Spatiotemporal Structure Heterogeneity Evolution during Latex Film Formation Investigated by <italic style="font-style: italic">Operando</italic> Single-sided Nuclear Magnetic Resonance Relaxometry

Xiao-Jie Chen; Ling-Han Shi; Jun Chen; Ling-Xun Qi; Yi-Zhen Yan; Zhong Zeng; Yi-Qun Yang; Zheng-Nan Yang; Jie Sun; Wei Chen

doi:10.1007/s10118-026-3755-x

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Spatiotemporal Structure Heterogeneity Evolution during Latex Film Formation Investigated by Operando Single-sided Nuclear Magnetic Resonance Relaxometry

RESEARCH ARTICLE | Updated：2026-09-23

- Spatiotemporal Structure Heterogeneity Evolution during Latex Film Formation Investigated by Operando Single-sided Nuclear Magnetic Resonance Relaxometry
- Spatiotemporal Structure Heterogeneity Evolution during Latex Film Formation Investigated by Operando Single-sided Nuclear Magnetic Resonance Relaxometry
- Chinese Journal of Polymer Science 2026年44卷第10期页码：3574-3585
- Affiliations：
  
  a.School of Nuclear Science and Technology, National Synchrotron Radiation Laboratory, State Key Laboratory of Advanced Glass Materials, School of Chemistry and Materials Science, Anhui Provincial Engineering Research Center for Advanced Functional Polymer Films, University of Science and Technology of China, Hefei 230029, China
  b.National Key Laboratory of Chemical Explosion Safety, Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, China
  c.BASF Advanced Chemicals Co., Ltd., Shanghai 200137, China
- Author bio：
  
  wc003@ustc.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 52422302) and Anhui Provincial Natural Science Foundation (Nos. 2308085UM02, 2208085UM01, 2208085UM04 and 2408055UM001). We thank BASF for its support in funding and sampling this work. This work was partially conducted at the Instruments Center for Physical Science, University of Science and Technology of China.;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/s10118-026-3755-x.The data that support the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3755-x
  中图分类号：
- 收稿：2026-03-16，
  
  录用：2026-05-21，
  
  网络首发：2026-08-22，
  
  纸质出版：2026-10-05
- Accepted：
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Chen, X. J.; Shi, L. H.; Chen, J.; Qi, L. X.; Yan, Y. Z.; Zeng, Z.; Yang, Y. Q.; Yang, Z. N.; Sun, J.; Chen, W. Spatiotemporal structure heterogeneity evolution during latex film formation investigated by Operando single-sided nuclear magnetic resonance relaxometry. Chinese J. Polym. Sci. 2026, 44, 3574–3585

Xiao-Jie Chen, Ling-Han Shi, Jun Chen, et al. Spatiotemporal Structure Heterogeneity Evolution during Latex Film Formation Investigated by Operando Single-sided Nuclear Magnetic Resonance Relaxometry[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3574-3585. DOI: 10.1007/s10118-026-3755-x.
Chen, X. J.; Shi, L. H.; Chen, J.; Qi, L. X.; Yan, Y. Z.; Zeng, Z.; Yang, Y. Q.; Yang, Z. N.; Sun, J.; Chen, W. Spatiotemporal structure heterogeneity evolution during latex film formation investigated by Operando single-sided nuclear magnetic resonance relaxometry. Chinese J. Polym. Sci. 2026, 44, 3574–3585 DOI： 10.1007/s10118-026-3755-x.

Xiao-Jie Chen, Ling-Han Shi, Jun Chen, et al. Spatiotemporal Structure Heterogeneity Evolution during Latex Film Formation Investigated by Operando Single-sided Nuclear Magnetic Resonance Relaxometry[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3574-3585. DOI: 10.1007/s10118-026-3755-x. DOI：

摘要

This work employs a custom-built Operando single-sided NMR hyphenated instrument to track the spatiotemporal evolution of latex film formation

revealing how environmental factors drive the competition between capillary-driven fast water diffusion and the formation of a premature skin-core structure that inhibits particle coalescence.

Abstract

Understanding the film formation mechanism of waterborne latex is crucial for developing high-performance

eco-friendly coatings. However

the influence of various enviromental factors

i.e.

temperature and wind

on spatiotemporal structure heterogeneity induced during drying complicates the establishment of the structure-process-property of coating. Here

we track a polyacrylate latex film formation using a custom-built single-sided nuclear magnetic resonance (NMR) hyphenated instrument. Two-dimensional correlation spectra reveal highly restricted water dynamics within the latex suspension

evidenced by a decreased self-diffusion coefficient

from 2.00×10

–9

/s of pure water to 1.39×10

–9

/s in suspension with a plummeted

of 30

which is about 111 for pure water. For film drying under mild conditon (24 °C without

airflow)

dense particle packing induces strong capillary forces

generating anomalous fast-diffusion channels (

up to 31.05×10

–9

/s) to accelerate water evaporation resulting in homogeneous structure along the thickness direction. Conversely

after introducing airflow

i.e.

35 °C with 10 L/min airflow

the accelerated drying rate (3.72 μm/min) drastically amplifies the spatiotemporal heterogeneity and triggers premature surface skinning. Such skin-core structure traps residual water inside and inhibit further coalescing of latex particles. The uncoalesced bottom layer thicknesses quantitatively predicted by non-destructive single-sided NMR (about 100

200

and 400 μm)

which is well consistent with SEM measurements (93

240

and 409 μm

respectively). This work provides direct physical insights and theoretical guidance for the formulation and application of waterborne coatings during real service condition.

关键词

Keywords

references

dos Santos Lima, K. T.; de Matos Fonseca, J.; Monteiro, A. R.; Valencia, G. A. Progress in biopolymer coatings for achieving sustainable paper and paperboard packaging for food applications: a brief review. Packag. Technol. Sci. 2025 , 38 , 109−116..

Zhu, R.; Lv, W.; Sun, C.; Qin, C.; Zhang, D.; Long, Z. A facile strategy to fabricate high-barrier, water- and oil-repellent paper with carboxymethyl cellulose/collagen fiber/modified polyvinyl alcohol. Carbohydr. Polym. 2023 , 314 , 120933..

Deng, J.; Wu, L.; Chen, X.; Qi, L.; Wu, H.; Chen, J.; Palloks, S.; Chen, W. Janus optical clear adhesive with tunable crosslinking density gradient for foldable display. Polymer 2026 , 351 , 129841..

[Wang, Q.; Wang, Y.; Han, S.; Han, L.; Han, G. Hydration behaviour of cement in polymer cement waterproof coating and its effect on the macroscopic performance. Constr. Build. Mater . 2023 , 408 , 133825..

Meng, Y.; Lu, T.; Fang, G.; Li, W.; He, G.; Pan, Z. Study on modification mechanism and properties of SBR/WER composite modified emulsified asphalt waterproof binder. Constr. Build. Mater. 2025 , 465 ,140246..

Lee, E.; Ariff, Z. M.; Shafiq, M. D.; Shuib, R. K.; Musa, M. S. Tuning the mechanical properties of epoxy-acrylate core–shell nanostructured film via epoxy concentration in the core layer. J. Coat. Technol. Res. 2024 , 21 , 1241−1254..

[Toriseva, J.; Lahti, J.; Kuusipalo, J. Pilot-scale demonstration of novel tandem coating process: combining dispersion and extrusion coating with enhanced barrier properties. J. Appl. Polym. Sci . 2023 , 140 , e53959..

Abdeldaim, H.; Reck, B.; Roschmann, K. J.; Asua, J. M. Cracking in films cast from soft core/hard shell waterborne polymer dispersions. Macromolecules 2023 , 56 , 3304−3315..

Aguirre, M.; Ballard, N.; Gonzalez, E.; Hamzehlou, S.; Sardon, H.; Calderon, M.; Paulis, M.; Tomovska, R.; Dupin, D.; Bean, R. H. Polymer colloids: current challenges, emerging applications, and new developments. Macromolecules 2023 , 56 , 2579−2607..

Kumar, S. K.; Douglas, J. F. Gelation in physically associating polymer solutions. Phys. Rev. Lett. 2001 , 87 , 188301..

Wu, Z.; Xiong, Y.; Li, C.; Cheng, H.; Li, Y.; Chen, W. Exploring the interphase structure of poly(vinyl alcohol) during sol–gel transition using selective probes with varied molecular sizes. Macromolecules 2023 , 56 , 7113−7124..

[Okuzono, T.; Ozawa, K. y.; Doi, M. Simple model of skin formation caused by solvent evaporation in polymer solutions. Phys. Rev. Lett . 2006, 97 , 136103..

[De Gennes, P.-G. in Scaling concepts in polymer physics . Cornell university press, Ithaca and London, 1979 , p. 27..

Van Franeker, J. J.; Turbiez, M.; Li, W.; Wienk, M. M.; Janssen, R. A. A real-time study of the benefits of co-solvents in polymer solar cell processing. Nat. Commun. 2015 , 6 , 6229..

Cheng, H.; Zhao, Y.; Wei, X.; Zhang, Q.; Yang, E.; Xiong, Y.; Zhu, J.; Wu, Z.; Chen, J.; Chen, W. Supercooling and solvent depletion-driven poly(vinyl alcohol) film formation mechanism as elucidated by in situ synchrotron radiation X-ray scattering. Macromolecules 2024 , 57 , 1569−1580..

Arjmandi, A.; Bi, H.; Nielsen, S. U.; Dam-Johansen, K. From wet to protective: film formation in waterborne coatings. ACS Appl. Mater. Interfaces 2024 , 16 , 58006−58028..

Jiménez, N.; B allard, N.; Asua, J. M. Hard coatings from soft latexes: A review of routes to overcome the film formation dilemma. Macromol. Mater. Eng. 2024 , 309 , 2400026..

Joanicot, M.; Wong, K.; Cabane, B. Interdiffusion in cellular latex films. Macromolecules 1996 , 29 , 4976−4984..

Abdeldaim, H.; González, E.; Duarte, N.; Asua, J. M. Solving the film formation dilemma: blends of soft core–hard “shell” particles. Macromolecules 2023 , 56 , 9054−9061..

Eckersley, S. T.; Helmer, B. J. Mechanistic considerations of particle size effects on film properties of hard/soft latex blends. J. Coat. Technol. 1997 , 69 , 97−107..

Cheaburu-Yilmaz, C. N.; Yilmaz, O.; Darie-Nita, R. N. The effect of different soft core/hard shell ratios on the coating performance of acrylic copolymer latexes. Polymers 2021 , 13 , 3521..

Keddie, J. L. Film formation of latex. Mater. Sci. Eng.: R: Rep. 1997 , 21 , 101−170..

Steward, P. A.; Hearn, J.; Wilkinson, M. C. An overview of polymer latex film formation and properties. Adv. Colloid Interface Sci. 2000 , 86 , 195−267..

Winnik, M. A. Latex film formation. Curr. Opin. Colloid Interface Sci. 1997 , 2 , 192−199..

Dobler, F.; Pith, T.; Lambla, M.; Holl, Y. Coalescence mechanisms of polymer colloids: I. Coalescence under the influence of particle-water interfacial tension. J. Colloid Interface Sci. 1992 , 152 , 1−11..

Keddie, J.; Meredith, P.; Jones, R.; Donald, A. Kinetics of film formation in acrylic latices studied with multiple-angle-of-incidence ellipsometry and environmental SEM. Macromolecules 1995 , 28 , 2673−2682..

Li, J.; Cabane, B.; Sztucki, M.; Gummel, J.; Goehring, L. Drying dip-coated colloidal films. Langmuir 2011 , 28 , 200−208..

Pohl, K.; König, R.; Römermann, H.; Schulz, M.; Johannsmann, D. Coarsening of the pore network in drying latex films upon interparticle aggregation. Langmuir 2014 , 30 , 9384−9389..

Ryu, S.-a.; Kim, J. Y.; Kim, S. Y.; Weon, B. M. Drying-mediated patterns in colloid-polymer suspensions. Sci. Rep. 2017 , 7 , 1079..

Talini, L.; Lequeux, F. Formation of glassy skins in drying polymer solutions: approximate analytical solutions. Soft Matter 2023 , 19 , 5835−5845..

[Zhou, J.; Man, X.; Jiang, Y.; Doi, M. Structure formation in soft-matter solutions induced by solvent evaporation. Adv. Mater . 2017, 29 , 1703769..

Schlotter, N.; Furlan, P. A review of small molecule diffusion in polyolefins. Polymer 1992 , 33 , 3323−3342..

Cao, L.; He, X.; Jiang, Z.; Li, X.; Li, Y.; Ren, Y.; Yang, L.; Wu, H. Channel-facilitated molecule and ion transport across polymer composite membranes. Chem. Soc. Rev. 2017 , 46 , 6725−6745..

Hülagü, D.; Tobias, C.; Climent, E.; Gojani, A.; Rurack, K.; Hodoroaba, V.-D. Generalized analysis approach of the profile roughness by electron microscopy with the example of hierarchically grown polystyrene–iron oxide–silica core–shell–shell particles. Adv. Eng. Mater. 2022 , 24 , 2101344.

Xie, H.; Cui, B.; Hao, S.; Li, S.; Jia, X.; Wang, W. Exploring the macroscopic and microscopic characteristics of rice stalk for utilization in bio-composites. Compos. Sci. Technol. 2022 , 230 , 109728..

Wei, X.; Cheng, H.; Li, Y.; Chen, W. Numerical modeling of solvent evaporation in poly(vinyl alcohol) film formation during solution casting. Acta Polymerica Sinica (in Chinese) 2025 , 56 , 946−958..

Chen, L.; Wu, L.; Liu, Y.; Chen, W. In situ observation of void evolution in 1,3,5-triamino-2,4,6-trinitrobenzene under compression by synchrotron radiation X-ray nano-computed tomography. J. Synchrotron Radiat. 2020 , 27 , 127−133..

Patel, Z. S.; Sridhar, S.; Nadella, K.; Kumar, V.; Nuhnen, A.; Janiak, C. Nanoporous structure development in PEI thin film foams. J. Mater. Sci. 2023 , 58 , 17113−17125..

Blümich, B.; Perlo, J.; Casanova, F. Mobile single-sided NMR. Prog. Nucl. Magn. Reson. Spectrosc. 2008 , 52 , 197−269..

Eidmann, G.; Savelsberg, R.; Blümler, P.; Blümich, B. The NMR MOUSE, a Mobile Universal Surface Explorer. J. Magn. Reson., Ser. A 1996 , 122 , 104−109..

Chen, X.; Qi, L.; Chen, J.; Wu, L.; Shi, L.; Zeng, Z.; Yang, Y.; Yang, Z.; Sun, J.; Chen, W. Single-sided NMR for real-time tracking of porous structure formation of acrylate copolymer waterproof composites during erosion. Anal. Chem. 2026 , 98 , 8060−8069..

Perlo, J.; Casanova, F.; Blümich, B. Profiles with microscopic resolution by single-sided NMR. J. Magn. Reson. 2005 , 176 , 64−70..

Hürlimann, M. D.; Venkataramanan, L. Quantitative measurement of two-dimensional distribution functions of diffusion and relaxation in grossly inhomogeneous fields. J. Magn. Reson. 2002 , 157 , 31−42..

Tudisca, V.; Casieri, C.; Demma, F.; Diaz, M.; Piñol, L.; Terenzi, C.; De Luca, F. Firing technique characterization of black-slipped pottery in Praeneste by low field 2D NMR relaxometry. J. Archaeolog. Sci. 2011 , 38 , 352−359..

King, J. N.; Lee, V. J.; Ahola, S.; Telkki, V. V.; Meldrum, T. Ultrafast multidimensional laplace NMR using a single-sided magnet. Angew. Chem. Int. Ed. 2016 , 55 , 5040−5043..

King, J. N.; Fallorina, A.; Yu, J.; Zhang, G.; Telkki, V. V.; Hilty, C.; Meldrum, T. Probing molecular dynamics with hyperpolarized ultrafast Laplace NMR using a low-field, single-sided magnet. Chem. Sci. e 2018 , 9 , 6143−6149..

[Blumich, B. in NMR imaging of materials . Clarendon Press, Oxford, 2000, p.118..

[Song, Y. Q. Using internal magnetic fields to obtain pore size distributions of porous media. Concepts Magn. Reson. Part A 2003, 18A , 97−110..

Li, X.; Li, Y.; Chen, C.; Zhao, D.; Wang, X.; Zhao, L.; Shi, H.; Ma, G.; Su, Z. Pore size analysis from low field NMR spin–spin relaxation measurements of porous microspheres. J. Porous Mater. 2014 , 22 , 11−20..

Kiple, L.; Lee, T.; Zavaglia, G.; Meldrum, T. Characterization of molecular environments and chemical exchange in acrylic paints via single-sided NMR. Prog. Org. Coat. 2023 , 183 , 107770..

Gullion, T.; Baker, D. B.; Conradi, M. S. New, compensated Carr-Purcell sequences. J. Magn. Reson. 1990 , 89 , 479−484..

[Price, W. S. in Spin Dynamics: Basics of Nuclear Magnetic Resonance , 2nd edition, John Wiley & Sons Ltd, West Sussex, 2009 , p. 60..

[Blümich, F. C. J. P. B. in Single-sided NMR . Springer, Heidelberg, 2011, p. 43..

Konko, I.; Guriyanova, S.; Boyko, V.; Sun, L.; Liu, D.; Reck, B.; Men, Y. Role of the Hydrophilic Latex Parti cle Surface in Water Diffusion into Films from Waterborne Polymer Colloids. Langmuir 2019 , 35 , 6075−6088..

Hurtado, P. I.; Berthier, L.; Kob, W. Heterogeneous Diffusion in a Reversible Gel. Phys. Rev. Lett. 2007 , 98 , 135503..

Williamson, N. H.; Dower, A. M.; Codd, S. L.; Broadbent, A. L.; Gross, D.; Seymour, J. D. Glass dynamics and domain size in a solvent-polymer weak gel measured by multidimensional magnetic resonance relaxometry and diffusometry. Phys. Rev. Lett. 2019 , 122 , 068001..

Fujara, F.; Geil, B.; Sillescu, H.; Fleischer, G. Translational and rotational diffusion in supercooled orthoterphenyl close to the glass transition. Zeitschrift für Physik B Condensed Matter 1992 , 88 , 195−204..

Hürlimann, M. D. Diffusion and Relaxation Effects in General Stray Field NMR Experiments. J. Magn. Reson. 2001 , 148 , 367−378..

Umut, E.; Beira, M. J.; Oztop, M. H.; Sahiner, N.; Sebastião, P. J.; Kruk, D. Water dynamics in dextran-based hydrogel micro/nanoparticles studied by nm r diffusometry and relaxometry. J. Phys. Chem. B 2023 , 127 , 8950−8960..

Hummer, G.; Rasaiah, J. C.; Noworyta, J. P. Water conduction through the hydrophobic channel of a carbon nanotube. Nature 2001 , 414 , 188−190..

Das, B.; Ruiz-Barragan, S.; Bagchi, B.; Marx, D. Topological frustration triggers ultrafast dynamics of monolayer water confined in graphene slit pores. Nano Lett 2024 , 24 , 15623−15628..

[Zheng, W.; Zhang, S.; Jiang, J.; He, Y.; Stöhr, R.; Denisenko, A.; Wrachtrup, J.; Zeng, X. C.; Bian, K.; Wang, E.-G.; Jiang, Y. Observation of liquid-solid transition of nanoconfined water atambient temperature. arXiv preprint 2024, 2412 , 15001..

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Spatiotemporal Structure Heterogeneity Evolution during Latex Film Formation Investigated by Operando Single-sided Nuclear Magnetic Resonance Relaxometry

Spatiotemporal Structure Heterogeneity Evolution during Latex Film Formation Investigated by Operando Single-sided Nuclear Magnetic Resonance Relaxometry

DOI：10.1007/s10118-026-3755-x

摘要

Abstract

关键词

Keywords

references