非平衡相分离驱动的温敏水凝胶时间可调光学响应

张曼曼; 王驰宇; 王慧娟; 樊文豪; 叶子凡; 高稍轩; 孟献瑞; 彭闯; 张文凯

doi:10.14028/j.cnki.1003-3726.2026.26.054

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非平衡相分离驱动的温敏水凝胶时间可调光学响应

研究论文 | 更新时间：2026-07-06

- 非平衡相分离驱动的温敏水凝胶时间可调光学响应
  增强出版
- Nonequilibrium Phase Separation‑driven Temporally Tunable Optical Response in Thermoresponsive Hydrogels
- 高分子通报 2026年39卷第7期页码：1204-1215
- 作者机构：
  
  河南大学化学与分子科学学院　开封 475004
- 作者简介：
  
  pc@henu.edu.cn
  zhangwenkai@henu.edu.cn
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2026.26.054
  中图分类号：
- 收稿：2026-03-25，
  
  录用：2026-04-10，
  
  网络首发：2026-06-08，
  
  纸质出版：2026-07-20
- 稿件说明：
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张曼曼, 王驰宇, 王慧娟, 樊文豪, 叶子凡, 高稍轩, 孟献瑞, 彭闯, 张文凯. 非平衡相分离驱动的温敏水凝胶时间可调光学响应. 高分子通报, 2026, 39(7), 1204–1215.

Zhang, M. M.; Wang, C. Y.; Wang, H. J.; Fan, W. H.; Ye, Z. F.; Gao, S. X.; Meng, X. R.; Peng, C.; Zhang, W. K. Nonequilibrium phase separation‑driven temporally tunable optical response in thermoresponsive hydrogels. Polym. Bull. (in Chinese), 2026, 39(7), 1204–1215.
张曼曼, 王驰宇, 王慧娟, 樊文豪, 叶子凡, 高稍轩, 孟献瑞, 彭闯, 张文凯. 非平衡相分离驱动的温敏水凝胶时间可调光学响应. 高分子通报, 2026, 39(7), 1204–1215. DOI： 10.14028/j.cnki.1003-3726.2026.26.054.

Zhang, M. M.; Wang, C. Y.; Wang, H. J.; Fan, W. H.; Ye, Z. F.; Gao, S. X.; Meng, X. R.; Peng, C.; Zhang, W. K. Nonequilibrium phase separation‑driven temporally tunable optical response in thermoresponsive hydrogels. Polym. Bull. (in Chinese), 2026, 39(7), 1204–1215. DOI： 10.14028/j.cnki.1003-3726.2026.26.054.

摘要

温敏水凝胶的光学响应通常由平衡相行为决定，而对溶剂交换过程中产生的非平衡效应仍缺乏系统性的认识。本研究以P(NIPAM-

-AAm)水凝胶为模型体系，考察其在水–乙醇混合溶剂中的透光率随时间的变化行为。在相同终态温度与溶剂组成条件下，不同处理方式得到的光学状态存在明显差异。水溶胀态样品直接进入高温乙醇环境时，乙醇向内扩散在凝胶内部形成瞬时组成梯度，使局部区域进入LCST敏感区间并发生相分离，出现短时浑浊；而先完成溶剂交换再升温时，体系始终处于均一溶剂环境，保持透明。通过分析透光率–时间曲线，提取相分离时间

与恢复时间

rel

，发现两者随乙醇浓度显著变化，其比值由约11.7降低至1.5，对应由长时间维持浑浊到快速恢复透明的转变。冷冻干燥扫描电子显微镜与原位光学显微结果表明，不同处理路径对应的结构形貌存在明显差异。通过调控乙醇浓度或环境温度，可在数十秒至数千秒范围内连续调节相分离特征时间，实现对光学响应时间的精准控制，为动态光学调控材料的设计提供了可行思路。

Abstract

The optical response of thermoresponsive hydrogels is typically governed by equilibrium phase behavior

whereas the nonequilibrium effects arising from solvent exchange processes remain insufficiently understood. In this study

we used P(NIPAM-

-AAm) hydrogels as a model system to investigate the temporal evolution of transmittance in water-ethanol mixed solvents. Under identical final-state temperatures and solvent compositions

distinct optical states were observed depending on the treatment pathway. When a water-swollen sample is directly introduced i

nto a high-temperature ethanol environment

the inward diffusion of ethanol generates transient compositional gradients within the gel

causing localized regions to enter the LCST-sensitive range and undergo phase separation

resulting in temporary turbidity. In contrast

when solvent exchange was completed prior to heating

the system remained in a homogeneous solvent environment and remained transparent. Analysis of the transmittance-time curves revealed the characteristic phase separation time

and recovery time

rel

both of which varied significantly with ethanol concentration

with their ratio decreasing from approximately 11.7 to 1.5

corresponding to a transition from prolonged turbidity to rapid recovery of transparency. Cryo-SEM and

in situ

optical microscopy results revealed distinct structural morphologies depending on the treatment pathway. The phase separation characteristic time can be continuously tuned from tens to thousands of seconds by varying the ethanol concentration or temperature

allowing precise regulation of the optical response time and offering a promising strategy for dynamic optical materials.

关键词

Keywords

references

Wang, Z. W. ; Qiu, W. L. ; Zhang, Q. Constructing phase separation in polymer gels: strategies, functions and applications . Prog. Polym. Sci. , 2024 , 154 , 101847 .

Shen, Y. ; Le, X. X. ; Wu, Y. ; Chen, T. Stimulus-responsive polymer materials toward multi-mode and multi-level information anti-counterfeiting: Recent advances and future challenges . Chem. Soc. Rev. , 2024 , 53 ( 2 ), 606 – 623 .

Sha, Z. H. ; Chen, X. ; Song, H. ; Zheng, Y. ; Cui, W. ; Ran, R. Toughening hydrogels with small molecules: tiny matter, big impact . Mater. Horiz. , 2025 , 12 ( 18 ), 7244 – 7276 .

Zhu, F. B. ; Feng, S. H. ; Wang, Z. Q. ; Zuo, Z. C. ; Zhu, S. L. ; Yu, W. W. ; Ye, Y. N. ; An, M. ; Qian, J. ; Wu, Z. L. ; Zheng, Q. Co-ion specific effect aided phase separation in polyelectrolyte hydrogels toward extreme strengthening and toughening . Macromolecules , 2023 , 56 ( 15 ), 5881 – 5890 .

Cheng, R. D. ; Xu, M. W. ; Zhang, X. H. ; Jiang, J. Q. ; Zhang, Q. Y. ; Zhao, Y. Hydrogen bonding enables polymer hydrogels with pH-induced reversible dynamic responsive behaviors . Angew. Chem. Int. Ed. , 2023 , 62 ( 23 ), e202302900 .

Chen, G. Q. ; Wang, K. ; Yang, J. H. ; Huang, J. ; Chen, Z. F. ; Zheng, J. X. ; Wang, J. Q. ; Yang, H. L. ; Li, S. N. ; Miao, Y. Y. ; Wang, W. Q. ; Zhu, N. N. ; Jiang, X. C. ; Chen, Y. M. ; Fu, J. Printable thermochromic hydrogel-based smart window for all-weather building temperature regulation in diverse climates . Adv. Mater. , 2023 , 35 ( 20 ), 2211716 .

Li, M. ; Lu, H. L. ; Wang, X. Y. ; Wang, Z. S. ; Pi, M. H. ; Cui, W. ; Ran, R. Regulable mixed-solvent-induced phase separation in hydrogels for information encryption . Small , 2022 , 18 ( 52 ), e2205359 .

Shan, F. Q. ; Le, X. X. ; Shang, H. ; Xie, W. P. ; Sun, W. ; Chen, T. Regulating aggregated structures in organohydrogels for on-demand information encryption . ACS Appl. Mater. Interfaces , 2023 , 15 ( 5 ), 7405 – 7413 .

Wang, W. Y. ; Wang, K. ; Cheng, Y. ; Wu, C. ; Wu, R. Z. ; Huang, J. Y. ; Lai, Y. K. Bidirectional temperature-responsive thermochromic hydrogels with adjustable light transmission interval for smart windows . Adv. Funct. Mater. , 2026 , 36 ( 6 ), 2413102 .

Zhao, Y. L. ; Zhang, X. C. ; Hao, Y. L. ; Zhao, Y. H. ; Ding, P. ; Zhai, W. ; Dai, K. ; Zheng, G. Q. ; Liu, C. T. ; Shen, C. Y. Multifunctional PVA/PNIPAM conductive hydrogel sensors enabled human-machine interaction intelligent rehabilitation training . Adv. Compos. Hybrid Mater. , 2024 , 7 ( 6 ), 245 .

Ding, Y. T. ; Duan, Y. H. ; Yang, F. Y. ; Xiong, Y. ; Guo, S. Y. High-transmittance pNIPAm gel smart windows with lower response temperature and stronger solar regulation . Chem. Eng. J. , 2023 , 460 , 141572 .

Tang, L. ; Wang, L. ; Yang, X. ; Feng, Y. Y. ; Li, Y. ; Feng, W. Poly( N -isopropylacrylamide)-based smart hydrogels: design, properties and applications . Prog. Mater. Sci. , 2021 , 115 , 100702 .

Halperin, A. ; Kröger, M. ; Winnik, F. M. Poly( N -isopropylacrylamide) phase diagrams: Fifty years of research . Angew. Chem. Int. Ed. , 2015 , 54 ( 51 ), 15342 – 15367 .

Wang, K. ; Chen, G. Q. ; Weng, S. ; Hou, L. X. ; Ye, D. Z. ; Jiang, X. C. Thermo-responsive poly( N -isopropylacrylamide)/hydroxypropylmethyl cellulose hydrogel with high luminous transmittance and solar modulation for smart windows . ACS Appl. Mater. Interfaces , 2023 , 15 ( 3 ), 4385 – 4397 .

Chen, Z. ; Chen, Y. J. ; Guo, Y. T. ; Yang, Z. ; Li, H. ; Liu, H. Z. Paper-structure inspired multiresponsive hydrogels with solvent-induced reversible information recording, self-encryption, and multidecryption . Adv. Funct. Mater. , 2022 , 32 ( 23 ), 2201009 .

Dixit, A. ; Bag, D. S. Highly stretchable and tough thermo-responsive double network (DN) hydrogels: composed of PVA-borax and poly(AM- co -NIPAM) polymer networks . Eur. Polym. J. , 2022 , 175 , 111347 .

Thirupathi, K. ; Phan, T. T. V. ; Santhamoorthy, M. ; Ramkumar, V. ; Kim, S. C. pH and thermoresponsive PNIPAm- co -polyacrylamide hydrogel for dual stimuli-responsive controlled drug delivery . Polymers , 2023 , 15 ( 1 ), 167 .

Lou, D. Y. ; Sun, Y. J. ; Li, J. ; Zheng, Y. Y. ; Zhou, Z. P. ; Yang, J. ; Pan, C. X. ; Zheng, Z. K. ; Chen, X. D. ; Liu, W. Double lock label based on thermosensitive polymer hydrogels for information camouflage and multilevel encryption . Angew. Chem. Int. Ed. , 2022 , 61 ( 16 ), e202117066 .

Li, Y. X. ; Xu, M. F. ; Wang, D. Y. ; Liu, Z. Q. ; Mao, W. ; Sun, J. ; Shen, W. ; Lee, H. K. ; Tang, S. Phase-changing NIPAM-AM/ATO hydrogels for thermochromic smart windows with highly adaptive solar modulation . Chem. Eng. J. , 2024 , 499 , 156394 .

Zhang, H. J. ; Gao, T. Y. ; Jiang, L. ; Meng, X. Q. ; Wang, J. ; Ma, N. ; Wei, H. ; Zhang, X. Y. Conductive and transparent poly( N -isopropylacrylamide) hydrogels with tunable LCST copolymerized by the green acrylamide-based deep eutectic solvent . Eur. Polym. J. , 2022 , 173 , 111266 .

Yong, H. S. ; Sommer, J. U. Cononsolvency effect: when the hydrogen bonding between a polymer and a cosolvent matters . Macromolecules , 2022 , 55 ( 24 ), 11034 – 11050 .

Winnik, F. M. ; Ringsdorf, H. ; Venzmer, J. Methanol-water as a co-nonsolvent system for poly( N -isopropy-lacrylamide) . Macromolecules , 1990 , 23 ( 8 ), 2415 – 2416 .

Costa, R. O. R. ; Freitas, R. F. S. Phase behavior of poly( N -isopropylacrylamide) in binary aqueous solutions . Polymer , 2002 , 43 ( 22 ), 5879 – 5885 .

Zhang, P. F. Phase separation of homopolymers in binary mixed solvents—the co-nonsolvency effect . Macromolecules , 2024 , 57 ( 9 ), 4298 – 4311 .

Alsaid, Y. ; Wu, S. W. ; Wu, D. ; Du, Y. J. ; Shi, L. X. ; Khodambashi, R. ; Rico, R. ; Hua, M. T. ; Yan, Y. C. ; Zhao, Y. S. ; Aukes, D. ; He, X. M. Tunable sponge-like hierarchically porous hydrogels with simultaneously enhanced diffusivity and mechanical properties . Adv. Mater. , 2021 , 33 ( 20 ), 2008235 .

Pan, J. G. ; Zhang, W. ; Zhu, J. ; Tan, J. Y. ; Huang, Y. ; Mo, K. L. ; Tong, Y. ; Xie, Z. H. ; Ke, Y. B. ; Zheng, H. D. ; Ouyang, H. ; Shi, X. T. ; Gao, L. Arrested phase separation enables high-performance keratoprostheses . Adv. Mater. , 2023 , 35 ( 16 ), 2207750 .

Sato, K. ; Nakajima, T. ; Hisamatsu, T. ; Nonoyama, T. ; Kurokawa, T. ; Gong, J. P. Phase-separation-induced anomalous stiffening, toughening, and self-healing of polyacrylamide gels . Adv. Mater. , 2015 , 27 ( 43 ), 6990 – 6998 .

Guo, H. ; Sanson, N. ; Hourdet, D. ; Marcellan, A. Thermoresponsive toughening with crack bifurcation in phase-separated hydrogels under isochoric conditions . Adv. Mater. , 2016 , 28 ( 33 ), 7043 .

Wang, M. X. ; Zhang, P. Y. ; Shamsi, M. ; Thelen, J. L. ; Qian, W. ; Truong, V. K. ; Ma, J. ; Hu, J. ; Dickey, M. D. Tough and stretchable ionogels by in situ phase separation . Nat. Mater. , 2022 , 21 ( 3 ), 359 – 365 .

Wang, Z. W. ; Heck, M. ; Yang, W. W. ; Wilhelm, M. ; Levkin, P. A. Tough PEGgels by in situ phase separation for 4D printing . Adv. Funct. Mater. , 2024 , 34 ( 20 ), 2300947 .

Cui, W. ; Zhu, R. J. ; Zheng, Y. ; Mu, Q. F. ; Pi, M. H. ; Chen, Q. ; Ran, R. Transforming non-adhesive hydrogels to reversible tough adhesives via mixed-solvent-induced phase separation . J. Mater. Chem. A , 2021 , 9 ( 15 ), 9706 – 9718 .

Ishikawa, S. ; Iwanaga, Y. ; Uneyama, T. ; Li, X. ; Hojo, H. ; Fujinaga, I. ; Katashima, T. ; Saito, T. ; Okada, Y. ; Chung, U. I. ; Sakumichi, N. ; Sakai, T. Percolation-induced gel–gel phase separation in a dilute polymer network . Nat. Mater. , 2023 , 22 ( 12 ), 1564 – 1570 .

Wang, H. C. ; Fu, X. M. ; Gu, G. Y. ; Bai, S. Y. ; Li, R. L. ; Zhong, W. M. ; Guo, X. H. ; Eelkema, R. ; van Esch, J. H. ; Cao, Z. X. ; Wang, Y. M. Dynamic growth of macroscopically structured supramolecular hydrogels through orchestrated reaction-diffusion . Angew. Chem. Int. Ed. , 2023 , 62 ( 43 ), e202310162 .

Jia, D. ; Muthukumar, M. Topologically frustrated dynamics of crowded charged macromolecules in charged hydrogels . Nat. Commun. , 2018 , 9 , 2248 .

Tang, J. D. ; Cheng, Y. B. ; Ding, M. H. ; Wang, C. Bio-inspired far-from-equilibrium hydrogels: design principles and applications . ChemPlusChem , 2023 , 88 ( 12 ), e202300449 .

Celora, G. L. ; Hennessy, M. G. ; Münch, A. ; Wagner, B. ; Waters, S. L. A kinetic model of a polyelectrolyte gel undergoing phase separation . J. Mech. Phys. Solids , 2022 , 160 , 104771 .

László, K. ; Fluerasu, A. ; Moussaïd, A. ; Geissler, E. Kinetics of jammed systems: PNIPA gels . Macromol. Symp. , 2011 , 306-307 ( 1 ), 27 – 32 .

Korevaar, P. A. ; Kaplan, C. N. ; Grinthal, A. ; Rust, R. M. ; Aizenberg, J. Non-equilibrium signal integration in hydrogels . Nat. Commun. , 2020 , 11 , 386 .

Yavari, N. ; Azizian, S. Mixed diffusion and relaxation kinetics model for hydrogels swelling . J. Mol. Liq. , 2022 , 363 , 119861 .

Zhao, W. ; Wu, B. H. ; Lei, Z. Y. ; Wu, P. Y. Hydrogels with differentiated hydrogen-bonding networks for bioinspired stress response . Angew. Chem. Int. Ed. , 2024 , 63 ( 21 ), e202400531 .

Shirzad, K. ; Viney, C. A critical review on applications of the Avrami equation beyond materials science . J. R. Soc. Interface , 2023 , 20 ( 203 ), 20230242 .

Wang, F. ; Altschuh, P. ; Ratke, L. ; Zhang, H. D. ; Selzer, M. ; Nestler, B. Progress report on phase separation in polymer solutions . Adv. Mater. , 2019 , 31 ( 26 ), 1806733 .

Zhang, M. M. ; Peng, C. ; Kim, J. J. ; Fan, W. H. ; Wang, C. Y. ; Liu, Y. ; Meng, X. R. ; Ren, Y. R. ; Zhang, W. K. ; Lee, G. J. Solvent-programmable photonic hydrogels with tunable transmittance, fluorescence, and diffraction . Chem. Mater. , 2025 , 37 ( 17 ), 6562 – 6573 .

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