ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Swelling and Inflation in Polyelectrolyte Complexes

Cite this: Macromolecules 2019, 52, 2, 610–619
Publication Date (Web):December 31, 2018
Copyright © 2018 American Chemical Society

Article Views





Read OnlinePDF (6 MB)
Supporting Info (1)»


Abstract Image

The properties of polyelectrolyte complexes, PECs, made from blended polycations, Pol+, and polyanions, Pol, are routinely studied under conditions where they are at least partially swollen with water. Water plasticizes PECs, transforming them from an intractable, glassy, and brittle state when dry to tough and viscoelastic when wet. In the present work the supreme efficiency of water, compared to other solvents on a polarity scale, in swelling a PEC is illustrated. Using a PEC of poly(diallyldimethylammonium) and poly(styrenesulfonate) with precisely determined density, we show that swelling tracks a Dimroth–Reichardt polarity scale until the molecular volume exceeds ∼50 Å3, whereupon the degree of swelling drops sharply. Long-term (>1 year) swelling of this PEC in pure water reveals an instability, wherein the material substantially inflates, generating large pores even though T < Tg. The mechanism for this instability is attributed to a small population of counterions, resulting from slight nonstoichiometry of polyelectrolytes, as well as the polymers themselves, a contribution estimated using Des Cloizeaux’s theory of osmotic pressure for overlapping chains. Low concentrations of salt in the bathing solution are enough to overcome the osmotic pressure within the PEC, and it remains dimensionally stable over the long time periods studied. The universal practice of rinsing PECs, whether they are in macroscopic or thin-film morphology, in pure water should be re-evaluated.

Supporting Information

Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.8b01838.

  • Additional scanning electron microscopy images of PEC samples (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

Cited By

This article is cited by 46 publications.

  1. Amir Azinfar, Christiane A. Helm. Self-Patterning of Polyelectrolyte Multilayer Films: The Roles of PSS Molecular Weight, the Top Layer, and Post-Preparation Treatment. Macromolecules 2023, 56 (8) , 3095-3109.
  2. Kai Chi, Jiamu He, Wei-Shu Lin, Syed M. Q. Bokhari, Jeffrey M. Catchmark. Electrostatically Complexed Natural Polysaccharides as Aqueous Barrier Coatings for Sustainable and Recyclable Fiber-Based Packaging. ACS Applied Materials & Interfaces 2023, 15 (9) , 12248-12260.
  3. John Akintola, Zachary A. Digby, Joseph B. Schlenoff. Polyelectrolyte Complexes as Desiccants: Thirsty Saloplastics. ACS Applied Materials & Interfaces 2023, 15 (7) , 9962-9969.
  4. Wilfredo Mendez-Ortiz, Kathleen J. Stebe, Daeyeon Lee. Ionic Strength-Dependent Assembly of Polyelectrolyte-Nanoparticle Membranes via Interfacial Complexation at a Water–Water Interface. ACS Nano 2022, 16 (12) , 21087-21097.
  5. Belda Amelia Junisu, Iris Ching-Ya Chang, Ya-Sen Sun. Film Instability Induced by Swelling and Drying. Langmuir 2022, 38 (43) , 13009-13020.
  6. Mo Yang, Swapnil L. Sonawane, Zachary A. Digby, Jin G. Park, Joseph B. Schlenoff. Influence of “Hydrophobicity” on the Composition and Dynamics of Polyelectrolyte Complex Coacervates. Macromolecules 2022, 55 (17) , 7594-7604.
  7. Chikaodinaka I. Eneh, Tuuva Kastinen, Suyash Oka, Piotr Batys, Maria Sammalkorpi, Jodie L. Lutkenhaus. Quantification of Water–Ion Pair Interactions in Polyelectrolyte Multilayers Using a Quartz Crystal Microbalance Method. ACS Polymers Au 2022, 2 (4) , 287-298.
  8. Samir Abou Shaheen, Rachel L. Abbett, Khalil Akkaoui, Joseph B. Schlenoff. Long-Range Electron Transfer through Ultrathin Polyelectrolyte Complex Films: A Hopping Model. The Journal of Physical Chemistry C 2021, 125 (41) , 22797-22808.
  9. YuLing Chen, Kenneth R. Shull. Processing Polyelectrolyte Complexes with Deep Eutectic Solvents. ACS Macro Letters 2021, 10 (10) , 1243-1247.
  10. Yuhui Chen, Mo Yang, Samir Abou Shaheen, Joseph B. Schlenoff. Influence of Nonstoichiometry on the Viscoelastic Properties of a Polyelectrolyte Complex. Macromolecules 2021, 54 (17) , 7890-7899.
  11. Elif Nur Durmaz, Sevil Sahin, Ettore Virga, Sissi de Beer, Louis C. P. M. de Smet, Wiebe M. de Vos. Polyelectrolytes as Building Blocks for Next-Generation Membranes with Advanced Functionalities. ACS Applied Polymer Materials 2021, 3 (9) , 4347-4374.
  12. Yuhui Chen, Mo Yang, Joseph B. Schlenoff. Glass Transitions in Hydrated Polyelectrolyte Complexes. Macromolecules 2021, 54 (8) , 3822-3831.
  13. Rachel L. Abbett, Rodney A. Tigaa, Swapnil L. Sonawane, Geoffrey F. Strouse, Joseph B. Schlenoff. Hydrophobic Versus Hydrophilic Polyelectrolyte Multilayers for Emissive Europium Films. ACS Applied Polymer Materials 2021, 3 (2) , 691-698.
  14. Lu Li, Artem M. Rumyantsev, Samanvaya Srivastava, Siqi Meng, Juan J. de Pablo, Matthew V. Tirrell. Effect of Solvent Quality on the Phase Behavior of Polyelectrolyte Complexes. Macromolecules 2021, 54 (1) , 105-114.
  15. Sabrina S. Alam, Youngwoo Seo, Yakov Lapitsky. Highly Sustained Release of Bactericides from Complex Coacervates. ACS Applied Bio Materials 2020, 3 (12) , 8427-8437.
  16. Scott P. O. Danielsen, Sergey Panyukov, Michael Rubinstein. Ion Pairing and the Structure of Gel Coacervates. Macromolecules 2020, 53 (21) , 9420-9442.
  17. Mohsen Ghasemi, Sean Friedowitz, Ronald G. Larson. Analysis of Partitioning of Salt through Doping of Polyelectrolyte Complex Coacervates. Macromolecules 2020, 53 (16) , 6928-6945.
  18. Samir Abou Shaheen, Mo Yang, Banghao Chen, Joseph B. Schlenoff. Water and Ion Transport through the Glass Transition in Polyelectrolyte Complexes. Chemistry of Materials 2020, 32 (14) , 5994-6002.
  19. Tristan D. Harrison, Alexandre J. Salmon, John R. de Bruyn, Paul J. Ragogna, Elizabeth R. Gillies. Phosphonium versus Ammonium Compact Polyelectrolyte Complex Networks with Alginate—Comparing Their Properties and Cargo Encapsulation. Langmuir 2020, 36 (28) , 8253-8264.
  20. Mo Yang, Zachary A. Digby, Joseph B. Schlenoff. Precision Doping of Polyelectrolyte Complexes: Insight on the Role of Ions. Macromolecules 2020, 53 (13) , 5465-5474.
  21. Elif Nur Durmaz, Muhammad Irshad Baig, Joshua D. Willott, Wiebe M. de Vos. Polyelectrolyte Complex Membranes via Salinity Change Induced Aqueous Phase Separation. ACS Applied Polymer Materials 2020, 2 (7) , 2612-2621.
  22. Khalil Akkaoui, Mo Yang, Zachary A. Digby, Joseph B. Schlenoff. Ultraviscosity in Entangled Polyelectrolyte Complexes and Coacervates. Macromolecules 2020, 53 (11) , 4234-4246.
  23. Konstantin G. Nikolaev, Sviatlana A. Ulasevich, Olga Luneva, Olga Yu. Orlova, Daria Vasileva, Semen Vasilev, Alexander S. Novikov, Ekaterina V. Skorb. Humidity-Driven Transparent Holographic Free-Standing Polyelectrolyte Films. ACS Applied Polymer Materials 2020, 2 (2) , 105-112.
  24. Joseph B. Schlenoff, Mo Yang, Zachary A. Digby, Qifeng Wang. Ion Content of Polyelectrolyte Complex Coacervates and the Donnan Equilibrium. Macromolecules 2019, 52 (23) , 9149-9159.
  25. Artem M. Rumyantsev, Juan J. de Pablo. Liquid Crystalline and Isotropic Coacervates of Semiflexible Polyanions and Flexible Polycations. Macromolecules 2019, 52 (14) , 5140-5156.
  26. Kazi Sadman, David E. Delgado, Yechan Won, Qifeng Wang, Kimberly A. Gray, Kenneth R. Shull. Versatile and High-Throughput Polyelectrolyte Complex Membranes via Phase Inversion. ACS Applied Materials & Interfaces 2019, 11 (17) , 16018-16026.
  27. Mo Yang, Jianbing Shi, Joseph B. Schlenoff. Control of Dynamics in Polyelectrolyte Complexes by Temperature and Salt. Macromolecules 2019, 52 (5) , 1930-1941.
  28. Kazi Sadman, Qifeng Wang, Kenneth R. Shull. Guanidinium Can Break and Form Strongly Associating Ion Complexes. ACS Macro Letters 2019, 8 (2) , 117-122.
  29. Juan Luo, Chenjun Dong, Rongrong He, Chang Liu, Tao He. Impact of support pore properties on the performance of layer-by-layer self-assembly nanofiltration membrane. Desalination 2023, 557 , 116596.
  30. Jiarui Chen, Shanshan Xu, Chuyang Y. Tang, Binjie Hu, Begum Tokay, Tao He. Stability of layer-by-layer nanofiltration membranes in highly saline streams. Desalination 2023, 555 , 116520.
  31. Thomas J. Kolibaba, Callie I. Higgins, Nathan C. Crawford, Joseph R. Samaniuk, Jason P. Killgore. Sustainable Additive Manufacturing of Polyelectrolyte Photopolymer Complexes. Advanced Materials Technologies 2023, 8 (9)
  32. Simon van Hurne, Marijn Kisters, Maarten M. J. Smulders. Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes. Frontiers in Chemistry 2023, 11
  33. Wesam A. Hatem, Yakov Lapitsky. Accelerating Payload Release from Complex Coacervates through Mechanical Stimulation. Polymers 2023, 15 (3) , 586.
  34. Abraham García-Jiménez, Angélica Román-Guerrero, César Pérez-Alonso, Benoit Fouconnier. Liquid-liquid and liquid-solid separation in self-assembled chitosan-alginate and chitosan-pectin complexes. International Journal of Biological Macromolecules 2022, 223 , 1368-1380.
  35. Rafael F.N. Quadrado, André R. Fajardo. Vapor-induced polyelectrolyte complexation of chitosan/pectin: A promising strategy for the preparation of hydrogels for controlled drug delivery. Journal of Molecular Liquids 2022, 361 , 119604.
  36. Chenjun Dong, Rongrong He, Shanshan Xu, Hailong He, Hao Chen, Yue-Biao Zhang, Tao He. Layer-by-layer (LBL) hollow fiber nanofiltration membranes for seawater treatment: Ion rejection. Desalination 2022, 534 , 115793.
  37. Jun Gao, Qiang‐wei Zhan, Ziyao Tang, Yan Huang. The Critical Transition from Soluble Complexes to Colloidal Aggregates of Polyelectrolyte Complexes at Non‐Stoichiometric Charge Ratios. Macromolecular Rapid Communications 2022, 43 (7) , 2100880.
  38. Da Zhang, Qing‐Shuang Li, Zi‐Xuan Liang, Xia‐Chao Chen, Junran Hao, Juming Yao, Chun‐Xin Lu, Yahong Zhou, Lei Jiang. Laser‐Directed Foaming of Hydroplastic Polyelectrolyte Films toward Tunable Structures and Programmable Routes. Advanced Functional Materials 2022, 32 (8) , 2107598.
  39. Sabrina S. Alam, Carolina B. Mather, Youngwoo Seo, Yakov Lapitsky. Poly(allylamine)/tripolyphosphate coacervates for encapsulation and long-term release of cetylpyridinium chloride. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2021, 629 , 127490.
  40. Dezhong Liu, Liping Zhu, Wentao Huang, Shuguang Yang. Humidity induced relaxation transition of hydrogen-bonded complex fibers. Polymer 2021, 225 , 123794.
  41. Artem M. Rumyantsev, Nicholas E. Jackson, Juan J. de Pablo. Polyelectrolyte Complex Coacervates: Recent Developments and New Frontiers. Annual Review of Condensed Matter Physics 2021, 12 (1) , 155-176.
  42. Frances J. Morin, Marissa L. Puppo, Jennifer E. Laaser. Decoupling salt- and polymer-dependent dynamics in polyelectrolyte complex coacervates via salt addition. Soft Matter 2021, 17 (5) , 1223-1231.
  43. Flavien Sciortino, Sajjad Husain Mir, Amir Pakdel, Anjaneyulu Oruganti, Hideki Abe, Agnieszka Witecka, Dayangku Noorfazidah Awang Shri, Gaulthier Rydzek, Katsuhiko Ariga. Saloplastics as multiresponsive ion exchange reservoirs and catalyst supports. Journal of Materials Chemistry A 2020, 8 (34) , 17713-17724.
  44. Ivana Škugor Rončević, Denis Krivić, Maša Buljac, Nives Vladislavić, Marijo Buzuk. Polyelectrolytes Assembly: A Powerful Tool for Electrochemical Sensing Application. Sensors 2020, 20 (11) , 3211.
  45. Piotr Batys, Samu Kivistö, Suvesh Manoj Lalwani, Jodie L. Lutkenhaus, Maria Sammalkorpi. Comparing water-mediated hydrogen-bonding in different polyelectrolyte complexes. Soft Matter 2019, 15 (39) , 7823-7831.
  46. Yahui Zhang, Huanyu Xu, Weiquan Xu, Chen Zhang, Jianbing Shi, Bin Tong, Zhengxu Cai, Yuping Dong. Conformational sensitivity of tetraphenyl-1,3-butadiene derivatives with aggregation-induced emission characteristics. Science China Chemistry 2019, 62 (10) , 1393-1397.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Your Mendeley pairing has expired. Please reconnect