1

Simulation of block copolymer interfaces

Andrei Zvelindovsky

School of Computing, Engineering and Physical Sciences

University of Central Lancashire, Preston, United Kingdom

2

BCP

ODT

Structure Dynamics

3

Model

A

B

SCFT or Ginzburg-Landau

noise

I=A,B

ODT

Structure Dynamics

I

I FD

t

2

4

Cell dynamics simulation

δψ

ψδFM

t

ψ 2

r'rr'rr'rr(r)

Gdd

BDHdF

22

2

432

432

ECAH

Ohta-Kawasaki, 1986

● T. Kawakatsu,

Stat. Phys. of Polymers, 2004,

Springer

5

Block copolymers under external fields

Outlook

• Thin films

• Shear

• Vesicles

• Electric field

6

Outlook

• Thin films

• Shear

• Vesicles

• Electric field

7

Dynamic AFM

SBS film

A. Knoll,

K. Lyakhova,

A. Horvat,

G. Krausch,

A. Sevink,

AZ,

R. Magerle

(2004)

Nature Materials

8

contour lines

Thin films Experiment vs Simulation

SFM

A. Knoll,

A. Horvat,

K. Lyakhova,

G. Krausch,

A. Sevink,

AZ

R. Magerle

(2002)

Phys. Rev. Lett.

K. Lyakhova,

A. Horvat,

AZ ,

A. Sevink

(2006)

Langmuir

9

A. Knoll,

A. Horvat,

K. Lyakhova,

G. Krausch,

A. Sevink,

AZ

R. Magerle

(2002)

Phys. Rev. Lett.

10

Thin film simulation

ABA-block

copolymer

A. Knoll,

K. Lyakhova,

A. Horvat,

G. Krausch,

A. Sevink,

AZ,

R. Magerle

(2004)

Nature Materials

11

Details: Experiment vs Simulation

Nucleation

Experiment

Simulation

A. Knoll,

K. Lyakhova,

A. Horvat,

G. Krausch,

A. Sevink,

AZ,

R. Magerle

(2004)

Nature Materials

12

Kinetics of Cylinder-to-PL transition

A. Knoll, K. Lyakhova, A. Horvat, G. Krausch, A. Sevink, A. Zvelindovsky, R. Magerle (2004) Nature Materials

Annihilation

Experiment

Simulation

A

Details: Experiment vs Simulation

13

Outlook

• Thin films

• Shear

• Vesicles

• Electric field

14

sh

ea

r ra

te

Block copolymer spheres in shear flow

Experiment I.W. Hamley, et al.

J. Chem. Phys. (1998)

polymer

M. Pinna, A. Zvelindovsky, S. Todd, G. Goldbeck-Wood

(2006) J. Chem. Phys.

15

Ordering under shear

shear rate

M. Pinna, A. Zvelindovsky, S. Todd, G. Goldbeck-Wood

(2006) J. Chem. Phys.

Double layer

Single layer

Y-T Hong, D. H. Adamson,

P. M. Chaikin, R. A. Register,

Soft Matter 5 (2009), 1687.

y

z

polymer

Double layer

Poster P.24

Pinna M., Zvelindovsky A. V., Guo X., Stokes Ch. L.,

Soft Matter 7 (2011) 6991.

Single layer “puzzle”

Pinna M., Zvelindovsky A. V., Guo X., Stokes Ch. L.,

Soft Matter 7 (2011) 6991.

19

Outlook

• Thin films

• Shear

• Vesicles

• Electric field

How

?

20

Dynamics

A

B

2

2

zG I

I

Electric field

z E

I

I FD

t

2G

noise

I=A,B

external fields

I

I FD

t

2

21

Lamellae in electric field

A. Böker, H. Elbs, H. Hänsel, A Knoll, S Ludwigs,

H. Zettl, V. Urban, V. Abetz, A. Müller, G. Krausch (2002) Phys. Rev. Lett.

22

Lamellae in electric field

Experimental scattering function

ODT

A

B

A. Böker, H. Elbs, H. Hänsel, A. Knoll, S. Ludwigs,

H. Zettl, V. Urban, V. Abetz, A. Müller, G. Krausch (2002) Phys. Rev. Lett.

Kinetic or Thermodynamic factors ?

23

E

AZ, A. Sevink (2003) Phys. Rev. Lett.

Lamellae in electric field

simulation

ODT

6

8

M. Pinna,

L. Schreier,

AVZ

(2009) Soft Matter

CDS

Lamellae in electric field

25

Spheres in electric field

250 nm TEM

E

AFM

E

simulation

T. Xu,

AZ,

A. Sevink,

O. Gang,

B. Ocko,

Yu. Zhu,

S. Gido,

T. Russell

(2004)

Macromolecules

E

250 nm

26

Cylinders in electric field

E

?

27

simulation

E

TEM

Cylinders in electric field

T. Xu,

AZ,

A. Sevink,

K. Lyakhova,

H. Jinnai,

T. Russell

(2005)

Macromolecules tim

e

28

simulation

E

TEM

Cylinders in electric field

T. Xu, AZ, A. Sevink, K. Lyakhova, H. Jinnai, T. Russell

(2005) Macromolecules

Intermediate stages of transition

29

X

Y

X

Y

[110] -

[112] -

D. Ly, T. Honda, T. Kawakatsu, AZ

(2007) Macromolecules

Gyroid under electric field

30

Y

X

Electric field along [111]

E

D. Ly, T. Honda, T. Kawakatsu, AZ

(2007) Macromolecules

31

Gyroid: Electric field along [111]

5-fold connections

D. Ly, T. Honda, T. Kawakatsu, AZ

(2007) Macromolecules

32

Gyroid: intermediates

Eskimergen, Mortensen, Vigild (2005)

Macromolecules

D. Ly, T. Honda, T. Kawakatsu, AZ (2007)

Macromolecules

Simulation

33

Gyroid: Threshold of Electric Field T

ran

sitio

n t

ime

~ E 2

D. Ly, T. Honda, T. Kawakatsu, AZ (2007) Macromolecules

2/3

3/1

2/1

)(~~

~

)(~

C

C

TT

TT

Landau

Lifshitz-Slyozov

34

Outlook

• Thin films

• Shear

• Vesicles

• Electric field

35

Micelle-vesicle transition

J. Leng, S. U. Egelhaaf, M. E. Cates, Biophys. J. 85 (2003) 1624.

kinetic control

collapse coalescence growth

Ostwald ripening

& vesicle fusion

and fission closure

36

Large-scale field-theoretical computer simulation on spontaneous vesicle formation

Spontaneous vesicle formation by SCFT based computer simulation

AiBj Gaussian chain in a one bead solvent

A B

S hydrophilic hydrophobic

Micelle-vesicle transition

A. Sevink, AZ (2005) Macromolecules

37

Vesicles

A. Sevink,

AZ

(2005)

Macromolecules

20% of

A B

in a selectile

bad solvent

2 2

micro-

vs.

macrophase

separation

38

Vesicle formation

uni-layer vesicle

time

A. Sevink, AZ (2005) Macromolecules

39

Vesicle fusion

time

A. Sevink, AZ (2005) Macromolecules

40

Vesicle fusion

uni-layer vesicle

time

A. Sevink, AZ (2005) Macromolecules

41

A B 2 3

A B 2 5

L. Zhang, C. Bartels, Yi. Yu, H. Shen,

A. Eisenberg (1997) Phys. Rev. Lett.

TEM

Nano-structured particles

A. Sevink, AZ (2005)

Macromolecules

42

Contributors

Leiden University, NL

Agur Sevink

University of Bayreuth, Germany

Armin Knoll

Andriana Horvat

Alexander Böker

Larisa Tsarkova

Georg Krausch

Reading University

Ian Hamley Chemnitz University, Germany

Robert Magerle

MesoDyn team:

Hans Fraaije

Olaf Evers

Peter Altevoght

Bernard van Vlimmeren

Natasha Maurits

… ++

Eindhoven University, NL

Katya Lyakhova

UCLan, Preston

Marco Pinna

Dung Ly

Xiaohu Guo

Ludwig Schreier

UMass, USA

Tom Russell

SGI Origin 3800, SARA, Amsterdam

SGI Altix 3700, UCLan, Preston

UC Berkeley, USA

Ting Xu

Accelrys Ltd, Cambridge

Stephen Todd

Gerhard Goldbeck-Wood Tohoku University, Sendai, Japan

Toshihiro Kawakatsu

Tokyo Institute of Technology

Takashi Honda