

FOLLOWUS
a.School of Physics and Electronic Engineering, Qilu Normal University, Jinan 250200, China
b.Key Laboratory of Weak-Light Nonlinear Photonics, Ministry of Education, School of Physics, Nankai University, Tianjin 300071, China
c.Department of Thermal Engineering, Shandong Jianzhu University, Jinan 250101, China
liuzhiyaonku@163.com
Received:26 November 2025,
Revised:2025-12-20,
Accepted:05 January 2026,
Online First:06 February 2026,
Published:15 March 2026
Scan QR Code
Liu, Z. Y.; Wang, H.; Bu, H. X.; Wang, J.; Li, B. H.; Liu, L. L. Reentrant phase behavior in diblock copolymer AB/homopolymer C blends: a combined effect of solvent selectivity and block interactions. Chinese J. Polym. Sci. 2026, 44, 857–868
Zhi-Yao Liu, Hui Wang, Hong-Xia Bu, et al. Reentrant Phase Behavior in Diblock Copolymer AB/Homopolymer C Blends: A Combined Effect of Solvent Selectivity and Block Interactions[J]. Chinese Journal of Polymer Science, 2026, 44(3): 857-868.
Liu, Z. Y.; Wang, H.; Bu, H. X.; Wang, J.; Li, B. H.; Liu, L. L. Reentrant phase behavior in diblock copolymer AB/homopolymer C blends: a combined effect of solvent selectivity and block interactions. Chinese J. Polym. Sci. 2026, 44, 857–868 DOI: 10.1007/s10118-025-3546-9.
Zhi-Yao Liu, Hui Wang, Hong-Xia Bu, et al. Reentrant Phase Behavior in Diblock Copolymer AB/Homopolymer C Blends: A Combined Effect of Solvent Selectivity and Block Interactions[J]. Chinese Journal of Polymer Science, 2026, 44(3): 857-868. DOI: 10.1007/s10118-025-3546-9.
The phase behavior of diblock copolymer AB/homopolymer C blends in concentrated aqueous solutions was investigated using a simulated annealing method. The studies reveal reentrant phase behavior in the system with increasing homopolymer content
driven by the competing swelling effects of the solvent and homopolymer.
We investigated the phase behavior of diblock copolymer AB/homopolymer C blends in concentrated aqueous solutions using a simulated annealing method. Phase diagrams were constructed as a function of the concentration of all polymers (
Φ
) and the volume fraction of homopolymer (
f
C
). Rich phase transition sequences
were observed
especially reentrant phase transitions
such as lamellae → inverted cylinders → gyroids → lamellae → disorder
for a given
Φ
with increasing
f
C
. By analyzing the variations in the average contact numbers between different components and the effective volume fractions of B-domains
we elucidated the mechanisms of the reentrant phase transitions. We found that the strong attraction between B and C leads to the swelling of B-domains upon addition of homopolymer. Concurrently
the solvent preferentially swells the A-domains over the B+C-domains. The competing swelling effects of the solvent and homopolymer on the A-domains and B-domains
respectively
triggered the reentrant phase behavior in the symmetric AB copolymer system upon addition of homopolymer.
Doerk, G. S.; Kulkarni, A. A.; Li, R. Engineering self-assembled domain asymmetry in solvent vapor annealed block copolymer-homopolymer blend films. Macromolecules 2024 , 57 , 181−190..
Maekawa, S.; Seshimo, T.; Dazai, T.; Sato, K.; Sato, K. H.; Nabae, Y.; Hayakawa, T. Chemically tailored block copolymers for highly reliable sub-10-nm patterns by directed self-assembly. Nat. Commun. 2024 , 15 , 1−11..
[Polymeropoulos, G.; Zapsas, G.; Ntetsikas, K.; Bilalis, P.; Gnanou, Y.; Hadjichristidis, N. 50 th Anniversary perspective: polymers with complex architectures. Macromolecules 2017 , 50 , 1253−1290..
[Zhang, W. J.; Hong, C. Y.; Pan, C. Y. Polymerization-induced self-assembly of functionalized block copolymer nanoparticles and their application in drug delivery, Macromol. Rapid Commun . 2018 , 1800279..
Parkin, H. C.; Street, S. T. G.; Gowen, B.; Da-Silva-Correa, L. H.; Hof, R.; Buckley, H. L.; Manners, I. Mechanism of action and design of potent antibacterial block copolymer nanoparticles. J. Am. Chem. Soc. 2024 , 146 , 5128−5141..
Hur, Y. H.; Song, S. W.; Kim, J. M.; Park, W. I.; Kim, K. H.; Kim, Y. J.; Jung, Y. S. Thermodynamic and kinetic tuning of block copolymer based on random copolymerization for high-quality sub-6 nm pattern formation. Adv. Funct. Mater . 2018 , 1800765..
Tao, Y. X.; Chen, L. L.; Liu, Y. H.; Hu, X.; Zhu, Z.; Guo, K. Synthesis and self-assembly of silicon-containing block copolym ers for sub 5 nm nanolithography. Acta Polymerica Sinica (in Chinese) 2022 , 53 , 1445−1458..
Su, G.; Zhang, Z.; Xiao, M.; Wang, S.; Huang, S.; Guo, H.; Han, D.; Meng, Y. Boosting electrochemical performance by regulating rigid-flexible microphase separation of multiblock copolymers. Chem. Eng. J. 2024 , 500 , 157050..
Wang, T.; Zhong, L.; Xiao, M.; Han, D.; Wang, S.; Huang, Z.; Huang, S.; Sun, L.; Meng, Y. Block copolymer electrolytes for lithium metal batteries: strategies to boost both ionic conductivity and mechanical strength. Prog. Polym. Sci. 2023 , 146 , 101743..
Moirangthem, P. M.; Shagolsem, L. S. Phase and order behavior of charged asymmetric diblock-copolymer melts in bulk. Macromol. Symp. 2024 , 413 , 2300028..
Masten, M. W.; Schick, M. Stable and unstable pha se in diblock copolymer melt. Phys. Rev. Lett. 1994 , 72 , 2660−2663..
Beardsley, T. M.; Matsen, M. W. Monte carlo phase diagram for diblock copolymer melts. Eur. Phys. J. E. 2010 , 32 , 255−264..
Matsen, M. W. Effect of architecture on the phase behavior of AB-type block copolymer melts. Macromolecules 2012 , 45 , 2161−2165..
Chen, H.; Dong, Q.; Qiang, Y.; Peng, L.; Huang, X.; Li, W. Mechanisms of multiple reentrant transitions between Frank-Kasper and classical spherical phases in AB-type dendron-like copolymer. Macromolecules 2025 , 58 , 10192−10202..
Shi, W.; Li, W.; Delaney, K. T.; Fredrickson, G. H.; Kramer, E. J.; Ntaras, C.; Avgeropoulos, A.; Lynd, N. A. Morphology re-entry in asymmetric PS-PI-PS’ triblock copolymer and PS homopolymer blends. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54 , 169−179..
Chen, L.; Qiang, Y.; Li, W. Tuning arm architecture leads to unusual phase behaviors in a (BAB) 5 star copolymer melt. Macromolecules 2018 , 51 , 9890−9900..
Peng, Z.; Ghasemi, M.; Michels, J. J.; Ade, H. Re-entrant phase behaviour of organic semiconductors. Nat. Mater. 2025 , 24 , 1785−1792..
Liu, J.; Jiang, Y.; Liu, R.; Jin, J.; Wei, S.; Ji, W.; He, X.; Wu, F.; Yu, P.; Mao, L. Vitamin C drives reentrant actin phase transition: biphasic exocytosis regulation revealed by single-vesicle electrochemistry. J. Am. Chem. Soc. 2024 , 146 , 17747−17756..
Su, L.; Mosquera, J.; Mabesoone, M. F. J.; Schoenmakers, S. M. C.; Muller, C.; Vleugels, M. E. J.; Dhiman, S.; Wijker, S.; Palmans, A. R. A.; Meijer, E. W. Dilution-induced gel-sol-gel-sol transitions by competitive supramolecular pathways in water. Science 2022 , 377 , 213−218..
[Pegoraro, C.; Karpova, E.; Qutbuddin, Y.; Sanchis, E. M.; Dimitrijevs, P.; Huck-Iriart, C.; Gavrilović, S.; Arsenyan, P.; Schwille, P.; Felip-León, C.; Duro-Castano, A.; Conejos-Sanchez, I.; Vicent, M. J. Polyproline-polyornithine diblock copolymers with inherent mitochondria tropism. Adv. Mater . 2025 , 2411595..
Chrysostomou, V.; Da Vela, S.; Pispas, S.; Papadakis, C. M. PH and temperature dependence of low-core tg micellar structures formed by PDMAEMA- b -PLMA diblock copolymers in aqueous solution. J. Polym. Sci. 2025 , 63 , 1684−1694..
Constantin, M.; Ailiesei, G.; Fundueanu, G.; Tarabukina, E.; Krasova, A.; Filippov, A. Synthesis and behavior in aqueous solution of carboxymethyl pullulan-graft-poly( N -isopropylacrylamide- co -methacrylamide). J. Mol. Liq. 2024 , 399 , 124338..
Bednarek, M.; Grabowski, M. Polylactide/poly(vinyl monomer) block copolymers for specific applications. Polym. Rev . 2024 , 2310105..
Yokota, K.; Usuda, S.; Nishimura, T.; Takahashi, R.; Taoka, Y.; Kobayashi, S.; Tanaka, M.; Matsumura, K.; Yusa, S. I. Self-assembly and drug encapsulation properties of biocompatible amphiphilic diblock copolymers. Langmuir 2025 , 41 , 765−773..
Han, Y.; Lu, Y.; Song,T.; Cui, J.; Fan, J. Topology-directed coassembly of linear and cyclic amphiphilic diblock copolymers: a Monte Carlo study. Langmuir 2024 , 40 , 16103−16112..
Pavlenko, S. A.; Larin, D. E.; Govorun, E. N. Self-assembly of hydrophobic-amphiphilic diblock copolymers in solution. J. Phys. Condens. Matter. 2022 , 34 , 125001..
Fischer, J.; Porcar, L.; Cabral, J. T.; Sottmann, T. Using an amphiphilic diblock copolymer to understand the shear-induced structural transformation of bicontinuous microemulsions. J. Colloid Interface Sci. 2024 , 671 , 124−133..
[Yokota, K.; Takahashi, R.; Ngan, V. T.; Nishimura, T.; Kappl, M.; Fujii, S.; Yusa, S. I. Preparation of water-soluble polyion complex (pic) micelles with pH-responsive carboxybetaine block. Macromol. Rapid Commun . 2024 , 2400532..
Higaki, Y.; Toyama, H.; Masuda, T.; Kobayashi, S.; Tanaka, M. Microphase separation of double-hydrophilic poly(carboxybetaine acrylate)-poly(2-methoxyethyl acrylate) block copolymers in water. Polym. J. 2023 , 55 , 1357−1365..
Wu, R.; Yan, Y.; Li, X.; Tan, Y. Preparation and evaluation of double-hydrophilic diblock copolymer as viscosity reducers for heavy oil. J. Appl. Polym. Sci. 2023 , 140 , e53278..
Blanazs, A.; Warren, N. J.; Lewis, A. L.; Armes, S. P.; Ryan, A. J. Self-assembly of double hydrophilic block copolymers in concentrated aqueous solution. Soft Matter 2011 , 7 , 6399−64 03..
Casse, O.; Shkilnyy, A.; Linders, J.; Mayer, C.; Häussinger, D.; Völkel, A.; Thünemann, A. F.; Dimova, R.; Cölfen, H.; Meier, W.; Schlaad, H.; Taubert, A. Solution behavior of double-hydrophilic block copolymers in dilute aqueous solution. Macromolecules 2012 , 45 , 4772−4777..
Wu, J. P.; Wang, Z.; Yin, Y. H.; Jiang, R.; Li, B. H. A simulation study of phase behavior of double-hydrophilic block copolymers in aqueous solutions. Macromolecules 2015 , 48 , 8897−8906..
Xie, J. Y.; Lai, C. T.; Shi, A. C. Regulating the self-assembly of AB/CD diblock copolymer blends via secondary interactions. J. Polym. Sci. 2024 , 62 , 716−732..
Toth, K.; Bae, S.; Osuji, C. O.; Yager, K. G.; Doerk, G. S. Film thickness and composition effects in symmetric ternary block copolymer/homopolymer blend films: domain spacing and orientation. Macromolecules 2021 , 54 , 7970−7986..
Bezik, C. T.; Mysona, J. A.; Schneider, L.; Ramírez-Hernández, A.; Müller, M.; de Pablo, J. J. Is the “bricks-and-mortar” mesophase bicontinuous? Dynamic simulations of miktoarm block copolymer/homopolymer blends. Macromolecules 2022 , 55 , 745−758..
Hong, S. J.; Kim, G. R.; Kim, N. K.; Shin, J.; Kim, Y. W. Poly(amide11)-incorporated block copolymers as compatibilizers to toughen a poly(lactide)/polyamide 11 blend. ACS Appl. Polym. Mater. 2024 , 6 , 1224−1235..
Dobrosielska, K.; Wakao, S.; Suzuki, J.; Noda, K.; Takano, A.; Matsushita, Y. Effect of homopolymer molecular weight on nanophase-separated structures of AB block copolymer/C homopolymer blends with hydrogen-bonding interactions. Macromolecules 2009 , 42 , 7098−7102..
Matsushita, Y. Creation of hierarchically ordered nanophase structures in block polymers having various competing interactions. Macromolecules 2007 , 40 , 771−776..
Dobrosielska, K.; Wakao, S.; Takano, A.; Matsushita, Y. Nanophase-separated structures of AB block copolymer/C homopolymer blends with complementary hydrogen-bonding interactions. Macromolecules 2008 , 41 , 7695−7698..
[Dehghan, A.; Shi, A. C. Modeling hydrogen bonding in diblock copolymer/homopolymer blends. Macromolecules 2013 , 46 , 5796–5805..
Hameed, N.; Guo, Q. Nanostructure and hydrogen bonding in interpolyelectrolyte complexes of poly( ε -caprolactone)-block-poly(2-vinyl pyridine) and poly(acrylic acid). Polymer 2008 , 49 , 5268−5275..
Hameed, N.; Liu, J.; Guo, Q. Self-assembled complexes of poly(4-vinylphenol) and poly( ε -caprolactone)-block-poly(2-vinylpyr-idine) via competitive hydrogen bonding. Macromolecules 2008 , 41 , 7596−7605..
Hameed, N.; Guo, Q. Selective hydrogen bonding and hierarchical nanostructures in poly(hydroxyether of bisphenol A)/poly( ε -caprolactone)-block-poly(2-vinyl pyridine) blends. Polymer 2008 , 49 , 922−933..
Salim, N. V.; Hanley, T.; Guo, Q. Microphase separation through competitive hydrogen bonding in double crystalline diblock copolymer/homopolymer blends. Macromolecules 2010 , 43 , 7695−7704..
Li, J. G.; Lin, Y. D.; Kuo, S. W. From microphase separation to self-organized mesoporous phenolic resin through competitive hydrogen bonding with double-crystalline diblock copolymers of poly(ethylene oxide- b - ε -caprolactone). Macromolecules 2011 , 44 , 9295−9309..
Salim, N. V.; Hameed, N.; Guo, Q. Competitive hydrogen bonding and self-assembly in poly(2-vinyl pyridine)-block-poly(methyl methacrylate)/poly(hydroxyether of bisphenol A) blends. J. Polym. Sci., Part B: Polym. Phys. 2009 , 47 , 1894−1905..
Hameed, N.; Salim, N. V.; Guo, Q. Microphase separation through competitive hydrogen bonding in self-assembled diblock copolymer/homopolymer complexes. J. Chem. Phys. 2009 , 131 , 214905..
Chen, S. C.; Kuo, S. W.; Jeng, U. S.; Su, C. J.; Chang, F. C. On modulating the phase behavior of block copolymer/homopolymer blends via hydrogen bonding. Macromolecules 2010 , 43 , 1083−1092..
Xia, B.; Li, W.; Qiu, F. Self-assembling behaviors of symmetric diblock copolymers in C homopolymers. Acta Chim. Sin. 2014 , 72 , 30−34..
Qiu, H.; Oliver, A. M.; Gwyther, J.; Cai, J.; Harniman, R. L.; Hayward, D. W.; Manners, I. Uniform toroidal micelles via the solution self-assembly of block copolymer-homopolymer blends using a “frustrated crystallization” approach. Macromolecules 2019 , 52 , 113−120..
Liu, J. Y.; Song, H. R.; Wang, M.; Jin, S. H.; Liang, Z.; Mao, X.; Li, W.; Deng, R. H.; Zhu, J. T. Asymmetric mesoporous carbon microparticles by 3D-confined self-assemblyof block copolymer/homopolymer blends and selective carbonization. Chinese J. Polym. Sci. 2023 , 41 , 787−793..
Liu, Z. Y.; Wang, Z.; Yin, Y. H.; Jiang, R.; Li, B. H. A simulation study of enhancing the compatibility in block copolymer AB/homopolymer C blends by solvents. Acta Polymerica Sinica (in Chinese) 2019 , 50 , 1220−1228..
Tan, J. Y.; Liu, Z. Y.; Wang, R.; Zhou, Y.; Xie, S. Y.; Li, B. H.; Wan, X. H.; Zhang, J. Modulation of thermodynamic and kinetic inverted phase behavior of block copolymers by inorganic polyoxometalates. Soft Matter 2019 , 15 , 6988−6993..
Zheng, X. H.; Ren, M.; Wang, H.; Wang, H. Y.; Geng, Z.; Xu, J. P.; Deng, R. H.; Chen, S. B.; Binder, W. H.; Zhu, J. T. Halogen-bond mediated 3D confined assembly of AB diblock copolymer and C homopolymer blends. Small 2021 , 17 , 1−10..
Carmesin, I.; Kremer, K. The bond fluctuation method: a new effective algorithm for the dynamics of polymers in all spatial dimensions. Macromolecules 1988 , 21 , 2819−2823..
Larson, R. G. Monte Carlo simulation of micro-structural transitions in surfactant systems. J. Chem. Phys. 1992 , 96 , 7904−7918..
Grest, G. S.; Soukoulis, C. M.; Levin, K. Cooling-rate dependence for the spin-glass ground-state energy: implications for optimization by simulated annealing. Phys. Rev. Lett. 1986 , 56 , 1148−1151..
Wu, J.; Wang, X.; Wang, Z.; Yin, Y.; Jiang, R.; Li, Y.; Li, B. Nanospheres with patches arranged in polyhedrons from self-assembly of solution-state diblock copolymers under spherical confinement. Macromolecules 2023 , 56 , 335−348..
Li, X. Y.; Wang, Z.; Yin, Y. H.; Jiang, R.; Li, B. H. Interfacial frustration-induced novel self-assembled structure s from block copolymers under janus spherical confinement. Chinese J. Polym. Sci. 2025 , 43 , 1423−1432..
Sun, P.;Yin, Y.; Li, B.; Chen, T.; Jin, Q.; Ding, D.; Shi, A. C. Simulated annealing study of gyroid formation in diblock copolymer solutions. Phys. Rev. E 2005 , 72 , 061408..
Zhang, J.; Kong, W.; Duan, H. Soft confinement-induced morphologies of the blends of AB diblock copolymers and C homopolymers. Langmuir 2017 , 33 , 3123−3133..
Zheng, L. F.; Wang, Z.; Yin, Y. H.; Jiang, R.; Li, B. H. Monte carlo simulations of the self-assembly of ABA triblock copolymers inside an oil-in-water emulsion droplet. Acta Polymerica Sinica (in Chinese) 2019 , 50 , 915−924..
Wu, J.; Wang, Z.; Yin, Y.; Jiang, R.; Li, B. Phase behavior of ABC cyclic terpolymer melts: a simulation study. Soft Matter 2020 , 16 , 2706−2714..
Zheng, L.; Wu, J.; Wang, Z.; Yin, Y.; Jiang, R.; Li, B. Phase behavior of ABC-type triple-hydrophilic block copolymers in aqueous solutions. Eur. Phys. J. E. 2016 , 39 , 75..
Li, Q.; Woo, D.; Kim, J. K.; Li, W. Truly “inverted” cylinders and spheres formed in the A(AB) 3 /AC blends of B/C hydrogen bonding interactions. Macromolecules 2022 , 55 , 6525−6535..
0
Views
1059
Downloads
0
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution
京公网安备11010802046900号