Comparative study of various defects in monolayer graphene using molecular dynamics

simulation

Presented by –
Aditya Roy
Ph.D. Scholar

D E PA RT M E N T O F M E C H A N I C A L E N G I N E E R I N G
N AT I O N A L I N S T I T U T E O F T E C H N O L O G Y S I L C H A R I N D I A
 OUTLINE
● Motivation ● Validation
● Problem Statement ● Results and Discussion
● Objectives ● Conclusion
● Introduction ● Future Scope
● Potential Field ● Acknowledgement
● Methodology ● References
● Modelling and Simulation
● Calculation of stresses

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 Motivation

 Graphene has wide range of potential applications (*)

 High strength, stiffness, light weight of graphene (#)
 Unique properties such as- (*)
 High mechanical strength
 Outstanding electrical properties
 Unique optical properties
 High thermal conductivity
(*) Dewapriya, M.A.N., Rajapakse, R.K.N.D., “Molecular Dynamics Simulations and
Continuum Modelling of Temperature and Strain Rate Dependent Fracture Strength
of Graphene with Vacancy Defects”, “J. of Applied Mechanics”, 81, 2014,.
(*) Thomas, S., Ajith, K.M., “Molecular Dynamics Simulation of the Thermo-
mechanical Properties of Monolayer Graphene Sheet”, “International Conference on
Advances in Manufacturing and Materials Engineering”, Procedia Materials Science
5 (2014) 489-498.

(#) Lee, C., Wei, X., Kysar, J. W., and Hone, J. “Measurement of the elastic properties
and intrinsic strength of monolayer graphene,” Science, vol. 321, no. 5887, pp. 385–
388, 2008.

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 Problem Statement

 Methods to produce graphene

 Limitation of nano-scale experimentation

 Computational cost of nano-mechanical modelling and simulation

 The research so far is scattered in terms of influence of various defects on the strength of
graphene

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 Objectives
● To conduct the comprehensive MD simulation studies in order to gain a basic understanding
of the mechanics of defective graphene, this work includes-

 To model the graphene topologies, including defects

 To carry out the MD simulations of uniaxial deformation to determine the behavior of
perfect and defective graphene
 To compare the mechanical properties of graphene with four different defects
 To compare the strength of graphene sheet in both (armchair and zigzag) directions

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 Introduction
● Molecular Dynamic Simulation- • Force acting on atom 𝑖
1. Computational modelling of
material systems • Acceleration of the atom using
2. Performing MD simulations Newton’s second law
requires these important
ingredients-
• An initial system configuration
[r(t=0), v(t=0)] • Determining the new positions
and velocities of atoms at the end
• Interaction potentials for the of timestep (using numerical
system integration algorithms)
• A way to integrate F=ma 1. The use of statistical ensemble like
3. Simulation procedure in MD NPT, NVT, NVE

Source: Cai, W., “Introduction to Molecular Simulations – Stanford University – Winter 2007”.

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 Potential Field
● AIREBO Interatomic Potential - (Adaptive Intermolecular Reactive Empirical
Bond Order) This potential is created by the combination of three potentials.
1. The original REBO term.
2. Lennard Jones term.
3. TORSION term.
● The general form of AIREBO potential is -

REBO Term: L J term: TORSION term:

Source: S.J. Stuart, A.B. Tutein, J.A. Harrison, A reactive potential for hydrocarbons with intermolecular interactions, Journal of Chemical Physics, 112(14) (2000).

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 Methodology

Axial deformation
Creating topologies Generation of ‘Data Creating defects of created
in ‘LAMMPS’ Files’ in VMD using ‘Avogadro’ topologies through
‘LAMMPS’

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 Modelling and Simulation
● Modelling –

 The perfect graphene sheet, 5nm X 5nm with 1008 atoms

 Atoms manipulation (to induce defects)
● Simulation –

 Periodic boundary conditions

 Equilibration of system
 Noose Hover thermostat
 Uniaxial deformation in both directions (Armchair and Zigzag)

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 Modelling and Simulation

(a) (c)
(b) (d)

Fig. 1. A graphene sheet with (a) single vacancy defect, (b) Stone-Wales defect, (c) Nanopore
and (d) crack

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 Calculation of stresses
● Stress may be interpreted in two ways-
 Cauchy stress
 Virial stress
● The virial stress can be defined as-

where, (𝑖, 𝑗) are the directional indices

𝛽 is a number assigned to neighboring atoms which varies from 1 to 𝑁
𝑅 is the position of atom 𝛼 along direction 𝑖
𝐹 is the force along direction 𝑗 on atom 𝛼 due to atom 𝛽
𝑚 is the mass of atom 𝛼, 𝑣 is the velocity and 𝑉 is the total volume

Source: S.J. Stuart, A.B. Tutein, J.A. Harrison, A reactive potential for hydrocarbons with intermolecular interactions, Journal of Chemical Physics, 112(14) (2000).

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 Constant Strain Method
● To determine the Young’s modulus of graphene a constant strain with strain rate of
10^9/sec is applied
● The atomic stresses are captured after each timestep
● The relation between in-plane stress and stiffness matrix is written in terms of-
  11   C11 C12 0   11 
    

 22    C21 C22 0    22 
   0 0 C66    12 
 12  
C 11  C 12
C 11  C 22 , C 1 2  C 2 1 , C 66 
2
● Due to symmetry and
● With the help of elastic constants, the Young’s modulus and Poisson’s ratio may be C22
C C  C12C21
found as- E  11 22 12  12
C22
C

Source: Tsai, J.L., Tu, J.F., Characterizing mechanical properties of graphite using molecular dynamics simulation, Materials and Design, 31, 194-199, (2010).

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 Validation
Table 1. Validation
Reference
Parameters Present study
(*,#)

C11 (GPa) 1033.7 1094*

C12 (GPa) 142.6 136*

Young’s Modulus (TPa) 1.014 1.02 #

Poisson’s ratio 0.1379 0.1248*

Fracture strength (GPa) 165.7 130#

* Thomas, S., Ajith, K.M., Molecular dynamics simulation of the thermo mechanical properties of monolayer graphene sheet, Procedia Materials Science, 5, 489-498, (2014).
# Lee, C., Wei, X., Kysar, J.W., and Hone, J., Measurement of the elastic properties and intrinsic strength of monolayer graphene, Science, 321, 385–388, (2008).

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 Results and Discussion

● The simulations of uniaxial deformation of graphene with single defect has been
performed-

 Single Stone-Wales, single vacancy and single nanopore does not have much effect
on the Young’s modulus of graphene, where as the crack (length 12.28 angstrom,
width 4.25 angstrom) reduces the elasticity of graphene by 14% in its armchair
direction and 18% in its zigzag direction.
 The single defect available in the graphene structure has the adverse effect on the
fracture strength of the graphene in both the loading directions. However, the
presence of nanopore and crack effects the most.
 The graphene is stiffer in its armchair direction and stronger in its zigzag direction.

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 Results and Discussion

(a) (b)
Fig. 2. Stress-Strain plot of perfect and defective graphene, (a) for Armchair, and (b) for Zigzag direction

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 Results and Discussion

Table 2. Comparison of mechanical properties in armchair direction

C11 (GPa) C12(GPa) Y(TPa) mu Fracture strength (GPa)
Perfect SLGS 1074.08 169.04 1.047 0.1573 165.7
S-W defect 1058.34 181.90 1.027 0.1718 161.9
Single vacancy 1070.78 123.90 1.056 0.1157 151.1
Nanopore 1055.86 164.92 1.030 0.1562 141.4
Crack 935.32 180.16 0.9 0.192 143.1

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 Results and Discussion

Table 3. Comparison of mechanical properties in zigzag direction

C11 (GPa) C12(GPa) Y(TPa) mu Fracture strength (GPa)
Perfect SLGS 1025 273.29 0.952 0.266 346.2
S-W defect 1009.12 253.46 0.945 0.251 332.2
Single vacancy 992.99 257.94 0.925 0.259 294.2
Nanopore 970.43 235.86 0.913 0.243 257.9
Crack 848.67 233.83 0.784 0.275 165.2

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 Conclusion

● With the present work its been concluded that-

 Defects have the profound impact on the strength of graphene in both of the
loading directions.
 Apart from the crack, no other defects effect much the Young’s modulus of
graphene.
 The graphene sheet posses higher fracture strength in the zigzag direction as
compared to its armchair direction. However graphene has higher stiffness in its
armchair direction.

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 Future Scope
● Present study make a significant contribution to understand the certain aspects of the
strength of graphene with various defect present. Based on this study, the following
future work is suggested-

 Uncertainty quantification in potential field

 Crack propagation criterion using a comprehensive first-principle simulations
 Controlling fracture of graphene by structural modification

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 Acknowledgement
● The motivation and guidance of Dr. Sudip Dey, Asstt. Prof. NIT Silchar was the key to
explore this study.
● I’d also like to acknowledge the financial support made by TEQIP-III for my presence
in IC-AMER 2019.

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 References
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materials, 74, 90-99 (2017).

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 References
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 Thank You!

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