.5
144
151.5
147
154.5
150
157.5
153
160.5
156
163.5
159
166.5
162
169.5
165
172.5
168
175.5
171
178.5
174
181.5
177
184.5
180
187.5
183
190.5
186
193.5
189
196.5
192
199.5
195
202.5
198
205.5
201
208.5
204
211.5
207
214.5
210
217.5
213
220.5
216
223.5
219
226.5
222
229.5
225
232.5
228
235.5
231
238.5
234
241.5
237
244.5
240
247.5
243
250.5
246
253.5
249
256.5
252
259.5
255
262.5
258
265.5
261
268.5
264
271.5
267
274.5
270
277.5
273
280.5
276
283.5
279
286.5
282
289.5
285
292.5
288
295.5
291
298.5
294
301.5
297
304.5
300
307.5
303
310.5
306
313.5
309
316.5
312
319.5
315
322.5
318
325.5
321
328.5
324
331.5
327
334.5
330
337.5
333
340.5
336
343.5
339
346.5
342
349.5
345
352.5
348
355.5
351
358.5
354
361.5
357
364.5
360
367.5
363
370.5
366
373.5
369
376.5
372
379.5
375
382.5
378
385.5
381
388.5
384
391.5
387
394.5
390
397.5
393
400.5
396
403.5
399
406.5
402
409.5
405
412.5
408
415.5
411
418.5
414
421.5
417
424.5
420
427.5
423
430.5
426
433.5
429
436.5
432
439.5
435
442.5
438
445.5
441
448.5
444
451.5
447
454.5
450
457.5
453
460.5
456
463.5
459
466.5
462
469.5
465
472.5
468
475.5
471
478.5
474
481.5
477
484.5
480
487.5
483
490.5
486
493.5
489
496.5
492
499.5
495
498
Time (ps)
161
162 Fig. 3 – Density curve of three types of bitumen AAA-1, AAK-1, and AAM-1
163
164 3. 2. Models validation
165 We calculated densities, cohesive energy densities, solubility and glass transition to support our research
166 findings. These values were then compared to the results of molecular dynamics calculations and experimental

12
 13

167 studies. The contrasting analysis is listed in Table 4.

168 Table 4. Calculated Properties of three types of bitumen AAA-1 AAK-1 AAM-1 with MD Simulation
169
Parameters AAA-1 AAK-1 AAM-1 References
3
Density (gr/cm )
0.947 0.965 0.936 [14, 31-34]
(298.15 K)
CED (108 J/m3 ) 3.05 3.21 2.07 [35-37]
δ ((J/cm3 ) 1/2) 17.46 17.92 14.4 [29, 36-37]
Tg (K) 251.48 250.82 249.61 [14][19][31][38]
Viscosity (Cp)
0.45 0.6 0.94 [39][40]
(298.15 K)
170
171 The measure of cohesive energy density CED Eq. 5 determines the level of cohesion within a substance.
E coh
172 CED= (5)
V
173 Where:
174 Ecoh is the cohesive energy.
175 V is the model volume.
176 The assessment of intermolecular interaction within a bitumen molecule model is determined through the
177 mutual attraction of molecules, which can be used to define a solubility parameter that can be calculated
178 from the CED using Eq. (6).
179 δ=√ CED (6)
180 The point at which the mechanical states of asphalt shift from a viscoelastic state to a glassy state is called
181 the Tg, or glass transition temperature, as illustrated in Fig. 4.
182
1.05
AAA-1
1
Density (gr/cm3)

0.95 251.48 K

0.9

0.85

0.8
50 100 150 200 250 300 350 400 450
Temperature (K)
183

14
 15

1.02
1 AAK-1
0.98

Density (gr/cm3)
0.96
250.82 K
0.94
0.92
0.9
0.88
0.86
50 100 150 200 250 300 350 400 450
Temperature (K)
184
1
AAM-1
0.95
Density (gr/cm3)

249.61 K
0.9

0.85

0.8

0.75
50 100 150 200 250 300 350 400 450
Temperature (K)
185
186 Fig. 4 – Glass transition curve of three types of bitumen AAA-1, AAK-1, and AAM-1
187
188 The viscosity [41] [42] of bitumen MD models was calculated by Green Kubo formula. The code which is
189 based on LAMMPS documentation. The simulations were conducted under NVT ensemble for 10 ns and at a
190 temperature of 298.15 K.
191
192 3. 3. Young’s Modulus of three bitumen models
193 Following the equilibration of the three types of bitumen, a molecular dynamics (MD) tensile simulation is
194 conducted throughout 20 ps. The simulation involves subjecting the NPT ensemble to a total deformation along
195 the x-axis at a temperature of 298.15 K. Subsequently; the stress-strain outcomes were collected every 175 fs
196 and visually depicted in Fig. 5.

16
 17

0.35 0,264 GPA

0.3 0,236 GPa
0.25
0,234 GPa
0.2

Stress (GPa)
0.15
0.1
0.05
0
0 1 2 3 4 5 6 7
-0.05
-0.1

Strain

AAA-1 AAK-1 AAM-1

197
198 Fig. 5 – Stress-Strain curve of three types of bitumen AAA-1, AAK-1, and AAM-1 at 298.15 K
199 The values indicated on the curves signify the end of elastic limit. By calculating the slope of each straight
200 line within the elastic region of the three curves, the Young's modulus values of AAA-1, AAK-1, and AAM-1
201 were determined to be E = 1.506 GPa, E = 1.348 GPa, and E = 1.337 GPa, respectively. Based on the MDS and
202 experimental provided references, these values fall within the range of 1 GPa to 2 GPa [14, 43-44].
203 To investigate the impact of temperature on the tensile simulation outcomes for the AAA-1, AAK-1, and
204 AAM-1 bitumen models, a range of five temperatures (-75 °C (223.15 K), -25 °C (248.15 K), 0 °C (273.15 K),
205 50 °C (323.15 K), and 75 °C (348.15 K)) were chosen. These selected temperatures enable the examination and
206 analysis of the tensile properties of the three bitumen models across a spectrum from extremely low to
207 exceedingly high temperatures. The results are illustrated in Fig. 6, Fig. 7, and Fig. 8.
0.4 0.4
0,313 GPa 0,291 GPa
0.3 0.3
Stress (GPa)
Stress (GPa)

0.2 0.2
0.1 0.1
0 0
-1 0 1 2 3 4 5 6 7 -1 0 1 2 3 4 5 6 7
-0.1 -0.1
Strain Strain

223,15 K 248,15 K
208

18
 19

0.4 0.4
0,276 GPa 0,262 GPa
0.3 0.3

Stress (GPa)
Stress (GPa)
0.2
0.2
0.1
0.1
0
-1 0 1 2 3 4 5 6 7 0
-0.1
-1 0 1 2 3 4 5 6 7
-0.2 -0.1
Strain Strain

273,15 K 323,15 K
209
0.4
0,246 GPa
0.3
Stress (GPa)

0.2
0.1
0
-1 0 1 2 3 4 5 6 7
-0.1
Strain

348,15 K
210
211 Fig. 6 – Stress-Strain curves of AAA-1 bitumen under 223.15 K, 248.15 K, 273.15 K, 323.15 K and 348.15 K
212
0.4 0,304 GPa 0,276 GPa
0.3
0.3
Stress (GPa)

0.25
Stress (GPa)

0.2 0.2
0.15
0.1
0.1
0 0.05
-1 0 1 2 3 4 5 6 7 0
-0.1 -1
-0.05 0 1 2 3 4 5 6 7
Strain Strain

223,15 K 248,15 K
213
0,252 GPa 0.3
0.3
0.25 0.25 0,226 GPa
0.2
Stress (GPa)

0.2
Stress (GPa)

0.15 0.15
0.1 0.1
0.05 0.05
0 0
-1
-0.05 0 1 2 3 4 5 6 7 -1
-0.05 0 1 2 3 4 5 6 7
-0.1 -0.1
Strain Strain

273,15 K 323,15 K
214

20
 21

0.3
0,207 GPa
0.2

Stress (GPa)
0.1
0
-1 0 1 2 3 4 5 6 7
-0.1
-0.2
Strain

348,15 K
215

216 Fig. 7 – Stress-Strain curves of AAK-1 bitumen under 223.15 K, 248.15 K, 273.15 K, 323.15 K and 348.15 K
217
0.4 0,292 GPa 0,272 GPa
0.3
0.3 0.25
Stress (GPa)

Stress (GPa)
0.2 0.2
0.15
0.1 0.1
0.05
0 0
-1 0 1 2 3 4 5 6 7 -1
-0.05 0 1 2 3 4 5 6 7
-0.1 -0.1
Strain Strain

223,15 K 248,15 K
218
0.3 0,254 GPa 0.3 0,223 GPa
0.25 0.25
0.2 0.2
Stress (GPa)
Stress (GPa)

0.15 0.15
0.1 0.1
0.05 0.05
0 0
-0.05 0 1 2 3 4 5 6 7 -0.05 0 1 2 3 4 5 6 7
-0.1 -0.1
Strain Strain

273,15 k 323,15 K
219
0.4
0.3 0,221 GPa
Stress (GPa)

0.2
0.1
0
0 1 2 3 4 5 6 7
-0.1
Strain

348,15 K
220

221 Fig. 8 – Stress-Strain curves of AAM-1 bitumen under 223.15 K, 248.15 K, 273.15 K, 323.15 K and 348.15 K

22
 23

222
223 In line with the previous section, the Young's modulus values of each type of bitumen AAA-1, AAK-1, and
224 AAM-1, at various temperatures, are listed in the following Table 5.
225 Table 5. Young’s Modulus value of three types of bitumen AAA-1 AAK-1 AAM-1 under different
226 temperatures.
227
Temperatur E (GPa)
e
AAA-1 AAK-1 AAM-1
(K)

223.15 1.790 1.737 1.669

248.15 1.662 1.569 1.556

273.15 1.579 1.440 1.454

298.15 1.506 1.348 1.337

323.15 1.496 1.290 1.277

348.15 1.409 1.180 1.263

228

229
230 We observed that as the temperature increased, the Young's modulus decreased for all three materials. This
231 conforms to theoretical predictions [45, 46], where thermal energy weakens intermolecular bonds and makes
232 materials more easily deformed when heated.
233 Across the temperatures examined, AAA-1 was identified as having the greatest Young's modulus, hinting
234 at its elastic rigidity enduring the interference of thermal energy on molecular structure with a rigidity loss on
235 the order of 381 MPa between 223.15 K and 348.15 K. Conversely, AAK-1 and AAM-1 each had visibly lower
236 Young's modulus with a rigidity loss of 557 MPa and 406 MPa respectively; possibly suggesting their
237 structures were more susceptible to deformation with elevated temperatures.
238 To support these results and analyze them effectively, a (MDS) was conducted for the three types of
239 bitumen, AAA-1, AAK-1, and AAM-1, at room temperature (298.15 K) along the y and z-axis. Young’s
240 modulus results of the three types of bitumen are illustrated in Table 6.
241 Table 6. Young’s Modulus value of three types of bitumen AAA-1 AAK-1 AAM-1 at 298.15 K along y and z
242 axis.
E (GPa)
Axis
AAA-1 AAK-1 AAM-1
y 1.099 1.333 1.305
z 2.218 1.194 1.235
243

24
 25

244
245
246 The outcomes of the molecular dynamics calculations showed different variations in Young's modulus for
247 the different types of bitumen and the different loading directions. In the x-axis direction, AAA-1 demonstrated
248 the greatest Young's modulus, followed by AAK-1 and AAM-1. This trend is attributed to specific molecular
249 associations and chemical forces between molecules within each composition, these forces influence the
250 mechanical behavior of the composition.
251 In the y-axis direction, AAK-1 demonstrated the greatest Young's modulus with 1.333 GPa, indicating its
252 increased tensile strength compared to AAA-1 and AAM-1, with values of Young’s modulus 1.099 GPa and
253 1.305 GPa, respectively. The molecular composition of AAK-1 may have a role in the increased strength of the
254 intermolecular interactions and the more effective transmission of loads in this direction. The Young's modulus
255 of the y-axis was lower for the AAA-1 and AAM-1, which suggests that they have a decreased resistance to
256 deformation.
257 In the z-axis direction, AAA-1 exhibited once again the greatest Young's modulus with 2.218 GPa,
258 suggesting that it is more stiffer than other materials in this direction. The Young's modulus of the AAK-1 and
259 AAM-1 was lower in the z-axis with 1.194 GPa and 1.235 GPa. This indicates that they are more susceptible to
260 deformation when loaded in the z-axis.
261 The resultant Young's modulus, obtained by combining the individual directional moduli, provides an
262 overall measure of the material's stiffness. The resultant Young's modulus was highest for AAA-1, followed by
263 AAK-1 and AAM-1. This indicates that the overall stiffness of bitumen AAA-1 is greater than that of AAK-1
264 and AAM-1.
265 The mechanical properties of bitumen are essential to evaluate in civil engineering applications where they
266 are incorporated as cohesive materials in asphalt pavements. At the molecular level, variations in chemical
267 composition between AAA-1, AAK-1, and AAM-1 bitumen result in divergent network architectures. AAA-1
268 possesses a balanced and homogeneous molecular distribution relative to AAK-1 and AAM-1. This structural
269 configuration leads to enhanced intermolecular attractive forces and constrained molecular mobility. When
270 considering the scaling effects between the molecular and macro scales, the denser AAA-1 architecture
271 translates to a material form that is inherently more cohesive.
272 In contrast, the more flexible topological structures in AAK-1 and AAM-1 generate bitumen whose
273 behavior at the macroscopic scale is less restricted. Comprehending this scaling phenomenon enables civil
274 engineers to predict mechanical response under traffic loading conditions. Given its dense nature and ensuing
275 matrix cohesion, AAA-1 was anticipated to exhibit the highest Young's modulus. Conversely, the less
276 constrained architectures of AAK-1 and AAM-1 suggest their moduli would be lower and comparable.
277 Therefore, molecular insights can facilitate material selection by civil engineers by enabling forecasting of the
278 key stiffness property of Young's modulus for designing of resilient asphalt pavements.
279
280 4. Conclusion
281 This analysis of the molecular dynamics of these bitumen AAA-1, AAK-1, and AAM-1 materials provides

26
 27

282 important information about their temperature-dependent behavior regarding the Young's modulus. Our results
283 consistently demonstrate that the Young's modulus decreases as the temperature increases. This emphasizes the
284 significance of temperature regulation and the understanding of the mechanical properties of these substances.
285 Our research outcomes provide a precious resource for improving and establishing materials that rely heavily
286 on temperature to influence their mechanical properties and lifespan. Future studies can broaden the
287 temperature range and introduce nanoclusters to investigate other factors affecting Young’s modulus, such as
288 pressure and strain rate. This will enable us to obtain a more extensive understanding of the underlying
289 principles that operate.
290
291
292 References

293 [1] C. Li, Q. Liu, J. Lei, Z. Zhang, C. Fu, F. Pan, Influence of mineral fillers properties on the bonding properties
294 of bitumen mastics, Constr. Build. Mater.318 (2022). https://doi.org/10.1016/j.conbuildmat.2021.126013.
295 [2] M. Nandal, H. Sood, P. K. Gupta, A review study on sustainable utilisation of waste in bituminous layers of
296 flexible pavement, Case. Stud. Constr. Mater. 19 (2023). https://doi.org/10.1016/j.cscm.2023.e02525.
297 [3] S. Malinowski, A. Woszuk, W. Franus, Modern two-component modifiers inhibiting the aging process of road
298 bitumen, Constr. Build. Mater. 409 (2023). https://doi.org/10.1016/j.conbuildmat.2023.133838.
299 [4] S. Karahancer, M. Enieb, M. Saltan, S. Terzi, E. Eriskin, A. Cengizhan, M. Y. Akbas, Evaluating mechanical
300 properties of bitumen and hot mix asphalt modified with nano ferric oxide, Constr. Build. Mater. 234 (2020).
301 https://doi.org/10.1016/j.conbuildmat.2019.117381.
302 [5] M.S. Eisa, A. Mohamady, M.E. Basiouny, A. Abdulhamid, J. R. Kim, Mechanical properties of asphalt
303 concrete modified with carbon nanotubes (CNTs), Case. Stud. Constr. Mater. 16 (2022).
304 https://doi.org/10.1016/j.cscm.2022.e00930.
305 [6] M.J. Kim, S. Kim, D.Y. Yoo, H.O. Shin, Enhancing mechanical properties of asphalt concrete using synthetic
306 fibers, Constr. Build. Mater. 178 (2018) 233-243. https://doi.org/10.1016/j.conbuildmat.2018.05.070.
307 [7] C.J. Wei, S. Poovaneshvaran, M.R.M. Hasan, M.O. Hamzah, J. Valentin, A. Sani, Microscopic analysis and
308 mechanical properties of Recycled Paper Mill Sludge modified asphalt mixture using granite and limestone
309 aggregates, Constr. Build. Mater. 243 (2020). https://doi.org/10.1016/j.conbuildmat.2020.118172.
310 [8] H. Yao, J. Liu, M. Xu, J. Ji, Q. Dai, Z. You, Discussion on molecular dynamics (MD) simulations of the
311 asphalt materials, Adv. Colloid. Interface. Sci. 299 (2022). https://doi.org/10.1016/j.cis.2021.102565.
312 [9] G. Li, Z. Chen, Y. Tan, X. Cong, Y. Dong, S. Xiao, Experimental and molecular dynamics simulation of hard
313 asphalt microstructure, Constr. Build. Mater. 377 (2023). https://doi.org/10.1016/j.conbuildmat.2023.131025.
314 [10] W. Tian, Y. Gao, Y. Li, J. Zhu, M. Zhan, S. Wang, Molecular dynamics study on the effect of rheological
315 performance of asphalt with different plasticizers, Constr. Build. Mater. 400 (2023).
316 https://doi.org/10.1016/j.conbuildmat.2023.132791.
317 [11] Z. Chen, J. Pei, R. Li, F. Xiao, Performance characteristics of asphalt materials based on molecular dynamics
318 simulation - A review, Constr. Build. Mater. 189 (2018) 695-710.
319 https://doi.org/10.1016/j.conbuildmat.2018.09.038.

28
 29

320 [12] Z. Fan, F. Pan, L. Sun, D. Wang, P. Liu, Multiscale investigation on bitumen-aggregate interfacial debonding
321 using molecular dynamics and finite element method, Constr. Build. Mater. 397 (2023).
322 https://doi.org/10.1016/j.conbuildmat.2023.132326.
323 [13] L. Luo, P. Liu, M. Oeser, A molecular dynamics simulation study on enhancement of thermal conductivity of
324 bitumen by introduction of carbon nanotubes, Constr. Build. Mater. 353 (2022).
325 https://doi.org/10.1016/j.conbuildmat.2022.129166.
326 [14] J. Du, Y. Jin, S. Hou, R. Jin, Q. Wang, Effect of component characteristics on mechanical properties of
327 asphalt: A molecular dynamics study, Case. Stud. Constr. Mater. 18 (2023).
328 https://doi.org/10.1016/j.cscm.2023.e02007.
329 [15] T. Zhang, S. Gao, J. Yu, Y. He, X. Han, R. Zhuang, Preparation and performance of self-healing SBS
330 modified bitumen based on dynamic disulfide bonds, Constr. Build. Mater. 397 (2023).
331 https://doi.org/10.1016/j.conbuildmat.2023.132394.
332 [16] E. Chailleux, C. Queffélec, I. Borghol, F. Farcas, S. Marceau, B. Bujoli, Bitumen fractionation: Contribution
333 of the individual fractions to the mechanical behavior of road binders, Constr. Build. Mater. 271 (2021).
334 https://doi.org/10.1016/j.conbuildmat.2020.121528.
335 [17] R. Li, Q. Guo, H. Du, J. Pei, Mechanical Property and Analysis of Asphalt Components Based on Molecular
336 Dynamics Simulation, J. Chem. (2017). https://doi.org/10.1155/2017/1531632.
337 [18] G. Li, Y. Tan, Y. Fu, P. Liu, C. Fu, M. Oeser, Density, zero shear viscosity and microstructure analysis of
338 asphalt binder using molecular dynamics simulation, Constr. Build. Mater. Volume 345 (2022).
339 https://doi.org/10.1016/j.conbuildmat.2022.128332.
340 [19] Y. Kang, D. Zhou, Q. Wu, R. Liang, S. Shangguan, Z. Liao, N. Wei, Molecular dynamics study on the glass
341 forming process of asphalt, Constr. Build. Mater. 214 (2019) 430-44.
342 https://doi.org/10.1016/j.conbuildmat.2019.04.138.
343 [20] Q. Liu, R. Fang, W. Cha, J. Wu, P. Liu. Influence of SARA fractions on the bitumen property using
344 molecular dynamics simulation. (2023). https://doi.org/10.2139/ssrn.4387385.
345 [21] A.P. Thompson, H.M. Aktulga, LAMMPS - a flexible simulation tool for particle-based materials modeling
346 at the atomic, meso, and continuum scales, Comput. Phys. Commun. 271 (2022).
347 https://doi.org/10.1016/j.cpc.2021.108171.
348 [22] Y. Hou, H. Zhang, J. Wu, L. Wang, H. Xiong, Study on the microscopic friction between tire and asphalt
349 pavement based on molecular dynamics simulation, Int. J. Pavement. Res. Technol. 11 (2018) 205-212.
350 https://doi.org/10.1016/j.ijprt.2017.09.001.
351 [23] H. Sun, Force Field for Computation of Conformational Energies, Structures, and Vibrational Frequencies of
352 Aromatic Polyesters, J. Comput. Chem. 15 (1994) 752-768. https://doi.org/10.1002/jcc.540150708.
353 [24] H. Sun, Ab Initio Calculations and Force Field Development for Computer Simulation of Polysilanes,
354 Macromolecules. Vol. 28, No. 3, (1995). https://doi.org/10.1021/ma00107a006.
355 [25] H. Sun, S.J. Mumby, J.R. Maple, A.T. Hagler, An ab Initio CFF93 All-Atom Force Field for Polycarbonates.
356 J. Am. Chem. Soc. (1994). https://doi.org/10.1021/ja00086a030.

30
 31

357 [26] Y. Gao, Y. Zhang, C. Zhang, X. Liu, R. Jing, Quantifying oxygen diffusion in bitumen films using molecular
358 dynamics simulations, Constr. Build. Mater. 331 (2022). https://doi.org/10.1016/j.conbuildmat.2022.127325.
359 [27] Z. Du, X. Zhu, F. Li, S. Zhou, Z. Dai, Failure of the Asphalt-Aggregate Interface under Tensile Stress:
360 Insight from Molecular Dynamics, J. Mater. Civ. Eng. 33 (2021). https://doi.org/10.1061/(ASCE)MT.1943-
361 5533.0003601.
362 [28] D. Lesueur, The colloidal structure of bitumen: Consequences on the rheology and on the mechanisms of
363 bitumen modification, Adv Colloid Interface Sci. 145 (2009) 42–82. https://doi.org/10.1016/j.cis.2008.08.011.
364 [29] D.D. Li, M.L. Greenfield. Chemical compositions of improved model asphalt systems for molecular
365 simulations, Fuel. (2013). https://doi.org/10.1016/j.fuel.2013.07.012.
366 [30] F. Belabdelouahab, H. Trouzine, H. Hellal, B. Rahali, S. Ould Kaci, M. Medine: Comparative Analysis of
367 Estimated Young’s Modulus of Rubberized Mortar and Concrete, Int. J. Civ. Eng (2018) 16:243–253.
368 https://doi.org/10.1007/s40999-016-0119-x.
369 [31] R.E. Robertson, J.F. Branthaver, P.M. Harnsberger, J.C. Petersen, S.M. Dorrence, J.F. McKay, T.F. Turner,
370 A.T. Pauli, S.C. Huang, J.D. Huh, J. Tauer, K.P. Thomas, D.A. Netzel, F.P. Miknis, T.M. Williams, J.J. Duvall,
371 F.A. Barbour, C. Wright, Fundamental properties of asphalts and modified Asphalts, Interpretive Rep. Vol.1
372 (2001).
373 [32] W. Sun, H. Wang, Moisture effect on nanostructure and adhesion energy of asphalt on aggregate surface: A
374 molecular dynamics study, Appl. Surf. Sci. 510 (2020). https://doi.org/10.1016/j.apsusc.2020.145435.
375 [33] G. Xu, H. Wang, Molecular dynamics study of interfacial mechanical behavior between asphalt binder and
376 mineral aggregate, Constr. Build. Mater. 121 (2016) 246-254.
377 https://doi.org/10.1016/j.conbuildmat.2016.05.167.
378 [34] L. Zhang, M.L. Greenfield, Effects of Polymer Modification on Properties and Microstructure of Model
379 Asphalt Systems, Energy. Fuels. 22 (2008) 3363-3375. https://doi.org/10.1021/ef700699p.
380 [35] W. Xu, X. Qiu, S. Xiao, G. Hu, F. Wang, J. Yuan, Molecular Dynamic Investigations on the Adhesion
381 Behaviors of Asphalt Mastic-Aggregate Interface, Materials. 13 (2020). https://doi.org/10.3390/ma13225061.
382 [36] G. Xu, H. Wang, Study of cohesion and adhesion properties of asphalt concrete with molecular dynamics
383 simulation, Comput. Mater. Sci. 112 (2016) 161-169. https://doi.org/10.1016/j.commatsci.2015.10.024.
384 [37] G. Sun, Z. Niu, J. Zhang, X. Tan, Y. Jing, Z. Chen, Impacts of asphalt and mineral types on interfacial
385 behaviors: A molecular dynamics study, Case. Stud. Constr. Mater. 17 (2022).
386 https://doi.org/10.1016/j.cscm.2022.e01581.
387 [38] I.R. Harrison, G. Wang, T.C. Hsu, A Differential Scanning Calorimetry Study of Asphalt Binders, Strategic
388 Highway Research Program (SHRP), National Academy of Sciences, Washington, D.C, 1992. SHRP-A/UFR-
389 92-612.
390 [39] Y. Jiao, Y. Yao, H. Qiu, H. Chen, Y. Wu, A Molecular Dynamics Analysis of the Thickness and Adhesion
391 Characteristics of the Quasi-Liquid Layer at the Asphalt–Ice Interface, Materials 2024, 17, 1375.
392 https://doi.org/10.3390/ma17061375.
393 [40] F. Fallah, F. Khabaz, Y. R. Kim, S. R. Kommidi, H. F. Haghshenas, Molecular dynamics modeling and
394 simulation of bituminous binder chemical aging due to variation of oxidation level and saturate-aromatic-resin -

32
 33

395 asphaltene fraction, Fuel 237 (2019) 71–80. https://doi.org/10.1016/j.fuel.2018.09.110.

396 [41] S. Rosta, L. Gaspar, Dynamic Viscosity Prediction of Blends of Paving Grade Bitumen with Reclaimed
397 Bitumen, Period. Polytech. Transp. Eng. 51(2023), PP. 263-269. https://doi.org/10.3311/PPtr.21926.
398 [42] K. Z. Ramdan, S. A. Abo-Qudais, Effect of Superpave Short-Term Aging on Binder and Asphalt Mixture
399 Rheology, Period. Polytech. Transp. Eng. 45 (2017), pp. 196-205. https://doi.org/10.3311/PPtr.10477.
400 [43] H. Yao, Q. Dai, Z. You, A. Bick, M. Wang, Modulus simulation of asphalt binder models using Molecular
401 Dynamics (MD) method, Constr. Build. Mater. 162 (2018) 430-441.
402 https://doi.org/10.1016/j.conbuildmat.2017.09.106.
403 [44] E.R. Dourado, R.A. Simao, L.F.M. Leite, Mechanical properties of asphalt binders evaluated by atomic force
404 microscopy, J. Microsc, 245 (2012) 119-128. https://doi.org/10.1111/j.1365-2818.2011.03552.x.
405 [45] G. Huang, J. Zhang, B. Hui, H. Zhang, Y. Guan, F. Guo, Y. Li, Y. He, D. Wang, Analysis of Modulus
406 Properties of High-Modulus Asphalt Mixture and Its New Evaluation Index of Rutting Resistance,
407 Sustainability. 15 (2023). https://doi.org/10.3390/su15097574.
408 [46] S. Zhuang, J. Wang, M. Li, C. Yang, J. Chen, X. Zhang, Z. Zhao, D. Li, J. Ren, Rutting and Fatigue
409 Resistance of High-Modulus Asphalt Mixture Considering the Combined Effects of Moisture Content and
410 Temperature, Buildings. 13 (2023). https://doi.org/10.3390/buildings13071608.

34