Fully Atomistic Molecular Dynamics Simulation / Modelling of

Polybutadiene-Styrene

Submitted in fulfillment of the requirements of

Subject Code- MATERIAL TECHNOLOGY AND TESTING

(Assignment)
By

Name: VIVEK V
(ID NO: 2016SA30008)

BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE, PILANI

CAMPUS
Second Semester 2016-17
TABLE OF CONTENTS

1) Modeling of Monomer

1.1 Modeling of Styrene Monomer

1.2 Modeling of Butadiene Monomer

2) Analysis of Monomer

2.1 Properties of Styrene Monomer

2.2 Properties of Butadiene Monomer

3) Modeling of Poly Butadiene- Styrene

4) Analysis of Poly Butadiene- Styrene

5) Results

Page | 2
Given Problem:

Fully Atomistic Molecular Dynamics Simulation / Modeling of Polybutadiene-

Styrene

Input:
Butadiene 10 & Styrene 5 repeats

Reports:
1. Tabulate the Monomer properties
2. Tabulate the Polymer Structure properties
3. Tabulate Energy Batch Average
4. Add the plots of polymer, density distribution, 3D Molecular drawing

Page | 3
1) MODELING OF MONOMER

PolyButadiene-Styrene is derived from two monomers, Styrene and Butadiene

1.1 Modeling of Styrene Monomer

Page | 4
1.2 Modelling of Butadiene Monomer

Chemical Formula for Butadiene is C4H6

Page | 5
2) Analysis of Styrene Monomers
We need to configure the force field parameters for atomic species that make
up the monomers and also structure optimization and charge calculation
operations.

2.1 Properties of Styrene Monomer

=== Volumetric Properties ===

VOLUMETRIC PROPERTIES TEMP VALUE UNIT

van der Waals Volume Vw - 64.0369 cc/mol

Molar Volume at 298[K] V 298.0 96.9751 cc/mol

Molar Volume V(T) 298.0 96.9751 cc/mol

Density at 298[K] rho 298.0 1.074 g/cc

Density rho(T) 298.0 1.074 g/cc

Coefficient of Volumeric Thermal alpha_r 298.0 0.0 10^-6/K

Expansion (Rubbery)

Coefficient of Volumeric Thermal alpha(T) 298.0 255.6785 10^-6/K

Expansion

Coefficient of Linear Thermal beta(T) 298.0 85.2262 10^-6/K

Expansion

Page | 6
 === Thermodynamic Properties ===

THERMODYNAMIC PROPERTIES TEMP VALUE UNIT

Molar Heat Capacity at Constant Pressure (Glassy)

Cp^s 298.0 133.5052 J/(mol*K)
at 298[K]

Molar Heat Capacity at Constant Pressure

Cp^l 298.0 174.8015 J/(mol*K)
(Rubbery) at 298[K]

Molar Heat Capacity at Constant Pressure (Glassy) Cp^s(T) 298.0 133.5052 J/(mol*K)

Molar Heat Capacity at Constant Pressure

Cp^l(T) 298.0 174.8015 J/(mol*K)
(Rubbery)
Jump Delta_Cp(Tg) in Heat Capacity at Glass
delta_Cp(Tg) - 31.2071 J/(mol*K)
Transition

=== Cohesive Energy and Solubility Parameter ===

COHESIVR PROPERTY TEMP VALUE UNIT

Cohesive Energy (Fedors) E_coh1 - 39197.2216 J/mol

Cohesive Energy (Krevelen) E_coh2 - 36933.2444 J/mol

Cohesive Energy Density (Fedors) e_coh1 - 404.1987 J/cc

Cohesive Energy Density

e_coh2 - 380.8528 J/cc
(Krevelen)

Solubility Parameter (Fedors) delta1 - 20.1047 (J/cc)^(1/2)

Solubility Parameter (Krevelen) delta2 - 19.5154 (J/cc)^(1/2)

Dispersion Component of Molar

Fd - 1754.2296 (J^0.5*cm^1.5/mol)
Attraction Constant

Page | 7
 Dispersion Component of
delta_d - 18.0895 (J/cc)^0.5
Solubility Parameter

=== Glass Transition Temperature ===

Glass Transition
Tg - 381.672 K
Temperature
=== Surface Tension ===
SURFACE TENSION TEMP VALUE UNIT
Molar Parachor Ps - 252.4812 (cc/mol)*(dyn/cm)^(1/4)

Surface Tension at 298[K] by

gamma 298.0 41.0007 dyn/cm
e_coh1

Surface Tension at 298[K] by Ps gamma 298.0 45.9489 dyn/cm

Surface Tension by Ps gamma(T) 298.0 45.9489 dyn/cm

Dispersion Force Component of

gamma_d(T) 298.0 34.7786 dyn/cm
Surface Tension by delta_d

Dispersion Force Component of

gamma_d(T) 298.0 45.9489 dyn/cm
Surface Tension by n

=== Optical Properties ===

Refractive Index at 298[K] n 298.0 1.6037

Molar Refraction
according to R_LL - 33.3427 cc/mol
Lorentz and Lorenz

Molar Refraction
according to R_GD - 58.5472 cc/mol
Gladstone and Dale

Page | 8
 === Electrical Properties ===

ELECTRIC PROPERTY TEMP VALUE UNIT

Dielectric Constant
epsilon 298.0 2.572
(nonpolar) at 298[K]

Dielectric Constant at
epsilon 298.0 2.5671
298[K]

Molar Polarization
according to Lorentz and P_LL - 33.2742 cc/mol
Lorenz

Effective Dipole Moment

mu 298.0 0.0 Debye
at 298[K]

Dissipation Factor at
tan_delta 298.0 -1.0E-4
298[K] 50Hz to 100Hz

Dissipation Factor at
tan_delta 298.0 -1.0E-4
298[K] 1KHz to 10MHz

=== Magnetic Properties ===

Molar Diamagnetic xi_m - 70.9132 cc/mol
Susceptibility

=== Mechanical Properties ===

TEMP VALUE UNIT

Poisson's Ratio (Glassy) at 298[K] nu 298.0 0.3584

Poisson's Ratio (Glassy) vs T nu(T) 298.0 0.3584

Bulk Modulus (Glassy) vs T B(T) 298.0 3598.7036 MPa
Shear Modulus (Glassy) vs T G(T) 298.0 1125.5094 MPa

Young's Modulus (Glassy) vs T E(T) 298.0 3057.7533 MPa

Molar Rao Function (Glassy) U_R - 5866.8397 cm^(10/3)/(sec^(1/3)*mole)

Page | 9
Molar Hartmann Function (Glassy) U_H - 4652.9906 cm^(10/3)/(sec^(1/3)*mole)
Bulk Modulus (Glassy) via Rao
B(T) 298.0 5265.8526 MPa
Function vs T
Shear Modulus (Glassy) via
G(T) 298.0 1310.4981 MPa
Hartmann Function vs T
Entangl. Molecular Weight
M_e 298.0 12706.6558 g/mol
(Rubbery)
Bulk Modulus of Rubbery Polymer
B(T) 298.0 0.0 MPa
vs T
Shear Modulus of Rubbery
G_N(T) 298.0 0.0 MPa
Polymer vs T
Young's Modulus of Rubbery
E(T) 298.0 0.0 MPa
Polymer vs T

Poisson's Ratio (Rubbery) vs T nu(T) 298.0 0.0

Stress of Brittle Fracture sigma_f(T) 298.0 58.9588 MPa
Yield Stress via Young's Modulus
sigma_y(T) 298.0 85.6171 MPa
(Glassy)
Yield Stress via Characteristic Ratio
sigma_y(T) 298.0 146.1589 MPa
(Glassy)

=== Properties of Polymers in Dilute Solutions ===

TEMP VALUE UNIT

Steric Hindrance Parameter sigma - 2.2249

Characteristic Ratio C_infinity - 9.9003

Molar Intrinsic Viscosity Function J - 21.0077 g^0.25*cm^1.5/mol^0.75

Molar Stiffness Function K - 29.4077 g^0.25*cm^1.5/mol^0.75

Page | 10
 === Shear Viscosity ===
SHEAR VISCOSITY PROPERTIES UNIT TEMP VALUE UNIT
Critical Molecular Weight M_cr - 25413.3116 g/mol
A Sum of Group Contributions to the Molar
H_eta_sum - 3897.4764 g*J^(1/3)/mol^(4/3)
Viscosity-Temperature Function
A Side Chain Term of the Molar Viscosity-
H_eta_str - 0.0 g*J^(1/3)/mol^(4/3)
Temperature Function
Molar Viscosity-Temperature Function H_eta - 3897.4764 g*J^(1/3)/mol^(4/3)

Activation Energy for Viscous Flow at Zero Shear

E_eta_infinity - 52.4027 10^3*J/mol
Rate in the Limit of T->Infinity

Critical Zero-Shear Viscosity at 1.2Tg eta_cr(1.2Tg) - 19.7812 N*sec/m^2

critical Zero-Shear Viscosity eta_cr(T) 298.0 0.0 N*sec/m^2

Zero-Shear Viscosity at 1.2Tg eta_0(1.2Tg) - 0.0811 N*sec/m^2

Zero-Shear Viscosity vs T eta_0(T) 298.0 0.0 N*sec/m^2

=== Thermal Conductivity and Thermal Diffusivity ===

THERMAL CONDUCTIVITY TEMP VALUE UNIT

Thermal Conductivity at 298 [K] lambda 298.0 0.135 J/(K*m*sec)

Thermal Conductivity vs T lambda(T) 298.0 0.135 J/(K*m*sec)

Thermal Diffusivity (Glassy) a(T) 298.0 9.8036 cm^2/sec

Thermal Diffusivity (Rubbery) a(T) 298.0 7.4875 cm^2/sec

=== Transport of Small Penetrant Molecules ===

TRANSPORT OF SMALL PENETRANT MOLECULES TEMP VALUE UNIT
Newchor nu - 148.6335
Permeability of Oxygen P_O2 - 363.6868 DU

Permeability of Nitrogen P_N2 - 99.8872 DU

Page | 11
 Permeability of Carbon Dioxide P_CO2 - 1792.2605 DU

=== Thermal Stability ===

Temperature of Half-decomposition T_d,1/2 - 643.3604 K

Molar Thermal Decomposition Function Y_d,1/2 - 67.007 K*kg/mol

2.2 Properties of Butadiene Monomer

=== Volumetric Properties ===
VOLUMETRIC PROPERTY TEMP VALUE UNIT
van der Waals Volume Vw - 37.4859 cc/mol
Molar Volume at 298[K] V 298.0 59.0742 cc/mol
Molar Volume V(T) 298.0 59.0742 cc/mol
Density at 298[K] rho 298.0 0.9157 g/cc
Density rho(T) 298.0 0.9157 g/cc

Coefficient of Volumeric Thermal Expansion (Rubbery) at

alpha_r 298.0 968.5075 10^-6/K
298[K]

Coefficient of Volumeric Thermal Expansion alpha(T) 298.0 968.5075 10^-6/K

Coefficient of Linear Thermal Expansion beta(T) 298.0 322.8358 10^-6/K

=== Thermodynamic Properties ===

THERMODYNAMIC PROPERTY TEMP VALUE UNIT

Molar Heat Capacity at Constant Pressure (Glassy) at 298[K] Cp^s 298.0 81.8441 J/(mol*K)

Molar Heat Capacity at Constant Pressure (Rubbery) at 298[K] Cp^l 298.0 108.1557 J/(mol*K)

Molar Heat Capacity at Constant Pressure (Glassy) Cp^s(T) 298.0 81.8441 J/(mol*K)

Page | 12
 Molar Heat Capacity at Constant Pressure (Rubbery) Cp^l(T) 298.0 108.1557 J/(mol*K)

Jump Delta_Cp(Tg) in Heat Capacity at Glass Transition delta_Cp(Tg) - 27.7893 J/(mol*K)

=== Cohesive Energy and Solubility Parameter ===

COHESIVE ENERY AND SOLUBILITY PROPERTY TEMP VALUE UNIT
Cohesive Energy (Fedors) E_coh1 - 17971.5 J/mol

Cohesive Energy (Krevelen) E_coh2 - 18579.3369 J/mol

Cohesive Energy Density (Fedors) e_coh1 - 304.219 J/cc

Cohesive Energy Density (Krevelen) e_coh2 - 314.5084 J/cc

Solubility Parameter (Fedors) delta1 - 17.4419 (J/cc)^(1/2)

Solubility Parameter (Krevelen) delta2 - 17.7344 (J/cc)^(1/2)

Dispersion Component of Molar Attraction Constant Fd - 941.2075 (J^0.5*cm^1.5/mol)

Dispersion Component of Solubility Parameter delta_d - 15.9326 (J/cc)^0.5

=== Glass Transition Temperature ===

Glass Transition Temperature Tg - 173.6446 K

=== Surface Tension ===

SURFACE TENSION PROPERTY TEMP VALUE UNIT

Molar Parachor Ps - 146.5485 (cc/mol)*(dyn/cm)^(1/4)

Surface Tension at 298[K] by e_coh1 gamma 298.0 33.9249 dyn/cm

Surface Tension at 298[K] by Ps gamma 298.0 37.8733 dyn/cm

Surface Tension by Ps gamma(T) 298.0 37.8733 dyn/cm

Dispersion Force Component of Surface Tension by

gamma_d(T) 298.0 24.4473 dyn/cm
delta_d

Page | 13
Dispersion Force Component of Surface Tension by
gamma_d(T) 298.0 36.4617 dyn/cm
n

=== Optical Properties ===

TEMP VALUE UNIT

Refractive Index at 298[K] n 298.0 1.5188

Molar Refraction according to Lorentz and Lorenz R_LL - 17.9247 cc/mol

Molar Refraction according to Gladstone and Dale R_GD - 30.6486 cc/mol

=== Electrical Properties ===

TEMP Value UNIT
Dielectric Constant (nonpolar) at 298[K] epsilon 298.0 2.3068

Dielectric Constant at 298[K] epsilon 298.0 2.3167

Molar Polarization according to Lorentz and Lorenz P_LL - 18.0189 cc/mol

Effective Dipole Moment at 298[K] mu 298.0 0.0676 Debye

Dissipation Factor at 298[K] 50Hz to 100Hz tan_delta 298.0 2.0E-4

Dissipation Factor at 298[K] 1KHz to 10MHz tan_delta 298.0 2.0E-4

=== Magnetic Properties ===

Molar Diamagnetic Susceptibility xi_m - 36.13 cc/mol

=== Mechanical Properties ===

MECHANICAL PROPERTY TEMP VALUE UNIT
Poisson's Ratio (Glassy) at 298[K] nu 298.0 0.0
Poisson's Ratio (Glassy) vs T nu(T) 298.0 0.0

Page | 14
 Bulk Modulus (Glassy) vs T B(T) 298.0 0.0 MPa
Shear Modulus (Glassy) vs T G(T) 298.0 0.0 MPa
Young's Modulus (Glassy) vs T E(T) 298.0 0.0 MPa
Molar Rao Function (Glassy) U_R - 3143.0418 cm^(10/3)/(sec^(1/3)*mole)
Molar Hartmann Function (Glassy) U_H - 2616.5189 cm^(10/3)/(sec^(1/3)*mole)
Bulk Modulus (Glassy) via Rao Function
B(T) 298.0 0.0 MPa
vs T
Shear Modulus (Glassy) via Hartmann
G(T) 298.0 0.0 MPa
Function vs T
Entangl. Molecular Weight (Rubbery) M_e 298.0 1789.0396 g/mol
Bulk Modulus of Rubbery Polymer vs T B(T) 298.0 2514.5412 MPa
Shear Modulus of Rubbery Polymer vs T G_N(T) 298.0 1.2681 MPa
Young's Modulus of Rubbery Polymer vs
E(T) 298.0 3.8044 MPa
T
Poisson's Ratio (Rubbery) vs T nu(T) 298.0 0.4997
Stress of Brittle Fracture sigma_f(T) 298.0 186.0238 MPa
Yield Stress via Young's Modulus (Glassy) sigma_y(T) 298.0 0.0 MPa
Yield Stress via Characteristic Ratio
sigma_y(T) 298.0 0.0 MPa
(Glassy)
=== Properties of Polymers in Dilute Solutions ===
Steric Hindrance
sigma - 1.674
Parameter
Characteristic
C_infinity - 5.6047
Ratio
Molar Intrinsic
Viscosity J - 4.7286 g^0.25*cm^1.5/mol^0.75
Function
Molar Stiffness
K - 21.5286 g^0.25*cm^1.5/mol^0.75
Function
=== Shear Viscosity ===

TEMP VALUE UNIT

Critical Molecular Weight M_cr - 3578.0791 g/mol

A Sum of Group Contributions to the Molar
H_eta_sum - 1497.8775 g*J^(1/3)/mol^(4/3)
Viscosity-Temperature Function
A Side Chain Term of the Molar Viscosity-
H_eta_str - 0.0 g*J^(1/3)/mol^(4/3)
Temperature Function
Molar Viscosity-Temperature Function H_eta - 1497.8775 g*J^(1/3)/mol^(4/3)

Page | 15
Activation Energy for Viscous Flow at Zero Shear
E_eta_infinity - 21.2343 10^3*J/mol
Rate in the Limit of T->Infinity
Critical Zero-Shear Viscosity at 1.2Tg eta_cr(1.2Tg) - 1492.7314 N*sec/m^2

critical Zero-Shear Viscosity eta_cr(T) 298.0 7.4553 N*sec/m^2

Zero-Shear Viscosity at 1.2Tg eta_0(1.2Tg) - 22.5664 N*sec/m^2

=== Thermal Conductivity and Thermal Diffusivity ===

THERMAL CONDUCTIVITY AND DIFFUSIVITY TEMP VALUE UNIT

Thermal Conductivity at 298 [K] lambda 298.0 0.1786 J/(K*m*sec)

Thermal Conductivity vs T lambda(T) 298.0 0.1786 J/(K*m*sec)

Thermal Diffusivity (Glassy) a(T) 298.0 12.8886 cm^2/sec

Thermal Diffusivity (Rubbery) a(T) 298.0 9.7531 cm^2/sec

=== Transport of Small Penetrant Molecules ===

Newchor nu - 49.3418
Permeability of P_O2 - 2092.2809 DU
Oxygen
Permeability of P_N2 - 661.3981 DU
Nitrogen
Permeability of P_CO2 - 12053.8072 DU
Carbon Dioxide
=== Thermal Stability ===
Temperature of T_d,1/2 - 672.8085 K
Half-decomposition

Molar Thermal Y_d,1/2 - 36.3933 K*kg/mol

Decomposition
Function

Page | 16
 === Interaction ===
Interfacial Tension by Surface Tension gamma(T) ,delta_d gamma_12(T) 298.0 - dyn/cm

Interfacial Tension by Surface Tension gamma(T) ,n(T) gamma_12(T) 298.0 - dyn/cm

Interaction Parameter by Solubility Parameter (Fedors) chi_AB(T) 298.0 -

Interaction Parameter by Solubility Parameter (Krevelen) chi_AB(T) 298.0 -

3) MODELING OF POLUBUTADIENE STYRENE

Page | 17
4) ANALYSIS OF POLUBUTADIENE STYRENE
Force Field parameter of polymer:

Force Field parameter of polymer:

Page | 18
5) RESULTS
3D Molecular Drawing:

Molecular Drawing:

Page | 19
Density Distribution Drawing:

Page | 20
Energy (BATCH AVERAGE)

Page | 21
Page | 22