Title:
Polymer Physics and PCE Superplasticizers Revisited
Author(s):
Yanwei Wang, Xin Shu, Yong Yang, Qianping Ran, and Jiaping Liu
Publication:
Symposium Paper
Volume:
329
Issue:
Appears on pages(s):
305-318
Keywords:
polymer conformation; comb architecture; persistence length; wormlike chain; radius of gyration; polyelectrolyte; adsorption layer thickness.
DOI:
10.14359/51711223
Date:
9/26/2018
Abstract:
Conformational properties of comb-shaped copolymer polyelectrolytes such as polycarboxylate ether-based superplasticizers (PCEs) in aqueous solutions and at liquid/solid interfaces are fundamental to their performances as polymeric dispersants. Pioneering studies of Flatt and coworkers have demonstrated the great relevance of polymer theory to the PCE community. The present work revisits this topic with an emphasis on the semi-flexible characteristics of the anionic backbone decorated with flexible side chains. A simple physical picture, where the backbone adopts a "train-like" conformation on the surface, effectively as a two-dimensional worm-like chain, with the side chains mimicking surface-tethered chains, is presented for PCEs in the strongly adsorbed state.
Related References:
1. Aïtcin, P.-C., and Flatt, R. J., “Science and technology of concrete admixtures,” Woodhead Publishing, 2015.
2. Plank, J.; Sakai, E.; Miao, C. W.; Yu, C.; and Hong, J. X., “Chemical admixtures— Chemistry, applications and their impact on concrete microstructure and durability,” Cement and Concrete Research, V. 78, 2015, pp. 81-99. doi: 10.1016/j.cemconres.2015.05.016
3. Kraus, A.; Dengler, J.; Bokern, J.; Moins, N.; and Mazanec, O., “A New Admixture Generation for A New Concrete Generation,” Proceedings 11th CANMET/ACI International Conference on Superplasticizers and Other Chemical Admixtures in Concrete, V.M. Malhotra, P. R. Gupta, and P. Gupta, eds., Ottawa, Canada, 2015, Supplementary papers, pp. 303-320.
4. Flatt, R. J.; Schober, I.; Raohael, E.; Lesniewska, E.; and Plassard, C., “Polymer Physics and Superplasticizers,” Proceedings 9th CANMET/ACI International Conference on Superplasticizers and Other Chemical Admixtures in Concrete, T. C. Holland, P. R. Gupta, and V.M. Malhotra, eds., Seville, Spain, 2009, pp. 113-122.
5. Flatt, R. J.; Schober, I.; Raphael, E.; Plassard, C.; and Lesniewska, E., “Conformation of adsorbed comb copolymer dispersants,” Langmuir, V. 25, No. 2, 2009, pp. 845-855. doi: 10.1021/la801410e
6. Gay, C., and Raphael, E., “Comb-like polymers inside nanoscale pores,” Advances in Colloid and Interface Science, V. 94, No. 1, 2001, pp. 229-236. doi: 10.1016/ S0001-8686(01)00062-8
7. Houst, Y. F.; Bowen, P.; Perche, F.; Kauppi, A.; Borget, P.; Galmiche, L.; Le Meins, J. F.; Lafuma, F.; Flatt, R. J.; Schober, I.; Banfill, P. F.; Swift, D. S.; Myrvold, B. O.; Petersen, B. G.; and Reknes, K., “Design and function of novel superplasticizers for more durable high performance concrete (superplast project),” Cement and Concrete Research, V. 38, No. 10, 2008, pp. 1197-1209. doi: 10.1016/j.cemconres.2008.04.007
8. Ferrari, L.; Kaufmann, J.; Winnefeld, F.; and Plank, J., “Interaction of cement model systems with superplasticizers investigated by atomic force microscopy, zeta potential, and adsorption measurements,” Journal of Colloid and Interface Science, V. 347, No. 1, 2010, pp. 15-24. doi: 10.1016/j.jcis.2010.03.005
9. Hot, J.; Bessaies-Bey, H.; Brumaud, C.; Duc, M.; Castella, C.; and Roussel, N., “Adsorbing polymers and viscosity of cement pastes,” Cement and Concrete Research, V. 63, 2014, pp. 12-19. doi: 10.1016/j.cemconres.2014.04.005
10. Paturej, J.; Sheiko, S. S.; Panyukov, S.; and Rubinstein, M., “Molecular structure of bottlebrush polymers in melts,” Science Advances, V. 2, No. 11, 2016, p. e1601478 doi: 10.1126/sciadv.1601478
11. Paturej, J., and Kreer, T., “Hierarchical excluded volume screening in solutions of bottlebrush polymers,” Soft Matter, V. 13, No. 45, 2017, pp. 8534-8541. doi: 10.1039/ C7SM01968H
12. Wang, Y.; Zhao, H.; Shu, X.; Yang, Y.; and Ran, Q., “Radius of Gyration of Combshaped Copolymers by the Wormlike Chain Model: Theory and Its Applications to MPEG-type Polycarboxylate-type Superplasticizers,” Gaofenzi Xuebao, V. 11, 2017, pp. 1816-1831.
13. Nakamura, Y.; Wan, Y.; Mays, J. W.; Iatrou, H.; and Hadjichristidis, N., “Radius of gyration of polystyrene combs and centipedes in solution,” Macromolecules, V. 33, No. 22, 2000, pp. 8323-8328. doi: 10.1021/ma0007076
14. Yamakawa, H., and Yoshizaki, T., 1997. “Helical Wormlike Chains in Polymer Solutions”. Berlin: Springer.
15. Chen, J. Z. Y., “Theory of wormlike polymer chains in confinement,” Progress in Polymer Science, V. 54, 2016, pp. 3-46. doi: 10.1016/j.progpolymsci.2015.09.002
16. De Gennes, P. G., 1979. “Scaling Concepts in Polymer Physics”. Cornell university press.
17. Rubinstein, M., and Colby, R. H., 2003. “Polymer Physics”. New York: Oxford University Press.
18. Lee, H.; de Vries, A. H.; Marrink, S. J.; and Pastor, R. W., “A coarse-grained model for polyethylene oxide and polyethylene glycol: conformation and hydrodynamics,” The Journal of Physical Chemistry B, V. 113, No. 40, 2009, pp. 13186-13194. doi: 10.1021/ jp9058966
19. Feuz, L.; Leermakers, F. A.; Textor, M.; and Borisov, O., “Bending rigidity and induced persistence length of molecular bottle brushes: A self-consistent-field theory,” Macromolecules, V. 38, No. 21, 2005, pp. 8891-8901. doi: 10.1021/ma050871z
20. Sulatha, M. S., and Natarajan, U., “Molecular dynamics simulations of PAA–PMA polyelectrolyte copolymers in dilute aqueous solution: chain conformations and hydration properties,” Industrial & Engineering Chemistry Research, V. 51, No. 33, 2012, pp. 1083310839. doi: 10.1021/ie301244n
21. Giraudeau, C.; D’Espinose De Lacaillerie, J. B.; Souguir, Z.; Nonat, A.; and Flatt, R. J., “Surface and intercalation chemistry of polycarboxylate copolymers in cementitious systems,” Journal of the American Ceramic Society, V. 92, No. 11, 2009, pp. 2471-2488. doi: 10.1111/j.1551-2916.2009.03413.x
22. Hiemenz, P. C., and Lodge, T. P., 2007. “Polymer Chemistry”. CRC press.
23. Farmer, B. S.; Terao, K.; and Mays, J. W., “Characterization of model branched polymers by multi-detector SEC in good and theta solvents,” Int J Polym Anal Charact, V. 11, No. 1, 2006, pp. 3-19. doi: 10.1080/10236660500484213
24. Pamies, R.; Cifre, J. G. H.; Martínez, M. D. C. L.; and de la Torre, J. G., “Determination of intrinsic viscosities of macromolecules and nanoparticles. Comparison of singlepoint and dilution procedures,” Colloid & Polymer Science, V. 286, No. 11, 2008, pp. 1223-1231. doi: 10.1007/s00396-008-1902-2
25. Wang, Y.; Zhao, H.; Shu, X.; Yang, Y.; and Ran, Q., “Modelling the Equilibrium Sizes of Comb-shaped MPEG-type Polycarboxylate-type Superplasticizers in Dilute Solution and Their Apparent Molecular Weight in Conventional Size Exclusion Chromatography,” Gaofenzi Xuebao, V. 6, 2017, pp. 1008-1018.
26. Scheutjens, J. M. H. M., and Fleer, G. J., “Statistical theory of the adsorption of interacting chain molecules. 2. Train, loop, and tail size distribution,” Journal of Physical Chemistry, V. 84, No. 2, 1980, pp. 178-190. doi: 10.1021/j100439a011
27. Dobrynin, A. V.; Deshkovski, A.; and Rubinstein, M., “Adsorption of polyelectrolytes at oppositely charged surfaces,” Macromolecules, V. 34, No. 10, 2001, pp. 34213436. doi: 10.1021/ma0013713
28. Dobrynin, A. V., and Rubinstein, M., “Theory of polyelectrolytes in solutions and at surfaces,” Progress in Polymer Science, V. 30, No. 11, 2005, pp. 1049-1118. doi: 10.1016/j. progpolymsci.2005.07.006
29. Hsu, H. P.; Paul, W.; and Binder, K., “Breakdown of the Kratky-Porod wormlike chain model for semiflexible polymers in two dimensions,” EPL, V. 95, No. 6, 2011, p. 68004 doi: (Europhysics Letters)10.1209/0295-5075/95/68004
30. Huang, A.; Bhattacharya, A.; and Binder, K., “Conformations, transverse fluctuations, and crossover dynamics of a semi-flexible chain in two dimensions,” The Journal of Chemical Physics, V. 140, No. 21, 2014, p. 214902 doi: 10.1063/1.4879537
31. Milchev, A., and Binder, K., “Smectic C and nematic phases in strongly adsorbed layers of semiflexible polymers,” Nano Letters, V. 17, No. 8, 2017, pp. 4924-4928. doi: 10.1021/acs.nanolett.7b01948
32. De Gennes, P. G., “Conformations of polymers attached to an interface,” Macromolecules, V. 13, No. 5, 1980, pp. 1069-1075. doi: 10.1021/ma60077a009
33. Zhao, B., and Brittain, W. J., “Polymer brushes: surface-immobilized macromolecules,” Progress in Polymer Science, V. 25, No. 5, 2000, pp. 677-710. doi: 10.1016/ S0079-6700(00)00012-5
34. Dobrynin, A. V., “Electrostatic persistence length of semiflexible and flexible polyelectrolytes,” Macromolecules, V. 38, No. 22, 2005, pp. 9304-9314. doi: 10.1021/ ma051353r
35. Gelardi, G.; Sanson, N.; Nagy, G.; and Flatt, R. J., “Characterization of comb-shaped copolymers by multidetection SEC, DLS and SANS,” Polymers, V. 9, No. 2, 2017, p. 61 doi: 10.3390/polym9020061