Citation: Yi-Xin Liu, Hong-Dong Zhang. Structures and Surface States of Polymer Brushes in Good Solvents: Effects of Surface Interactions[J]. Chinese Journal of Polymer Science, ;2018, 36(9): 1047-1054. doi: 10.1007/s10118-018-2100-4 shu

Structures and Surface States of Polymer Brushes in Good Solvents: Effects of Surface Interactions

Yi-Xin Liu ^, ,
Hong-Dong Zhang

State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433, China

Corresponding author: Yi-Xin Liu, lyx@fudan.edu.cn
Received Date: 23 November 2017
Accepted Date: 3 December 2017
Available Online: 28 February 2018

The influence of the surface interaction on the mesoscopic structure of grafted polymers in good solvents has been examined. At high surface coverage, tethered polymers are in the brush state and the parabolic segment density profile is confirmed by self-consistent field theory (SCFT) calculations. It is found that this is a universal behavior for a whole range of surface interactions from complete repulsion to strong attraction. More interestingly, finite surface repulsion may lead to the maximum in the proximal layer of its segment density profile, which is significantly different from both the depletion layer of pure repulsion and the adsorbing layer of attraction. In addition to the brush state on both repulsive and attractive surfaces, three additional surface states were identified by analyzing the scaling behavior of the layer thickness of polymer brushes: the mushroom state on repulsive substrates, the dilute and the semidilute surface states on attractive substrates.
- Self-consistent field theory,
- Scaling theory,
- Polymer thin film,
- Polymer brush
1. [1]
  Chen, W. L.; Cordero, R.; Tran, H.; Ober, C. K. 50th Anniversary perspective: polymer brushes: novel surfaces for future materials. Macromolecules 2017, 50(11), 4089−4113 doi: 10.1021/acs.macromol.7b00450
2. [2]
  Binder, K.; Milchev, A. Polymer brushes on flat and curved surfaces: how computer simulations can help to test theories and to interpret experiments. J. Polym. Sci., Part B: Polym. Phys. 2012, 50(22), 1515−1555 doi: 10.1002/polb.v50.22
3. [3]
  Azzaroni, O. Polymer brushes here, there, and everywhere: Recent advances in their practical applications and emerging opportunities in multiple research fields. J. Polym. Sci., Part A: Polym. Chem. 2012, 50(16), 3225−3258 doi: 10.1002/pola.v50.16
4. [4]
  Cohen Stuart, M. A.; Huck, W. T. S.; Genzer, J.; Müller, M.; Ober, C.; Stamm, M.; Sukhorukov, G. B.; Szleifer, I.; Tsukruk, V. V.; Urban, M.; Winnik, F.; Zauscher, S.; Luzinov, I.; Minko, S. Emerging applications of stimuli-responsive polymer materials. Nat. Mater. 2010, 9(2), 101−113 doi: 10.1038/nmat2614
5. [5]
  Ayres, N. Polymer brushes: applications in biomaterials and nanotechnology. Polym. Chem. 2010, 1(6), 769−777 doi: 10.1039/B9PY00246D
6. [6]
  Brittain, W. J.; Minko, S. A structural definition of polymer brushes. J. Polym. Sci., Part A: Polym. Chem. 2007, 45(16), 3505−3512 doi: 10.1002/(ISSN)1099-0518
7. [7]
  Currie, E. P. K.; Norde, W.; Cohen Stuart, M. A. Tethered polymer chains: surface chemistry and their impact on colloidal and surface properties. Adv. Colloid Interface Sci. 2003, 100-102, 205–265.
8. [8]
  Granick, S. Macromolecules at surfaces? research challenges and opportunities from tribology to biology J. Polym. Sci., Part B: Polym. Phys. 2003, 41(22), 2755−2793 doi: 10.1002/(ISSN)1099-0488
9. [9]
  Halperin, A.; Tirrell, M.; Lodge, T. Tethered chains in polymer microstructures. Adv. Polym. Sci. 1992, 100, 31−71
10. [10]
  Alexander, S. Adsorption of chain molecules with a polar head a scaling description. J. Phys. 1977, 38(8), 983−987 doi: 10.1051/jphys:01977003808098300
11. [11]
  de Gennes, P. G. Conformations of polymers attached to an interface. Macromolecules 1980, 1075(19), 1069−1075
12. [12]
  Milner, S. T.; Witten, T.; Cates, M. Theory of the grafted polymer brush. Macromolecules 1988, 21(10), 2610−2619
13. [13]
  Milner, S. T. Polymer brushes. Science 1991, 251, 905−914 doi: 10.1126/science.251.4996.905
14. [14]
  Netz, R. R.; Schick, M. Polymer brushes: from self-consistent field theory to classical theory. Macromolecules 1998, 31(15), 5105−5122 doi: 10.1021/ma9717505
15. [15]
  Wijmans, C. M.; Scheutjens, J. M. H. M.; Zhulina, E. B. Self-consistent field theories for polymer brushes: lattice calculations and an asymptotic analytical description. Macromolecules 1992, 25(10), 2657−2665 doi: 10.1021/ma00036a016
16. [16]
  Matsen, M. W.; Griffiths, G. H. Melt brushes of diblock copolymer. Eur. Phys. J. E 2009, 29(2), 219−227 doi: 10.1140/epje/i2009-10470-2
17. [17]
  de Gennes, P. G., "Scaling concepts in polymer physics", Cornell University Press, Ithaca, 1979.
18. [18]
  Eisenriegler, E.; Kremer, K.; Binder, K. Adsorption of polymer chains at surfaces: scaling and Monte Carlo analyses. J. Chem. Phys. 1982, 77(12), 6296−6320 doi: 10.1063/1.443835
19. [19]
  Eisenriegler, E. Dilute and semidilute polymer solutions near an adsorbing wall. J. Chem. Phys. 1983, 79(2), 1052−1064 doi: 10.1063/1.445847
20. [20]
  Bouchaud, E.; Daoud, M. Polymer adsorption: concentration effects. J. Phys. 1987, 48(11), 1991−2000 doi: 10.1051/jphys:0198700480110199100
21. [21]
  Descas, R.; Sommer, J. U.; Blumen, A. Grafted polymer chains interacting with substrates: computer simulations and scaling. macromol. Theory Simul. 2008, 17(9), 429−453 doi: 10.1002/mats.v17:9
22. [22]
  Adamuti-Trache, M.; McMullen, W. E.; Douglas, J. F. Segmental concentration profiles of end-tethered polymers with excluded-volume and surface interactions. J. Chem. Phys. 1996, 105(11), 4798−4811 doi: 10.1063/1.472991
23. [23]
  Marko, J. F.; Johner, A.; Marques, C. M. Grafted polymers under the influence of external fields. J. Chem. Phys. 1993, 99(10), 8142−8153 doi: 10.1063/1.465641
24. [24]
  Bijsterbosch, H. D.; de Haan, V. O.; de Graaf, A. W.; Mellema, M.; Leermakers, F. A. M.; Cohen Stuart, M. A.; van Well, A. A. Tethered adsorbing chains: neutron reflectivity and surface pressure of spread diblock copolymer monolayers. Langmuir 1995, 29(14), 4467−4473
25. [25]
  Fredrickson, G.H., "The equilibrium theory of inhomogeneous polymers", Clarendon Press, Oxford, 2006.
26. [26]
  Chantawansri, T. L.; Hur, S. M.; García-Cervera, C. J.; Ceniceros, H. D.; Fredrickson, G. H. Spectral collocation methods for polymer brushes. J. Chem. Phys. 2011, 134(24), 244905 doi: 10.1063/1.3604814
27. [27]
  Liu, Y. X.; Zhang, H. D. Exponential time differencing methods with Chebyshev collocation for polymers confined by interacting surfaces. J. Chem. Phys. 2014, 140(22), 224101 doi: 10.1063/1.4881516
28. [28]
  Rasmussen, K. Ø.; Kalosakas, G. Improved numerical algorithm for exploring block copolymer mesophases. J. Polym. Sci., Part B: Polym. Phys. 2002, 40(16), 1777−1783 doi: 10.1002/(ISSN)1099-0488
29. [29]
  Tzeremes, G.; Rasmussen, K. Ø.; Lookman, T.; Saxena, A. Efficient computation of the structural phase behavior of block copolymers. Phys. Rev. E. 2002, 65(4), 041806.
30. [30]
  Müller, M. Phase diagram of a mixed polymer brush. Phys. Rev. E 2002, 65(3), 30802.
31. [31]
  Suo, T.; Whitmore, M. D. Self-consistent field theory of tethered polymers: One dimensional, three dimensional, strong stretching theories and the effects of excluded-volume-only interactions. J. Chem. Phys. 2014, 141(20), 204903.
32. [32]
  Meng, D.; Wang, Q. Solvent response of diblock copolymer brushes. J. Chem. Phys. 2009, 130(13), 134904.
33. [33]
  Trefethen, L. N., "Spectral methods in MATLAB", SIAM, Philadelphia, 2000.
34. [34]
  Douglas, J. F.; Nemirovsky, A. M.; Freed, K. F. Polymer-polymer and polymer-surface excluded volume effects in flexible polymers attached to an interface: comparison of renormalization group calculations with Monte Carlo and direct enumeration data. Macromolecules 1986, 19(7), 2041−2054 doi: 10.1021/ma00161a043
35. [35]
  Wu, D. T.; Fredrickson, G. H.; Carton, J. P. Surface segregation in conformationally asymmetric polymer blends: Incompressibility and boundary conditions. J. Chem. Phys. 1996, 104(16), 6387−6397 doi: 10.1063/1.471272
36. [36]
  Hur, S. M.; Garcॆa-Cervera, C. J.; Fredrickson, G. H. Chebyshev collocation in polymer field theory: application to wetting phenomena. Macromolecules 2012, 45(6), 2905−2919 doi: 10.1021/ma202427n
37. [37]
  Laradji, M.; Guo, H.; Zuckermann, M. Off-lattice Monte Carlo simulation of polymer brushes in good solvents. Phys. Rev. E 1994, 49(4), 3199−3206 doi: 10.1103/PhysRevE.49.3199
38. [38]
  de Gennes, P. G.; Pincus, P. Scaling theory of polymer adsorption: proximal exponent. J. Phys. Lett. 1983, 44(7), 241−246 doi: 10.1051/jphyslet:01983004407024100
39. [39]
  Chakrabarti, A.; Nelson, P.; Toral, R. Structure of polymer chains end-grafted on an interacting surface. Phys. Rev. A 1992, 46(8), 4930−4934 doi: 10.1103/PhysRevA.46.4930
40. [40]
  Grest, G. S. Grafted polymer brushes: a constant surface pressure molecular dynamics simulation. Macromolecules 1994, 27(2), 418−426 doi: 10.1021/ma00080a015
41. [41]
  Flatt, R. J.; Schober, I.; Raphael, E.; Plassard, C.; Lesniewska, E. Conformation of adsorbed comb copolymer dispersants. Langmuir 2009, 25(2), 845−855 doi: 10.1021/la801410e
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