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Study of Molecular Dynamic Simulations for binary mixture of thin liquid films in confined geometry

Rishab Jain1and Dr. Rajesh Khanna2 Department of Chemical Engineering, National Institute of Technology, Jalandhar Email:jain.rishab89@gmail.com 2 Asst. Prof, Department of Chemical Engineering, Indian Institute of Technology, Delhi Email: rajkh@chemical.iitd.ac.in Abstract Thin liquid films (<100 nm) have a very diverse and wide field of applications because of their presence in a lot of things around us. Thin liquid films form between bubbles and droplets in multiphase systems and an improved understanding of their stability and rupture is beneficial for various industries such as tertiary oil exploration, biotechnology, and microchip design and manufacturing. This pioneering paperdeals with the study of Molecular Dynamics simulations for mixture of thin liquid films confined between solid surfaces. In the present study, Molecular Dynamic simulations have been performed and the programming for it has been done in FORTRAN77 on a machine using LINUX based platform with NAG library installed. Simulations are run for the homogenous mixture of the 2 liquids confined between the solid surfaces such that the 2 liquid films lie between the solid surfaces under consideration and the instabilities generated in the system as result of the Van der Walls interaction among the substrate and the liquid films have been studied. Keywords: Molecular Dynamics, Hamaker constant, Dewetting, Lennard-Jones Potential 1.Introduction Thin liquid films have been the topic of extensive fundamental study for several decades due to their relevance in numerous natural phenomena and industrial applications [1].The stability of thin liquid films is an important issue in many applications. One important aspect is the behavior of thin liquid films (about 100 nm thick) whose dynamics is governed by van der Waals forces that can lead to either rupture (dewetting) or stabilization of the film [2-4]. Hydrodynamic behavior of such thin films has been extensively studied (see [1,5]for review). For film thickness less than about 100 nm, effective molecular interactions between the film surface and the substrate dominate all the other forces, like gravity, and thus determine the film stability. More recent research has focused on liquid bilayers [69], which are relevant to multilayer coatings such as pressure-sensitive adhesives and magnetic media, and also tear films in the human eye [10,11].As for the microscopic calculation approach, Molecular Dynamics (MD) and Monte Carlo (MC) simulation method are often used to investigate the physical phenomena of fluidsolid interactions with very small length scale [1219]. Moreover, as the film thickness continues to thin, layering phenomena [20] will also occur during the spreading procedure and then the continuum theory, and even the use of disjoining pressure corrections, will be useless in the analysis. To overcome this difficulty
1

we apply molecular dynamics (MD) theory to simulate the dynamic evolutions of the whole rupture process in both the cases of films between plates (the solid- liquid situation) and the free films (the liquid-liquid situation). The present simulations will verify qualitatively the dynamic behaviors of the film predicted by the continuum theory in the stage before the onset of the rupture and most importantly will present a clear insight into the evolutions of the occurrence of ruptures. 2.1 Modelling of Solid-Liquid-Solid System SOLID(3)

LIQUID(1) + LIQUID(2)

SOLID(3) Fig.1 : Solid-Liquid-Solid simulation System

The forces for the system can mainly be divided into 2 categories: 2.1.1 Pair interactions Most of the previous works take Lennard-Jones as pair potential. This is an empirical potential function and it has no relationship with continuum theories. Results obtained by MD simulations using LJ potential function cannot be compared with the results obtained from continuum theories. Although, molecular dynamic simulations are very extensive in nature but they cannot be performed beyond a certain limit because of computational constraints so it is very important to determine a critical length of the film where continuum approach becomes significant, in order to draw a parallel between continuum and MD approach a new potential have been proposed, this potential function is based on Born Repulsion forces and Van-Der Wall attraction forces. It is of the form .(1)[22]

i=1,2,3

j=1,2,3

So, expression for force due to pair interactions is Force (Fij) [ ] .(2)

Here represent the pair potential between particle I and j. r6 represents the long range Van-Der wall attraction force and r12 represent the short range Born repulsion force. depend on the material of particles considered. The mixed values i.e. can be determined using combining rules

( (

) )

(3) (4)

Van-Der Wall force of attraction is of the form W(r) = - C/r6 (5)

Where, C is a constant based on the bodies under consideration and is given by conventional Hamaker Constant A. i=1,2,3, j=1, 2,3 Where (particle number density) is known (7)[21] Again, Interaction energy per unit area is given by (8)[22] Writing above equation(8) for n=6 and n=12 and summing up gives . Comparing both the equations(7) & (9) give [ ] ..(10) (9) (6)[22]

where lo=0.137 nm 2.1.2 Molecule-Solid Surface Interactions (Integrated Force Expression) Molecule

Solid Wall Fig.2 : Interaction between molecule and solid surface

.(11)[22] So, net force due to interaction between Solid surface (S) and a molecule(i) by summing up for n=6 and n=12 for (11) Fij= Where D= Distance of the molecule from the solid surface 2.2 Implementation of Model 2.2.1 Net force and acceleration calculation For resolving Force F on a molecule i due to Pair Interactions with molecule j into x and y directions, we have, Fijx,PairPotential = F ( Fijy,PairPotential = F )/d /d ) .(13) .(14) .(12)

Where d= distance between the ith and jth molecule = ( So, net force on any molecule i in y-direction Fiy= F13(Top) - F13(Bottom)+ Similarly, net force on molecule i in x-direction Fix= 2.2.2 Integration algorithm

.(15)

The algorithm used for the system is given by the following set of kinematic equations: .(16) .(17) 2.2.3 Initial conditions The index i is assigned as follows: i= 1 for Pentane i= 2 for Ethylene Glycol i= 3 for graphite

Solving the above model for equilibrium (initial) conditions gives rij,equilibrium=
( )

dij,equilibrium=

3. Results and Discussions Homogeneous mixture case (50:50 liquid mixture) The simulations have been performed by taking 4096 molecules in total and the composition of the mixture, i.e., the ratio of number of molecule of first type liquid (i=1 for Pentane)(shown in red) to the number of molecules of second type liquid(i=2 for Ethylene Glycol)(shown in green) has been kept fixed in this homogeneous case as 50:50 mixture to study the change in patterns observed over the period of time for this particular case. In total there are 32 molecular layers in the simulation system, with 128 molecules of the two liquids mixed in a homogeneous fashion in each layer. For the simulation, time step has been taken to be 10-17 seconds.

Fig.3 : Initial Configuration at time step 0

Fig.4 : Configuration at time step 10000

Fig.5 :Configuration at time step 50000

Fig.6 :Configuration at time step 100000

Fig.7 :Configuration at time step 200000 As can be much seen from above shown simulations at various time steps, the ordering of the molecules close to the solid surface at the top and bottom doesnt change much due to the effect of the attraction on the molecular layers adjacent to the solid surfaces at the top and the bottom even as the time steps for the simulation increases. But in the middle thin liquid film molecular layers, the effect of the solid surface is not that pronounced. So the ordering of the molecular layers changes with time and the instabilities in the system increases with time. Also there is cluster formation in between the molecular layers and dewetting phenomenon at the solid surfaces at the top and bottom is also observed. 4. Conclusions In this we have taken the case of homogeneous liquid mixture, having 4096 molecules (128*32). The ratio of number of molecules of type 1 liquid to that of type 2 liquid is 50:50. Then results were observed for the simulations at various time steps. It is seen that the ordering of the molecules close to the solid surfaces at the top and bottom doesnt change much due to the effect of attraction on the molecular layers adjacent to the solid surfaces at the top and the bottom even as the time steps for the simulation increases. But in the middle thin liquid film molecular layer, the effect of the solid surface is not that pronounced. So the ordering of the molecular layers changes with time and the instabilities in the system increases with time. Also there is cluster formation in between the molecular layers and dewetting phenomenon at the solid surfaces at the top and bottom is also observed. 5. References [1] A. Oron, S.H. Davis, S.G. Bankoff, Rev. Mod. Phys. 69 (1997) 931980 [2] C. Renger, P. Mller-Buschbaum, M. Stamm, G. Hinrichsen, Macromolecules33 (2000) 8388. [3] R.V. Craster, O.K. Matar, J. Fluid Mech. 425 (2000) 235.

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