Microgels Deswell against Concentration and Solvent Molecular Mass

Yi-Hui Zhu; Qing-Zhi Zou; Zhan-Hui Gan; Yi-Fu Ruan; Kai Qi; Peng-Fei Zhang; Geng-Xin Liu

doi:10.1007/s10118-026-3744-0

Your Location：

Home >

Browse articles >

Microgels Deswell against Concentration and Solvent Molecular Mass

RESEARCH ARTICLE | Updated：2026-09-23

- Microgels Deswell against Concentration and Solvent Molecular Mass
  Enhanced Publication
- Microgels Deswell against Concentration and Solvent Molecular Mass
- Chinese Journal of Polymer Science 2026年44卷第10期页码：3323-3330
- Affiliations：
  
  a.State Key Laboratory of Advanced Fiber Materials, Center for Advanced Low-dimension Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
  b.2020 X-Lab, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, China
  c.Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
  d.South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter & Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou 510640, China
- Author bio：
  
  lgx@dhu.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 22403105 and 22473025), the China Postdoctoral Science Foundation (No. 2025M771120), and the Shanghai Municipal Education Commission.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3744-0.The data supporting the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3744-0
  中图分类号：
- 收稿：2026-04-10，
  
  录用：2026-05-12，
  
  网络首发：2026-07-10，
  
  纸质出版：2026-10-05
- Accepted：
Scan QR Code
Zhu, Y. H.; Zou, Q. Z.; Gan, Z. H.; Ruan, Y. F.; Qi, K.; Zhang, P. F.; Liu, G. X. Microgels deswell against concentration and solvent molecular mass. Chinese J. Polym. Sci. 2026, 44, 3323–3330

Yi-Hui Zhu, Qing-Zhi Zou, Zhan-Hui Gan, et al. Microgels Deswell against Concentration and Solvent Molecular Mass[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3323-3330.
Zhu, Y. H.; Zou, Q. Z.; Gan, Z. H.; Ruan, Y. F.; Qi, K.; Zhang, P. F.; Liu, G. X. Microgels deswell against concentration and solvent molecular mass. Chinese J. Polym. Sci. 2026, 44, 3323–3330 DOI： 10.1007/s10118-026-3744-0.

Yi-Hui Zhu, Qing-Zhi Zou, Zhan-Hui Gan, et al. Microgels Deswell against Concentration and Solvent Molecular Mass[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3323-3330. DOI： 10.1007/s10118-026-3744-0.

摘要

Microgel deswelling is controlled by two coupled factors: the nanoparticle concentration and solvent molecular mass. A higher nanoparticle concentration strengthens osmotic compression

whereas a larger solvent molecular mass reduces network penetration

thereby promoting a transition from swollen to compact particle bulk states

leading to a more fragile soft colloidal glass.

Abstract

The deswelling of microgels is governed by solvent characteristics and particle concentration. Soft nanoparticles have been synthesized and dispersed in small molecular solvents or oligomeric polystyrenes. Coarse-grained molecular dynamics simulations were performed to quantify particle dimensions. The linear viscoelasticity of these solutions was experimentally characterized. In good solvents

increasing the particle concentration induces deswelling because of the enhanced crowding-induced osmotic compression. Increasing the molecular mass of the solvent could also enhance deswelling by suppressing solvent penetration into the nanoparticle network. Equilibrium relations derived from the osmotic-pressure balance are developed to describe these two mechanisms and are shown to capture the simulation results. A single unified framework can describe the deswelling over a broad range of solvent masses and particle concentrations. In addition

varying the solvent mass shifts the fragility transition observed experimentally in solutions of soft nanoparticles

thereby linking deswelling to changes in the glassy dynamics. This work establishes a unified framework for understanding microgel deswelling across concentration- and solvent-controlled regimes.

关键词

Keywords

references

[Rubinstein, M.; Colby, R. H. Polymer physics ; Oxford university press, 2003 , p. 137−196..

Likos, C. N. Effective interactions in soft condensed matter physics. Phys. Rep. 2001 , 348 , 267−439..

Flory, P. J.; Rehner, J. Statistical mechanics of cross-linked polymer networks ii. Swelling. J. Chem. Phys. 1943 , 11 , 521−526..

Huggins, M. L. Solutions of long chain compounds. J. Chem. Phys. 1941 , 9 , 440−440..

Flory, P. J. Thermodynamics of high polymer solutions. J. Chem. Phys. 1942 , 10 , 51−61..

Berthier, L.; Biroli, G. Theoretical perspective on the glass transition and amorphous materials. Rev. Mod. Phys. 2011 , 83 , 587−645..

Ediger, M. D.; Angell, C. A.; Nagel, S. R. Supercooled liquids and glasses. J. Phys. Chem. 1996 , 100 , 13200−13212..

[Angell, C. A. Relaxation in liquids, polymers and plastic crystals — strong/fragile patterns and problems. J. Non·Cryst. Solids 1991 , 131-133 , 13-31..

Debenedetti, P. G.; Stillinger, F. H. Supercooled liquids and the glass transition. Nature 2001 , 410 , 259−267..

Adam, G.; Gibbs, J. H. On the temperature dependence of cooperative relaxation properties in glass-forming liquids. J. Chem. Phys. 1965 , 43 , 139−146..

Lopez, C. G.; Lohmeier, T.; Wong, J. E.; Richtering, W. Electrostatic expansion of polyelectrolyte microgels: Effect of solvent quality and added salt. J. Colloid Interface Sci. 2020 , 558 , 200−210..

Karg, M.; Pich, A.; Hellweg, T.; Hoare, T.; Lyon, L. A.; Crassous, J. J.; Suzuki, D.; Gumerov, R. A.; Schneider, S.; Potemkin, I. I.; et al. Nanogels and microgels: From model colloids to applications, recent developments, and future trends. Langmuir 2019 , 35 , 6231−6255..

Plamper, F. A.; Richtering, W. Functional microgels and microgel systems. Acc. Chem. Res. 2017 , 50 , 131−140..

Pellet, C.; Cloitre, M. The glass and jamming transitions of soft polyelectrolyte microgel suspensions. Soft Matter 2016 , 12 , 3710−3720..

Conley, G. M.; Aebischer, P.; Nöjd, S.; Schurtenberger, P.; Scheffold, F. Jamming and overpacking fuzzy microgels: deformation, interpenetration, and compression. Sci. Adv. 2017 , 3 , e1700969..

Del Monte, G.; Zaccarelli, E. Numerical study of neutral and charged microgel suspensions: from single-particle to collective behavior. Phys. Rev. X 2024 , 14 , 041067..

Zhu, Y.; Gao, Y.; Gao, J.; Zhang, R.; Liu, G. Quantifying the fragility–el asticity relationship in uncharged ultrasmall polymeric colloids. ACS Macro Letters 2026 , 15 , 137−142..

Marín-Aguilar, S.; Zaccarelli, E. Unexpected behavior of ultra-low-crosslinked microgels in crowded conditions. Proc. Natl. Acad. Sci. 2026 , 123 , e2530546123..

Ouyang, X.; Luo, J.; Li, T.; Zhu, Y.; Yu, W.; He, J.; Zhang, P.; Liu, G. The second network of soft-nanoparticles in linear polymers of the same chemistry. Polymer 2023 , 283 , 126216..

Lyon, L. A.; Fernandez-Nieves, A. The polymer/colloid duality of microgel suspensions. Annu. Rev. Phys. Chem. 2012 , 63 , 25−43..

Gerelli, Y.; Camerin, F.; Bochenek, S.; Schmidt, M. M.; Maestro, A.; Richtering, W.; Zaccarelli, E.; Scotti, A. Softness matters: effects of compression on the behavior of adsorbed microgels at interfaces. Soft Matter 2024 , 20 , 3653−3665..

Pelaez-Fernandez, M.; Souslov, A.; Lyon, L. A.; Goldbart, P. M.; Fernandez-Nieves, A. Impact of single-particle compressibility on the fluid-solid phase transition for ionic microgel suspensions. Phys. Rev. Lett. 2015 , 114 , 098303..

Scotti, A.; Pelaez-Fernandez, M.; Gasser, U.; Fernandez-Nieves, A. Osmotic pressure of suspensions comprised of charged microgels. Phys. Rev. E 2021 , 103 , 012609..

Camerin, F.; Gnan, N.; Ruiz-Franco, J.; Ninarello, A.; Rovigatti, L.; Zaccarelli, E. Microgels at interfaces behave as 2d elastic particles featuring reentrant dynamics. Phys. Rev. X 2020 , 10 , 031012..

Urich, M.; Denton, A. R. Swelling, structure, and phase stability of compressible microgels. Soft Matter 2016 , 12 , 9086−9094..

Bouhid de Aguiar, I.; van de Laar, T.; Meireles, M.; Bouchoux, A.; Sprakel, J.; Schroën, K. Deswelling and deformation of microgels in concentrated packings. Sci. Rep. 2017 , 7 , 1−11..

Mattsson, J.; Wyss, H. M.; Fernandez-Nieves, A.; Miyazaki, K.; Hu, Z.; Reichman, D. R.; Weitz, D. A. Soft colloids make strong glasses. Nature 2009 , 462 , 83−86..

Larin, D. E.; Shibaev, A. V.; Liu, C. Y.; Emelyanenko, A. V. The effect of dynamic cross-links and mesogenic groups on the swelling and collapse of polymer gels. Giant 2024 , 20 , 100341..

[Hwang, J.; Martinez, D. V.; Martinez, E. J.; Metavarayuth, G.;Goodlett, D.; Wang, Q.; Ganewatta, M.; Kent, M. S.; Tang, C. Highly swellable hydrogels prepared from extensively oxidized lignin. Giant 2022 , 10 , 100106..

Tuteja, A.; Duxbury, P. M.; Mackay, M. E. Polymer chain swelling induced by dispersed nanoparticles. Phys. Rev. Lett. 2008 , 100 , 077801..

Maiz, J.; Verde-Sesto, E.; Asenjo-Sanz, I.; Mangin-Thro, L.; Frick, B.; Pomposo, J. A.; Arbe, A.; Colmenero, J. Disentangling component dynamics in an all-polymer nanocomposite based on single-chain nanoparticles by quasielastic neutron scattering. Macromolecules 2022 , 55 , 2320−2332..

Xu, B.; Xu, H.; Song, Y.; Zheng, Q. Segmental dynamics and linear rheology of nearly athermal all-polystyrene nanocomposites. Compos. Sci. Technol. 2019 , 177 , 111−117..

Tuteja, A.; Mackay, M. E.; Hawker, C. J.; Van Horn, B.; Ho, D. L. Molecular architecture and rheological characterization of novel intramolecularly crosslinked polystyrene nanoparticles. J. Polym. Sci., Part B: Polym. Phys. 2006 , 44 , 1930−1947..

Mackay, M. E.; Dao, T. T.; Tuteja, A.; Ho, D. L.; Van Horn, B.; Kim, H.-C.; Hawker, C. J. Nanoscale effects leading to non-einstein-like decrease in viscosity. Nat. Mater. 2003 , 2 , 762−766..

Chen, T.; Zhao, H. Y.; Shi, R.; Lin, W. F.; Jia, X. M.; Qian, H. J.; Lu, Z. Y.; Zhang, X. X.; Li, Y. K.; Sun, Z. Y. An unexpected n-dependence in the viscosity reduction in all-polymer nanocomposite. Nat. Commun. 2019 , 10 , 1−8..

Cui, T.; Zhu, Y.; Liu, S.; Huang, Q. Extensional rheology of all-polystyrene nanocomposites. Phys. Fluids 2024 , 36 , 113120..

Luo, J.; Zhu, Y.; Ruan, Y.; Wu, W.; Ouyang, X.; Du, Z.; Liu, G. Diameter and elasticity governing the relaxation of soft-nanoparticle melts. Macromolecules 2021 , 54 , 8077−8087..

Rieger, J. The glass transition temperature tg of polymers—comparison of the values from differential thermal analysis (DTA, DSC) and dynamic mechanical measurements (torsion pendulum). Polym. Test. 2001 , 20 , 199−204..

Hagen, R.; Salmén, L.; Lavebratt, H.; Stenberg, B. Comparison of dynamic mechanical measurements and tg determinations with two different instruments. Polym. Test. 1994 , 13 , 113−128..

Gracia-Fernández, C. A.; Gómez-Barreiro, S.; López-Beceiro, J.; Tarrío Saavedra, J.; Naya, S.; Artiaga, R. Comparative study of the dynamic glass transition temperature by DMA and TMDSC. Polym. Test. 2010 , 29 , 1002−1006..

Napolitano, S.; Glynos, E.; Tito, N. B. Glass transition of polymers in bulk, confined geometries, and near interfaces. Rep. Prog. Phys. 2017 , 80 , 036602..

Zou, Q.; Zhu, Y.; Ruan, Y.; Zhang, R.; Liu, G. Coarse-grained soft-clusters remain non-diffusing in the melt state. Giant 2021 , 8 , 100070..

van der Scheer, P.; van de Laar, T.; van der Gucht, J.; Vlassopoulos, D.; Sprakel, J. Fragility and strength in nanoparticle glasses. ACS Nano 2017 , 11 , 6755−6763..

Voudouris, P.; Florea, D.; van der Schoot, P.; Wyss, H. M. Micromechanics of temperature sensitive microgels: Dip in the poisson ratio near the lcst. Soft Matter 2013 , 9 , 7158..

Hashmi, S. M.; Dufresne, E. R. Mechanical properties of individual microgel particles through the deswelling transition. Soft Matter 2009 , 5 , 3682..

Lopez, C. G.; Richtering, W. Does flory–rehner theory quantitatively describe the swelling of thermoresponsive microgels. Soft Matter 2017 , 13 , 8271−8280..

Speedy, R. J. The equation of state for the hard sphere fluid at high density. The glass transition. Physica B+C 1983 , 121 , 153−161..

Carnahan, N. F.; Starling, K. E. Equation of state for nonattracting rigid spheres. J. Chem. Phys. 1969 , 51 , 635−636..

Pyett, S.; Richtering, W. Structures and dynamics of thermosensitive microgel suspensions studied with three-dimensional cross-correlated light scattering. J. Chem. Phys. 2005 , 122 , 034709..

Stieger, M.; Pedersen, J. S.; Lindner, P.; Richtering, W. Are thermoresponsive microgels model systems for concentrated colloidal suspensions? A rheology and small-angle neutron scattering study. Langmuir 2004 , 20 , 7283−7292..

Carrier, V.; Petekidis, G. Nonlinear rheology of colloidal glasses of soft thermosensitive microgel particles. J. Rheol. 2009 , 53 , 245−273..

Wilcox, K. G.; Kozawa, S. K.; Morozova, S. Fundamentals and mechanics of polyelectrolyte gels: Thermodynamics, swelling, scattering, and elasticity. Chem. Phys. Rev. 2021 , 2 , 041309..

Richbourg, N. R.; Peppas, N. A. The swollen polymer network hypothesis: Quantitative models of hydrogel swelling, stiffness, and solute transport. Prog. Polym. Sci. 2020 , 105 , 101243..

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Swelling, Interfacial Behavior, and Rheology of Soft Core-Shell Microgels Introducing Acid Isomer for pH-Temperature Dual-responsiveness

Thermo-sensitive Microgels Supported Gold Nanoparticles as Temperature-mediated Catalyst

Assembly of Highly Ordered 2D Arrays of Silver-PNIPAM Hybrid Microgels

Self-assembly of Hollow PNIPAM Microgels to Form Discontinuously Hollow Fibers

Silk Sericin-inspired Poly-β-homoserine for Protein Protection