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Modification of Surfaces Using Polymers: A Self-consistent Field Theory Study David Trombly Advised by  Venkat Ganesan Thesis Defense June 29, 2011
Polymer-grafted surface Interacting surface Mediating  material Solvent Melt ,[object Object],[object Object],R drug H brush R protein σ Surface-surface interactions ,[object Object],[object Object]
Polymer-grafted surface Interacting surface Mediating  material Solvent Melt http://www.questline.com/images/content/CMPND_nanocomposites.jpg Surface-surface interactions ,[object Object],Surface-polymer interactions
Polymer-grafted surface Interacting material Homopolymer Surface-polymer interactions Diblock copolymer Random copolymer brush Stoykovich, et al., Science, 2005 B A
Polymer-grafted particle Interacting surface Mediating  material Solvent Melt ,[object Object],[object Object],[object Object],R drug H brush R protein σ R g 2 Interaction energy determined by: σ www.mdconsult.com Polymer-grafted sphere – bare sphere (Ch 2) R protein R drug H brush R drug
Drug design equation ,[object Object]
Polymer-grafted particle Interacting surface Mediating  material Solvent Melt The following contribute to miscibility: Decrease: Increase: N brush N free translational entropy σ R g 2 ,[object Object],Polymer-grafted spheres in a melt (Ch 3) R core H brush R particle N free N brush H brush R core R particle R g, free
Width/energy collapse, correlation ,[object Object]
Semiconductor devices (Ch 4-5) Equal surface energies  Perpendicular lamellae  High value semiconductor devices Random copolymer brush f A B f = volume fraction of A (in brush) B A ,[object Object],[object Object],[object Object],Objectives (Ch 4)
Wetting Dewetting σ  = 2.45,  α  = 0.5 σ  = 4.90,  α  = 1.5 ,[object Object],Happens sooner for larger  σ  (more stretched chains)! Surface energy ,[object Object],Background: f = 1 (autophobic) Increased free chain length ( α ) α   = Same effect from decrease of brush chain length (increases  α ) Ends of free chains are stretched at interface; reduction of interfacial area is preferred N free N brush
[object Object],Background: f = 0 ,[object Object],Objectives ,[object Object],[object Object]
Self-consistent field theory (SCFT) w A ( r ), w B ( r ) q( r ,s) q c ( r ,s) s Stretching energy Enthalpy Incompressibility Grafted Free
[object Object],Modeling random copolymers ,[object Object],[object Object],[object Object],[object Object],λ  = -0.5 λ  = 0.5 λ  = 0
[object Object],Chain rearrangement ,[object Object],f Eff f Eff f = 0. 5 f = 0. 5
Strong-stretching theory (SST) ,[object Object],Configurational entropy cost due to the interface Translational entropy Enthalpic interactions ,[object Object],[object Object],Stretching energy χ Eff  =  χ (1-f Eff )
Surface energy results Autophobic ~ 5 x 10 -3 ,[object Object],χ N = 10,  α  = 1,  σ  = 4.9,  λ  = 0 f = 0.5,  α  = 1,  σ  = 4.9,  λ  = 0 f = 0.5,  χ N = 10,  σ  = 4.9,  λ  = 0 f = 0.5,  χ N = 10,  α  = 1,  λ  = 0 ,[object Object]
Blockiness and chain rearrangement ,[object Object],[object Object],f = 0.5 f = 0.5
Blockiness and chain rearrangement ,[object Object],[object Object],f = 0.5 f = 0.5
Summary ,[object Object],[object Object],[object Object],Extension (Ch 5) ,[object Object]
Previous modeling work Matsen, JCP, 1997 B A Diblock on hard surface with preference for A Incommensurate Diblock on hard surface with chemical stripes Wang, et al, Macro, 2000 Commensurate D bulk B A
[object Object],[object Object],Parallel morphologies
[object Object],[object Object],Perpendicular morphologies
[object Object],[object Object],Blocky random copolymer
[object Object],[object Object],Increased A in brush (f = 0.6)
[object Object],[object Object],Energy picture D bulk ,[object Object]
Neutral windows ,[object Object],[object Object]
Neutral windows ,[object Object],[object Object]
Summary ,[object Object],[object Object],[object Object]
Future work ,[object Object],[object Object],[object Object],[object Object]
Acknowledgements  Prof. Venkat Ganesan, Committee members, Ganesan research group (Victor Pryamitsyn, Manas Shah, Landry Khounlavong, Paresh Chokshi, Ben Hanson, Arun Narayana, Chetan Mahajan, Thomas Lewis, Gunja Pandav), Brandon Rawlings Funding: NSF (Award # 1005739) Robert A. Welch Foundation Grant F1599 US Army Research Office Grant W911NF-10-1-0346 Texas Advanced Computing Center

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Defense

  • 1. Modification of Surfaces Using Polymers: A Self-consistent Field Theory Study David Trombly Advised by Venkat Ganesan Thesis Defense June 29, 2011
  • 2.
  • 3.
  • 4. Polymer-grafted surface Interacting material Homopolymer Surface-polymer interactions Diblock copolymer Random copolymer brush Stoykovich, et al., Science, 2005 B A
  • 5.
  • 6.
  • 7.
  • 8.
  • 9.
  • 10.
  • 11.
  • 12. Self-consistent field theory (SCFT) w A ( r ), w B ( r ) q( r ,s) q c ( r ,s) s Stretching energy Enthalpy Incompressibility Grafted Free
  • 13.
  • 14.
  • 15.
  • 16.
  • 17.
  • 18.
  • 19.
  • 20. Previous modeling work Matsen, JCP, 1997 B A Diblock on hard surface with preference for A Incommensurate Diblock on hard surface with chemical stripes Wang, et al, Macro, 2000 Commensurate D bulk B A
  • 21.
  • 22.
  • 23.
  • 24.
  • 25.
  • 26.
  • 27.
  • 28.
  • 29.
  • 30. Acknowledgements Prof. Venkat Ganesan, Committee members, Ganesan research group (Victor Pryamitsyn, Manas Shah, Landry Khounlavong, Paresh Chokshi, Ben Hanson, Arun Narayana, Chetan Mahajan, Thomas Lewis, Gunja Pandav), Brandon Rawlings Funding: NSF (Award # 1005739) Robert A. Welch Foundation Grant F1599 US Army Research Office Grant W911NF-10-1-0346 Texas Advanced Computing Center

Editor's Notes

  1. The reason polymer-particle systems are of interest is that they can be used to study a number of systems. For example… Don’t talk too long about this!
  2. The reason polymer-particle systems are of interest is that they can be used to study a number of systems. For example… Don’t talk too long about this!
  3. I: Au(2) PS(10)-SH; P = 125, N = 10; sigma = 1.67 II: Au(5) PS(10)-SH; P = 125, N = 10; sigma = 1.39 III: Au(2) PS(10)-SH; P = 125, N = 480; sigma = 9.21 Tell why we model plate + brush
  4. Say it right!
  5. poly~methyl methacrylate! ~PMMA! and poly~vinyl chloride! ~PVC!, poly~styrene! ~PS!, and poly~2,6-dimethyl-1,4-phenylene oxide! ~PXE! State objectives differently – motivate how we are extending the problem from the limiting cases
  6. Mention the presence of two kinds of chains We are proposing that SCFT provides a good way to study these systems
  7. I: Au(2) PS(10)-SH; P = 125, N = 10; sigma = 1.67 II: Au(5) PS(10)-SH; P = 125, N = 10; sigma = 1.39 III: Au(2) PS(10)-SH; P = 125, N = 480; sigma = 9.21 Tell why we model plate + brush
  8. What really matters is fEff
  9. Describe the interplay between enthalpy and entropy using SST Term 4 distinguishes the theory from autophobic Term 4 should be smaller for larger f Random copolymer should rearrange itself toward f = 1 Idea: modify term 4 based on fEff
  10. I: Au(2) PS(10)-SH; P = 125, N = 10; sigma = 1.67 II: Au(5) PS(10)-SH; P = 125, N = 10; sigma = 1.39 III: Au(2) PS(10)-SH; P = 125, N = 480; sigma = 9.21 Tell why we model plate + brush
  11. I: Au(2) PS(10)-SH; P = 125, N = 10; sigma = 1.67 II: Au(5) PS(10)-SH; P = 125, N = 10; sigma = 1.39 III: Au(2) PS(10)-SH; P = 125, N = 480; sigma = 9.21 Tell why we model plate + brush
  12. I: Au(2) PS(10)-SH; P = 125, N = 10; sigma = 1.67 II: Au(5) PS(10)-SH; P = 125, N = 10; sigma = 1.39 III: Au(2) PS(10)-SH; P = 125, N = 480; sigma = 9.21 Tell why we model plate + brush
  13. Curvature?
  14. Curvature?
  15. Curvature?
  16. Curvature?
  17. Curvature?
  18. Curvature?
  19. Curvature?
  20. Curvature?
  21. Curvature?
  22. Curvature?
  23. Curvature?