Aggregation of Hydroxypropyl Cellulose in Dilute Solutions with Salt Ions

Authors

  • V.I. Kovalchuk Taras Shevchenko National University of Kyiv, Faculty of Physics
  • Yu.F. Zabashta Taras Shevchenko National University of Kyiv, Faculty of Physics
  • L.A. Bulavin Taras Shevchenko National University of Kyiv, Faculty of Physics

DOI:

https://doi.org/10.15407/ujpe71.6.529

Keywords:

hydroxypropyl cellulose, salt ions, aggregation, Cahn–Hilliard equation

Abstract

The kinetics of the phase transition in an aqueous solution of hydroxypropyl cellulose with salt ions have been studied using mathematical modeling. Based on the nonlinear Cahn–Hilliard equation with a stochastic term, the hydrophobicity parameter, and the mobility parameter depending on the polymer concentration, the phase separation on a simple one-dimensional Flory lattice was simulated. Data on changes in the average sizes and masses of aggregates were obtained for a set of hydrophobicity parameter values. The simulation results allowed the distinction of three stages of spinodal decomposition: early, intermediate, and final. It was found that the kinetics of cluster mass growth at the intermediate and final stages are described by scaling dependencies, with the power exponents and the crossover time determining the transition from the mode of aggregate mass accumulation driven by surface tension effects to the diffusion mode. It was shown that the variation of the average cluster size can be approximated by a scaling function with a power exponent close to 1/3, which is typical of systems with a conservative scalar order parameter. From the results of computer simulation, it follows that the growth of the interfacial energy density (the enhancement of hydrophobic interactions) makes the size of polymer aggregates larger.

References

1. F. Tanaka. Polymer Physics: Applications to Molecular Association and Thermoreversible Gelation (Cambridge University Press, 2011).

https://doi.org/10.1017/CBO9780511975691

2. R. Bayer, M. Knarr. Thermal precipitation or gelling behaviour of dissolved methylcellulose (MC) derivatives behaviour in water and influence on the extrusion of ceramic pastes. Part 1: Fundamentals of MC-derivatives. J. Eur. Ceram. Soc. 32, 1007 (2012).

https://doi.org/10.1016/j.jeurceramsoc.2011.11.025

3. Y. Tian, Y. Liu, B. Ju, X. Ren, M. Dai. Thermoresponsive 2-hydroxy-3-isopropoxypropyl hydroxyethyl cellulose with tunable LCST for drug delivery. RSC Adv. 9, 2268 (2019).

https://doi.org/10.1039/C8RA09075K

4. M Gosecki, H. Setälä, T. Virtanen, A.J. Ryan. A facile method to control the phase behavior of hydroxypropyl cellulose. Carbohydr. Polym. 251, 117015 (2021).

https://doi.org/10.1016/j.carbpol.2020.117015

5. Z. Zhang, L. Chen, C. Zhao, Y. Bai, M. Deng, H. Shan, X. Zhuang, X. Chen, X. Jing. Thermo- and pH-responsive HPC-g-AA/AA hydrogels for controlled drug delivery applications. Polymer 52, 676 (2011).

https://doi.org/10.1016/j.polymer.2010.12.048

6. Y. Bai, Z. Zhang, A. Zhang, L. Chen, C. He, X. Zhuang, X. Chen. Novel thermo- and pH-responsive hydroxypropyl cellulose- and poly (l-glutamic acid)-based microgels for oral insulin controlled release. Carbohydr. Polym. 89, 1207 (2012).

https://doi.org/10.1016/j.carbpol.2012.03.095

7. X. Qiu, S. Hu. "Smart" materials based on cellulose: A review of the preparations, properties, and applications. Materials 6, 738 (2013).

https://doi.org/10.3390/ma6030738

8. F. Ofridam, M. Tarhini, N. Lebaz, É. Gagnière, D. Mangin, A. Elaissari. pH-sensitive polymers: Classification and some fine potential applications. Polym. Adv. Technol. 32, 1455 (2021).

https://doi.org/10.1002/pat.5230

9. Y. Xu, C. Wang, K.C. Tam, L. Li. Salt-assisted and salt-suppressed sol-gel transitions of methylcellulose in water. Langmuir 20, 646 (2004).

https://doi.org/10.1021/la0356295

10. Y. Xu, L. Li, P. Zheng, Y.C. Lam, X. Hu. Controllable gelation of methylcellulose by a salt mixture. Langmuir 20, 6134 (2004).

https://doi.org/10.1021/la049907r

11. P. Zheng, L. Li, X. Hu, X. Zhao. Sol-gel transition of methylcellulose in phosphate buffer saline solutions. J. Polym. Sci. B Polym. Phys. 42, 1849 (2004).

https://doi.org/10.1002/polb.20070

12. M. Lazarenko, A. Alekseev, Yu. Zabashta, S. Tkachev, V. Kovalchuk, D. Andrusenko, Yu. Grabovsky, L. Bulavin. Estimation of water content in cellulose materials. Cellul. Chem. Technol. 54, 199 (2020).

13. E. Weißenborn, B. Braunschweig. Hydroxypropyl cellulose as a green polymer for thermo-responsive aqueous foams. Soft Matter 15, 2876 (2019).

https://doi.org/10.1039/C9SM00093C

14. B. Nyström, J. Roots, A. Carlsson, B. Lindman. Light scattering studies of the gelation process in an aqueous system of a non-ionic polymer and a cationic surfactant. Polymer 33, 2875 (1992).

https://doi.org/10.1016/0032-3861(92)90071-4

15. S.C. Joshi. Sol-gel behavior of hydroxypropyl methylcellulose (HPMC) in ionic media including drug release. Materials 4, 1861 (2011).

https://doi.org/10.3390/ma4101861

16. M. Fettaka, R. Issaadi, N. Moulai-Mostefa, I. Dez, D. Le Cerf, L. Picton. Thermo sensitive behavior of cellulose derivatives in dilute aqueous solutions: From macroscopic to mesoscopic scale. J. Colloid Interface Sci. 357, 372 (2011).

https://doi.org/10.1016/j.jcis.2011.02.041

17. N. Almeida, L. Rakesh, J. Zhao. Monovalent and divalent salt effects on thermogelation of aqueous hypromellose solutions. Food Hydrocoll. 36, 323 (2014).

https://doi.org/10.1016/j.foodhyd.2013.10.020

18. M. Lazarenko, S. Nedilko, S. Gryn, V. Scherbatskyi, V. Kovalchuk, M. Lazarenko, A. Sobchuk, D. Andrusenko, O. Alekseev. Influence of Na+ and Cl− ions on the properties of hydroxypropyl cellulose solutions. In Proceedings of the 41st IEEE International Conference on Electronics and Nanotechnology (ELNANO), Kyiv, Ukraine, October 10-14, 2022 (Igor Sikorsky Kyiv Polytechnic Institute, 2022), p. 418.

https://doi.org/10.1109/ELNANO54667.2022.9927040

19. M.M. Lazarenko, O.M. Alekseev, S.G. Nedilko, A.O. Sobchuk, V.I. Kovalchuk, S.V. Gryn, V.P. Scherbatskyi, S.Yu. Tkachev, D.A. Andrusenko, E.G. Rudnikov, A.V. Brytan, K.S. Yablochkova, E.A. Lysenkov, R.V. Dinzhos, T. Sabu, T.R. Abraham. Impact of the alkali metals ions on the dielectric relaxation and phase transitions in water solutions of the hydroxypropylcellulose. In: NANO 2022: Nanoelectronics, Nanooptics, Nanochemistry and Nanobiotechnology, and Their Applications, Lviv, Ukraine, August 25-27, 2022 (Springer, 2023), p. 37.

https://doi.org/10.1007/978-3-031-42708-4_3

20. L.A. Bulavin, N.I. Lebovka, Yu.A. Kyslyi, S.V. Khrapatyi, A.I. Goncharuk, I.A. Mel'nyk, V.I. Koval'chuk. Microstructural, rheological, and conductometric studies of multiwalled carbon nanotube suspensions in glycerol. Ukr. J. Phys. 56, 217 (2011).

21. M. Stoian, T. Maurer, S. Lamri, I. Fechete. Techniques of preparation of thin films: Catalytic combustion. Catalysts 11, 1530 (2021).

https://doi.org/10.3390/catal11121530

22. A. Salama, R.E. Abouzeid, M.E. Owda, I. Cruz-Maya, V. Guarino. Cellulose-silver composites materials: Preparation and applications. Biomolecules 11, 1684 (2021).

https://doi.org/10.3390/biom11111684

23. G. Biliuta, A.-C. Bostănaru-Iliescu, M. Mareș, C. Pavlov-Enescu, V. Năstasă, O. Burduniuc, S. Coseri. Antibacterial and antifungal silver nanoparticles with tunable size embedded in various cellulose-based matrices. Molecules 27, 6680 (2022).

https://doi.org/10.3390/molecules27196680

24. A.R. Khokhlov, E.E. Dormidontova. Self-organization in ion-containing polymer systems. Phys.-Uspekhi 40, 109 (1997).

https://doi.org/10.1070/PU1997v040n02ABEH000191

25. V.I. Kovalchuk, Yu.F. Zabashta, L.A. Bulavin. Features of gelation and aggregation in aqueous solutions of hydroxypropyl cellulose with NaCl, NaI, and AgNO3 salts. Ukr. J. Phys. 69, 207 (2024).

https://doi.org/10.15407/ujpe69.3.207

26. Yu.F. Zabashta, V.I. Kovalchuk, S.V. Gryn. Phase transition and microgel formation in polymer solutions with salt ions. Ukr. J. Phys. 70, 200 (2025).

https://doi.org/10.15407/ujpe70.3.200

27. J.P.A. Fairclough, H. Yu, O. Kelly, A.J. Ryan, R.L. Sammler, M. Radler. Interplay between gelation and phase separation in aqueous solutions of methylcellulose and hydroxypropylmethylcellulose. Langmuir 28, 10551 (2012).

https://doi.org/10.1021/la300971r

28. N. Sarkar. Thermal gelation properties of methyl and hydroxypropyl methylcellulose. J. Appl. Polym. Sci. 24, 1073 (1979).

https://doi.org/10.1002/app.1979.070240420

29. H. Takeshita, K. Saito, M. Miya, K. Takenaka, T. Shiomi. Laser speckle analysis on correlation between gelation and phase separation in aqueous methyl cellulose solutions. J. Polym. Sci. B. 48, 168 (2010).

https://doi.org/10.1002/polb.21885

30. M.A. Villetti, V. Soldi, C. Rochas, R. Borsali. Phase-separation kinetics and mechanism in a methylcellulose/salt aqueous solution studied by time-resolved small-angle light scattering (SALS). Macromol. Chem. Phys. 212, 1063 (2011).

https://doi.org/10.1002/macp.201000697

31. V.P. Skripov, A.V. Skripov. Spinodal decomposition (phase transitions via unstable states). Sov. Phys. Usp. 22, 389 (1979).

https://doi.org/10.1070/PU1979v022n06ABEH005571

32. J.W. Cahn, J.E. Hilliard. Free energy of a nonuniform system. I. Interfacial free energy. J. Chem. Phys. 28, 258 (1958).

https://doi.org/10.1063/1.1744102

33. J. Cahn. On spinodal decomposition. Acta Metall. 9, 795 (1961).

https://doi.org/10.1016/0001-6160(61)90182-1

34. S.C. Glotzer, W. Paul. Molecular and mesoscale simulation methods for polymer materials. Annu. Rev. Mater. Res. 32, 401 (2002).

https://doi.org/10.1146/annurev.matsci.32.010802.112213

35. D. Lee, J.-Y. Huh, D. Jeong, J. Shin, A. Yun, J. Kim. Physical, mathematical, and numerical derivations of the Cahn-Hilliard equation. Comput. Mater. Sci. 81, 216 (2014).

https://doi.org/10.1016/j.commatsci.2013.08.027

36. P.E. L'vov, V.V. Svetukhin. Simulation of the decomposition of binary alloys on the basis of the free energy density functional method. Phys. Solid State 59, 335 (2017).

https://doi.org/10.1134/S1063783417020160

37. X. Li, G. Ji, H. Zhang. Phase transitions of macromolecular microsphere composite hydrogels based on the stochastic Cahn-Hilliard equation. J. Comput. Phys. 283, 81 (2015).

https://doi.org/10.1016/j.jcp.2014.11.032

38. P.G. de Gennes. Dynamics of fluctuations and spinodal decomposition in polymer blends. J. Chem. Phys. 72, 4756 (1980).

https://doi.org/10.1063/1.439809

39. P.J. Flory. Principles of Polymer Chemistry (Cornell University Press, 1953) [ISBN: 978-0801401343].

40. L.D. Landau, E.M. Lifshitz. Course of Theoretical Physics, Vol. 5: Statistical Physics (Butterworth-Heinemann, 1980) [ISBN: 978-0750633727].

41. M.L. Huggins. Physical Chemistry of High Polymers (Literary Licensing LLC, 2013) [ISBN: 978-1258783365].

42. V.I. Kovalchuk. Phase separation dynamics in aqueous solutions of thermoresponsive polymers. Cond. Matt. Phys. 24, 43601 (2021).

https://doi.org/10.5488/CMP.24.43601

43. R.A. Orwoll, P.A. Arnold. Polymer-Solvent Interaction Parameter χ. In: Physical Properties of Polymers Handbook (Springer-Verlag, 2007), Ch. 14, p. 233 [ISBN: 978-0387312354].

https://doi.org/10.1007/978-0-387-69002-5_14

44. Hydroxypropyl Cellulose. Available online: https://www.chemsrc.com/en/cas/9004-64-2_1198776.html (accessed on September 03, 2025).

45. E.D. Siggia. Late stages of spinodal decomposition in binary mixtures. Phys. Rev. A 20, 595 (1979).

https://doi.org/10.1103/PhysRevA.20.595

46. F. Georget, W. Wilson, T. Matschei. Long-term extrapolation of chloride ingress: An illustration of the feasibility and pitfalls of the square root law. Cem. Concr. Res. 170, 107187 (2023).

https://doi.org/10.1016/j.cemconres.2023.107187

47. Bray A.J., Rutenberg A.D. Growth laws for phase ordering. Phys. Rev. E 49, R27 (1994).

https://doi.org/10.1103/PhysRevE.49.R27

48. Lifshitz I.M., Slyozov V.V. The kinetics of precipitation from supersaturated solid solutions. J. Phys. Chem. Solids 19, 35 (1961).

https://doi.org/10.1016/0022-3697(61)90054-3

49. Bray A.J. Domain-growth scaling in systems with long-range interactions. Phys. Rev. E 47, 3191 (1993).

https://doi.org/10.1103/PhysRevE.47.3191

Published

2026-05-25

Issue

Section

Liquid crystals and polymers

How to Cite

Aggregation of Hydroxypropyl Cellulose in Dilute Solutions with Salt Ions. (2026). Ukrainian Journal of Physics, 71(6), 529. https://doi.org/10.15407/ujpe71.6.529

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