10

Molecular Dynamics Simulation

Double-network hydrogels are of interest because they offer superior mechanical perfor-
mance.1 They are composed of two networks:1
• The primary network provides hydrogel with functional properties (e.g., pH-, or
thermo-responsivity). In the mechanism of deformation of double network, it is
assumed that the primary network undergoes brittle fracture with load-bearing
chains bridging the damaged zone
• The secondary network is part of the system to prevent material failure. The sec-
ondary network is stable and less dense
The properties of double networks are not a simple combination of the properties of
both components but depend on the combination of crosslinks.1 Both networks are charac-
terized by their respective toughness:1
• the secondary network is referred to as the resistance to local damage (the energy
consumed during the deformation of the secondary network)
• the toughness of the gel is characterized as the global damage (the energy con-
sumed during deformation of the entire network, both primary and secondary).
The toughness of the secondary network is very small in comparison to that of
the primary network
The mechanical properties of network can be expressed, as follows1
σ W global
-----a = -----------------
- ( 1 – λ max ) [10.1]
E2 2W local
where:
σa the maximum stress reached in the primary network
E2 the elastic modulus of the secondary network
Wglobal the toughness of the double network
Wlocal the toughness of the secondary network
λmax the draw ratio

The models of a double network describe the softening of hydrogels as a result of

cracks in the primary network.1 In some models, the chains of the secondary networks
bridge the damaged zone.1 These models provide information about the dynamic develop-
ment of bridging chains.1
The healing process of asphalt materials was considered as the reverse process of
cracking.2 The self-healing is a combination of wetting and intrinsic healing processes.2
The wetting depends on the surface free energy of asphalt binder, and a self-healing
depends on the self-diffusion of asphalt molecules across the crack interface.2 This shows
that the self-healing process has hierarchical, multiscale character.2
94 Molecular Dynamics Simulation

Figure 10.1. Molecular structure of three components of asphalt and linear SBS. [Adapted, by permission, from
Sun, D; Lin, T; Tian, Y; Liu, F, Comput. Mater. Sci., 114, 86-93, 2016.]

Figure 10.2. Layer structure after molecular dynamics simulation. [Adapted, by permission, from Sun, D;
Lin, T; Tian, Y; Liu, F, Comput. Mater. Sci., 114, 86-93, 2016.]
The molecular dynamics simulation is a computer simulation with atoms and/or mol-
ecules interacting according to some basic laws of physics2. The molecular dynamics was
used to examine healing mechanism and evaluate the healing capability of neat and SBS-
 95

modified asphalt binders.2 Three types of molecules representing different constituent spe-
cies (asphaltenes, naphthene aromatics, and saturates) in neat asphalt were considered in
the model (Figure 10.1).2 Figure 10.2 shows that after the molecular dynamics simulation,
the asphalt molecules diffuse across the artificial crack interface (in the middle of each
model) and the traces of crack healing can be seen.2 For a system to attain equilibrium, the
particles move in accordance with the force field diffusing away from their original loca-
tion.2 The mean square displacement of the particles represents the motion of asphalt mol-
ecules.2 The increase in the mean square displacement with time is related to the diffusion
coefficient D, which can be written as follows2
Nα
1 d 2
D = --- lim -----   [ r i ( t ) – r i ( 0 ) ]  [10.2]
6 t → ∞dt
i=1

where:
ri(t) the position vector of particle i at time t.

It was found that the activation energy and the pre-exponential factor are two crucial
parameters for predicting self-healing capability of asphalt binders at different tempera-
tures.2 The activation energy of SBS-modified asphalt is higher than that for the neat
asphalt. The pre-exponential factor of SBS-modified asphalt is much larger than that for
the neat asphalt.2 This indicates that SBS-modified asphalt has a much stronger instanta-
neous healing ability.2 The molecular dynamic methods can provide accurate results in
simulation of the self-healing asphalt mixtures.2
The molecular structures of virgin and aged asphalt were analyzed by mean square
displacement and radial distribution function of molecules and diffusion coefficient.3
Aging weakens the nano-aggregation behavior of asphaltene molecules and reduces the
translational mobility of asphalt molecules.3 The aged asphalt has the higher activation
energy barrier for self-healing.3 The water molecules at the asphalt-aggregate interface
cause degradation of adhesion.3 The virgin asphalt has lower activation energy barrier and
thus the stronger instantaneous healing ability.3
The molecular dynamics modeling was conducted using an open-source code soft-
ware LAMMPS (Large-scale Atomic/Molecular Massively Parallel Simulator).4 Healing
was triggered by the diffusion of asphalt molecules.4 Higher temperature increases diffu-
sivity of molecules and thus higher healing rate.4 For the same crack length asphalt heals
faster when the width of crack is smaller.4
REFERENCES
1 Zidek, J; Milchev, A; Jancar, J; Vilgis, T A, J. Mech. Phys. Solids, 94, 372-87, 2016.
2 Sun, D; Lin, T; Tian, Y; Liu, F, Comput. Mater. Sci., 114, 86-93, 2016.
3 Xu, G; Wang, H; Fuel, 188, 1-10, 2017.
4 Shen, S; Lu, X; Liu, L; Zhang, C, Constr. Bldg. Mater., 126, 197-205, 2016.