Beyond Lattice Matching: Steric Confinement Enables Enhanced Nucleation of Poly(L-lactide) on Nanotalc

Yang Li; Yinshu Zhang; Dai-Wu Deng; Zi-Xuan Zhang; Guangdong Chen; Zizhun Wang; Ning-Ning Zhang; Bao Li; Irshad Hussain; Youliang Zhu; Yang Yang; Kun Liu

doi:10.1007/s10118-026-3840-1

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Beyond Lattice Matching: Steric Confinement Enables Enhanced Nucleation of Poly(L-lactide) on Nanotalc

RESEARCH ARTICLE | Updated：2026-09-29

- Beyond Lattice Matching: Steric Confinement Enables Enhanced Nucleation of Poly(L-lactide) on Nanotalc
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-11(2026)
- Affiliations：
  
  a.State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China
  b.School of Materials Science and Engineering, Jilin Jianzhu University, Changchun 130118, China
  c.Electron Microscopy Center, Jilin University, Changchun 130012, China
  d.Department of Chemistry & Chemical Engineering, SBA School of Science & Engineering, Lahore University of Management Sciences (LUMS), Lahore 54792, Pakistan
- Author bio：
  
  youliangzhu@jlu.edu.cn (Y.Z.)
  yangchem@jlu.edu.cn (Y.Y.)
  kliu@jlu.edu.cn (K.L.)
- Funds：
- DOI：10.1007/s10118-026-3840-1
  CLC：
- Received：23 June 2026，
  
  Accepted：11 August 2026，
  
  Online First：29 September 2026，
  
  Published：2026-09
- Accepted：
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Li, Y.; Zhang, Y.; Deng, D. W.; Zhang, Z. X.; Chen, G.; Wang, Z.; Zhang, N. N.; Li, B.; Hussain, I.; Zhu, Y.; Yang, Y.; Liu, K. Beyond lattice matching: steric confinement enables enhanced nucleation of poly(L-lactide) on nanotalc. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3840-1

Yang Li, Yinshu Zhang, Dai-Wu Deng, et al. Beyond Lattice Matching: Steric Confinement Enables Enhanced Nucleation of Poly(L-lactide) on Nanotalc[J/OL]. Chinese Journal of Polymer Science, 2026, 441-11.
Li, Y.; Zhang, Y.; Deng, D. W.; Zhang, Z. X.; Chen, G.; Wang, Z.; Zhang, N. N.; Li, B.; Hussain, I.; Zhu, Y.; Yang, Y.; Liu, K. Beyond lattice matching: steric confinement enables enhanced nucleation of poly(L-lactide) on nanotalc. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3840-1 DOI：

Yang Li, Yinshu Zhang, Dai-Wu Deng, et al. Beyond Lattice Matching: Steric Confinement Enables Enhanced Nucleation of Poly(L-lactide) on Nanotalc[J/OL]. Chinese Journal of Polymer Science, 2026, 441-11. DOI： 10.1007/s10118-026-3840-1.

摘要

Abstract

The incorporation of nucleating agents is widely regarded as an effective and practical strategy for overcoming the inherently slow cr

ystallization rate of poly(L-lactide) (PLLA). While talc has long been used to promote PLLA crystallization

primarily attributed to lattice matching between its (002) crystal facet and PLLA crystals

the underlying nucleation mechanism remains inadequately understood. In this work

we employed exfoliated nanotalc with a high proportion of exposed (002) nucleation-active facets to enhance the crystallinity and accelerate the crystallization rate of PLLA and reveal new molecular-level insights into its nucleating mechanism. Compared to conventional talc

nanotalc significantly accelerated PLLA crystallization

increasing its crystallinity from 40.0% to 49.5% and reducing the half-crystallization time from 2.21 min to 1.18 min. Correlative

in situ

high-resolution transmission electron microscopy (TEM) and atomic force microscopy (AFM) established a definitive interfacial orientation relationship

showing that PLLA preferentially aligns along the talc [310

]

direction. Combined with

in situ

characterization and molecular dynamics simulations

these results demonstrate that the nucleation of PLLA is driven not only by lattice matching but also by steric confinement of PLLA methyl groups within the six-membered rings of SiO

tetrahedra on the talc facet

which strengthens interfacial interactions and facilitates nucleation. This study provides a molecular-level understanding of heterogeneous polymer nucleation and offers guiding principles for the rational design of high-efficiency nucleating agents.

关键词

Keywords

references

Drumright, R. E.; Gruber, P. R.; Henton, D. E. Polylactic acid technology. Adv. Mater. 2000 , 12 , 1841−1846..

Saeidlou, S.; Huneault, M. A.; Li, H.; Park, C. B. Poly(lactic acid) crystallization. Prog. Polym. Sci. 2012 , 37 , 1657−1677..

Ouchiar, S.; Stoclet, G.; Cabaret, C.; Gloaguen, V. Influence of the filler nature on the crystalline structure of polylactide-based nanocomposites: new insights into the nucleating effect. Macromolecules 2016 , 49 , 2782−2790..

Han, Z. M.; Li, D. H.; Yang, H. B.; Zhao, Y. X.; Yin, C. H.; Yang, K. P.; Liu, H. C.; Sun, W. B.; Ling, Z. C.; Guan, Q. F.; Yu, S. H. Nacre-inspired nanocomposite films with enhanced mechanical and barrier properties by self-assembly of poly(lactic acid) coated mica nanosheets. Adv. Funct. Mater. 2022 , 32 , 2202221..

Wang, M.; Li, Q.; Shi, C.; Lv, J.; Xu, Y.; Yang, J.; Chua, S. L.; Jia, L.; Chen, H.; Liu, Q.; Huang, C.; Huang, Y.; Chen, J.; Fang, M. Oligomer nanoparticle release from polylactic acid plastics catalysed by gut enzymes triggers acute inflammation. Nat. Nanotechnol. 2023 , 18 , 403−411..

Pérez-Venegas, M.; Friščić, T.; Auclair, K. Efficient mechano-enzymatic hydrolysis of polylactic acid under moist-solid conditions. ACS Sustainable Chem. Eng. 2023 , 11 , 9924−9931..

Murariu, M.; Doumbia, A.; Bonnaud, L.; Dechief, A.-L.; Paint, Y.; Ferreira, M.; Campagne, C.; Devaux, E.; Dubois, P. High-performance polylactide/ZnO nanocomposites designed for films and fibers with special end-use properties. Biomacromolecules 2011 , 12 , 1762−1771..

Razavi, M.; Wang, S.-Q. Why is crystalline poly(lactic acid) brittle at room temperature. Macromolecules 2019 , 52 , 5429−5441..

Yang, H.; Shi, B.; Xue, Y.; Ma, Z.; Liu, L.; Liu, L.; Yu, Y.; Zhang, Z.; Annamalai, P. K.; Song, P. Molecularly engineered lignin-derived additives enable fire-retardant, UV-shielding, and mechanically strong polylactide biocomposites. Biomacromolecules 2021 , 22 , 1432−1444..

Auras, R.; Harte, B.; Selke, S. An overview of polylactides as packaging materials. Macromol. Biosci. 2004 , 4 , 835−864..

Villegas, C.; Torres, A.; Rios, M.; Rojas, A.; Romero, J.; de Dicastillo, C. L.; Valenzuela, X.; Galotto, M. J.; Guarda, A. Supercritical impregnation of cinnamaldehyde into polylactic acid as a route to develop antibacterial food packaging materials. Food Res. Int. 2017 , 99 , 650−659..

Zhang, L.; Huang, C.; Xu, Y.; Huang, H.; Zhao, H.; Wang, J.; Wang, S. Synthesis and characterization of antibacterial polylactic acid film incorporated with cinnamaldehyde inclusions for fruit packaging. Int. J. Biol. Macromol. 2020 , 164 , 4547−4555..

Yakdoumi, F. Z.; Hadj-Hamou, A. S.; Rahoui, N.; Rahman, M. M.; Abetz, V. Polylactic acid nanoco mposites containing functionalized multiwalled carbon nanotubes as antimicrobial packaging materials. Int. J. Biol. Macromol. 2022 , 213 , 55−69..

Vidal, C. P.; Luzi, F.; Puglia, D.; López-Carballo, G.; Rojas, A.; Galotto, M. J.; López de Dicastillo, C. Development of a sustainable and antibacterial food packaging material based in a biopolymeric multilayer system composed by polylactic acid, chitosan, cellulose nanocrystals and ethyl lauroyl arginate. Food Packag. Shelf Life 2023 , 36 , 101050..

Narayanan, G.; Vernekar, V. N.; Kuyinu, E. L.; Laurencin, C. T. Poly(lactic acid)-based biomaterials for orthopaedic regenerative engineering. Adv. Drug Deliv. Rev. 2016 , 107 , 247−276..

Basu, A.; Kunduru, K. R.; Doppalapudi, S.; Domb, A. J.; Khan, W. Poly(lactic acid) based hydrogels. Adv. Drug Deliv. Rev. 2016 , 107 , 192−205..

Cui, L.; Zhang, J.; Zou, J.; Yang, X.; Guo, H.; Tian, H.; Zhang, P.; Wang, Y.; Zhang, N.; Zhuang, X.; Li, Z.; Ding, J.; Chen, X. Electroactive composite scaffold with locally expressed osteoinductive factor for synergistic bone repair upon electrical stimulation. Biomaterials 2020 , 230 , 119617..

Feng, P.; Jia, J.; Liu, M.; Peng, S.; Zhao, Z.; Shuai, C. Degradation mechanisms and acceleration strategies of poly(lactic acid) scaffold for bone regeneration. Mater. Des. 2021 , 210 , 110066..

Zhang, S.; Fang, H.; Tian, H. Recent advances in degradable biomedical polymers for prevention, diagnosis and treatment of diseases. Biomacromolecules 2024 , 25 , 7015−7057..

Merino, D.; Zych, A.; Athanassiou, A. Biodegradable and biobased mulch films: highly stretchable PLA composites with different industrial vegetable waste. ACS Appl. Mater. Interfaces 2022 , 14 , 46920−46931..

Menossi, M.; Salcedo, F.; Rivilli, N.; Nicolini, A. T.; Alvarez, V. A.; Ludueña, L. N. Biodegradable mulch films based on starch/poly(lactic acid)/poly(ε-caprolactone) ternary blends. J. Polym. Environ. 2023 , 31 , 2114−2137..

Song, P.; Chen, G.; Wei, Z.; Chang, Y.; Zhang, W.; Liang, J. Rapid crystallization of poly(L-lactic acid) induced by a nanoscaled zinc citrate complex as nucleating agent. Polymer 2012 , 53 , 4300−4309..

Wei, Z.; Shao, S.; Sui, M.; Song, P.; He, M.; Xu, Q.; Leng, X.; Wang, Y.; Li, Y. Development of zinc salts of aminoacids as a new class of biocompatible nucleating agents for poly(L-lactide). Eur. Polym. J. 2019 , 118 , 337−346..

Zhang, X.; Yang, B.; Fan, B.; Sun, H.; Zhang, H. Enhanced nonisothermal crystallization and heat resistance of poly(L-lactic acid) by D-sorbitol as a homogeneous nucleating agent. ACS Macro Lett. 2021 , 10 , 154−160..

Cheng, Y.; Jiao, Z.; Li, M.; Xia, M.; Zhou, Z.; Song, P.; Xu, Q.; Wei, Z. A new class of nucleating agents for poly(L-lactic acid): environmentally-friendly metal saltswith biomass-derived ligands and advanced nucleation ability. Int. J. Biol. Macromol. 2023 , 225 , 1599−1606..

Bai, H.; Zhang, W.; Deng, H.; Zhang, Q.; Fu, Q. Control of crystal morphology in poly(L-lactide) by adding nucleating agent. Macromolecules 2011 , 44 , 1233−1237..

Bai, H.; Huang, C.; Xiu, H.; Zhang, Q.; Fu, Q. Enhancing mechanical performance of polylactide by tailoring crystal morphology and lamellae orie ntation with the aid of nucleating agent. Polymer 2014 , 55 , 6924−6934..

Li, C.; Luo, S.; Wang, J.; Wu, H.; Guo, S.; Zhang, X. Conformational regulation and crystalline manipulation of PLLA through a self-assembly nucleator. Biomacromolecules 2017 , 18 , 1440−1448..

Feng, Y.; Ma, P.; Xu, P.; Wang, R.; Dong, W.; Chen, M.; Joziasse, C. The crystallization behavior of poly(lactic acid) with different types of nucleating agents. Int. J. Biol. Macromol. 2018 , 106 , 955−962..

Schäfer, H.; Pretschuh, C.; Brüggemann, O. Reduction of cycle times in injection molding of PLA through bio-based nucleating agents. Eur. Polym. J. 2019 , 115 , 6−11..

Elsawy, M. A.; Saad, G. R.; Sayed, A. M. Mechanical, thermal, and dielectric properties of poly(lactic acid)/chitosan nano-composites. Polym. Eng. Sci. 2016 , 56 , 987−994..

Hijazi, N.; Le Moigne, N.; Rodier, E.; Sauceau, M.; Vincent, T.; Benezet, J.-C.; Fages, J. Biocomposite films based on poly(lactic acid) and chitosan nanoparticles: elaborati on, microstructural and thermal characterization. Polym. Eng. Sci. 2019 , 59 , E350−E360..

Ke, T.; Sun, X. Melting behavior and crystallization kinetics of starch and poly(lactic acid) composites. J. Appl. Polym. Sci. 2003 , 89 , 1203−1210..

Li, S.; Xiong, Z.; Fei, P.; Cai, J.; Xiong, H.; Tan, J.; Yu, Y. Parameters characterizing the kineticsof the nonisothermal crystallization of thermoplastic starch/poly(lactic acid) composites as determined by differential scanning calorimetry. J. Appl. Polym. Sci. 2013 , 129 , 3566−3573..

Wu, H.; Nagarajan, S.; Zhou, L.; Duan, Y.; Zhang, J. Synthesis and characterization of cellulose nanocrystal-graft-poly(d-lactide) and its nanocomposite with poly(L-lactide). Polymer 2016 , 103 , 365−375..

Fang, H. G.; Yang, K. J.; Xie, Q. Z.; Chen, X.; Wu, S. L.; Ding, Y. S. Influence of interfacial enantiomeric grafting on melt rheology and crystallizationof polylactide/cellulose nanocrystals composites. Chinese J. Polym. Sci. 2022 , 40 , 93−106..

Xu, J. Z.; Chen, T.; Yang, C. L.; Li, Z. M.; Mao, Y. M.; Zeng, B. Q.; Hsiao, B. S. Isothermal crystallization of poly(L-lactide) induced by graphene nanosheets and carbon nanotubes: a comparative study. Macromolecules 2010 , 43 , 5000−5008..

Park, S. H.; Lee, S. G.; Kim, S. H. Isothermal crystallization behavior and mechanical properties of polylactide/carbon nanotube nanocomposites. Compos. Part A Appl. Sci. Manuf. 2013 , 46 , 11−18..

Pan, P.; Liang, Z.; Cao, A.; Inoue, Y. Layered metal phosphonate reinforced poly(L-lactide) composites with a highly enhanced crystallization rate. ACS Appl. Mater. Interfaces 2009 , 1 , 402−411..

Chen, P.; Zhou, H.; Liu, W.; Zhang, M.; Du, Z.; Wang, X. The synergistic effect of zinc oxide and phenylphosphonic acid zinc salt on the crystallization behavior of poly(lactic acid). Polym. Degrad. Stab. 2015 , 122 , 25−35..

Kusumi, R.; Teranishi, S.; Kobayashi, K.; Wada, M.; Kimura, F.; Kimura, T. Three-dimensional orientation of a crystalline polymer via epitaxial growth from a magnetically oriented nucleating agent. Macromolecules 2024 , 57 , 4889−4896..

Huang, S.-M.; Hwang, J.-J.; Liu, H.-J.; Lin, L.-H. Crystallization behavior of poly(L-lactic acid)/montmorillonite nanocomposites. J. Appl. Polym. Sci. 2010 , 117 , 434−442..

Zhao, H.; Bian, Y.; Xu, M.; Han, C.; Li, Y.; Dong, Q.; Dong, L. Enhancing the crystallization of poly(L-lactide) using a montmorillonitic substrate favoring nucleation. CrystEngComm 2014 , 16 , 3896−3905..

Pastorek, M.; Kovalcik, A. Effects of thermal annealing as polymer processing step on poly(lactic acid). Mater. Manuf. Process. 2018 , 33 , 1674−1680..

Yu, F.; Liu, T.; Zhao, X.; Yu, X.; Lu, A.; Wang, J. Effects of talc on the mechanical and thermal properties of polylactide. J. Appl. Polym. Sci. 2012 , 125 , E99−E109..

Shakoor, A.; Thomas, N. L. Talc as a nucleating agent and reinforcing filler in poly(lactic acid) composites. Polym. Eng. Sci. 2014 , 54 , 64−70..

Petchwattana, N.; Covavisar uch, S.; Petthai, S. Influence of talc particle size and content on crystallization behavior, mechanical properties and morphology of poly(lactic acid). Polym. Bull. 2014 , 71 , 1947−1959..

Li, Y.; Han, C.; Yu, Y.; Xiao, L.; Shao, Y. Effect of content and particle size of talc on nonisothermal melt crystallization behavior of poly(L-lactide). J. Therm. Anal. Calorim. 2019 , 135 , 2049−2058..

Zong, L.; Li, M.; Li, C. Bioinspired coupling of inorganic layered nanomaterials with marine polysaccharides for efficient aqueous exfoliation and smart actuating hybrids. Adv. Mater. 2017 , 29 , 1604691..

Pan, X. F.; Yu, G. H.; Gao, H. L.; Wang, Z. Z.; Bao, Z.; Li, X.; Yu, S. H. Large-scale production of rectorite nanosheets and their co-assembly with aramid nanofibers for high-performance electrical insulating nanopapers. Adv. Mater. 2022 , 34 , 2206855..

Shao, Q.; Long, L.; Zhao, J.; Li, Y.; Wang, Z. Directional epitaxy intensifying intermolecular =C–H···O=C hydrogen bonding to expedite bulk crystallization of biobased poly(butylene 2, 5-furandicarboxylate). Macromolecules 2024 , 57 , 3282−3294..

Avrami, M. Kinetics of phase change. I general theory. J. Chem. Phys. 1939 , 7 , 1103−1112..

Zhang, X. X.; Li, Y. K.; Sun, Z. Y. Acceleration of crystal transformation from crystal form II to form I in Polybutene-1 induced by nanoparticles. Polymer 2018 , 150 , 119−129..

Guan, G.; Zhang, J.; Sun, X.; Li, H.; Yan, S.; Lotz, B. Oriented overgrowths of poly(L-lactide) on oriented isotactic polypropylene: a sequence of soft and hard epitaxies. Macromol. Rapid Commun. 2018 , 39 , 1800353..

Li, L.; Hu, J.; Li, Y.; Huang, Q.; Sun, X.; Yan, S. Evidence for the soft and hard epitaxies of poly(L-lactic acid) on an oriented polyethylene substrate and their dependence on the crystallization temperature. Macromolecules 2020 , 53 , 1745−1751..

Li, L.; Xin, R.; Li, H.; Sun, X.; Ren, Z.; Huang, Q.; Yan, S. Tacticity-dependent epitaxial crystallization of poly(L-lactic acid) on an oriented polyethylene substrate. Macromolecules 2020 , 53 , 8487−8493..

Li, Y.; Xin, R.; Wang, S.; Guo, Z.; Sun, X.; Ren, Z.; Li, H.; Li, L.; Yan, S. Structure and mechanical property of melt-drawn oriented PLA ultrathin films. Macromolecules 2021 , 54 , 9124−9134..

Li, Y.; Ma, M.; Xu, B.; Xin, R.; Yan, S. Impact of the exposure plane on the homoepitaxy of poly(L-lactic acid). Macromolecules 2025 , 58 , 4547−4554..

Claverie, M.; Dumas, A.; Carême, C.; Poirier, M.; Le Roux, C.; Micoud, P.; Martin, F.; Aymonier, C. Synthetic talc and talc-like structures: preparation, features and applications. Chem. Eur. J. 2018 , 24 , 519−542..

Legras, R.; Mercier, J. P.; Nield, E. Polymer crystallization by chemical nucleation. Nature 1983 , 304 , 432−434..

Ferrage, E.; Martin, F.; Boudet, A.; Petit, S.; Fourty, G.; Jouffret, F.; Micoud, P.; De Parseval, P.; Salvi, S.; Bourgerette, C.; Ferret, J.; Saint-Gerard, Y.; Buratto, S.; Fortune, J. P. Talc as nucleating agent of polypropylene: morphology induced by lamellar particles addition and interface mineral-matrix modelization. J. Mater. Sci. 2002 , 37 , 1561−1573..

[Xin, R.; Zhang, J.; Sun, X.; Li, H.; Qiu, Z.; Yan, S. Epitaxial effects on polymer crystallization. in Polymer crystallization II: from chain microstructure to processing , Auriemma, F., Alfonso, G. C., de Rosa, C. Eds.; Springer International Publishing, 2017 , pp. 55−94..

Wen, L.; Xin, Z. Effect of a novel nucleating agent on isothermal crystallization of poly(L-lactic acid). Chin. J. Chem. Eng. 2010 , 18 , 899−904..

Xie, K.; Shen, J.; Ye, L.; Liu, Z.; Li, Y. Increased gt conformer contents of PLLA molecular chains induced by Li-TFSI in melt: another route to promote PLLA crystallization. Macromolecules 2019 , 52 , 7065−7072..

Tan, C.; Chen, J.; Wu, X.-J.; Zhang, H. Epitaxial growth of hybrid nanostructures. Nat. Rev. Mater. 2018 , 3 , 17089..

Mauritz, K. A.; Baer, E.; Hopfinger, A. J. Molecular energetics of the epitaxial crystallization of polyethylene on alkali halide substrates. J. Polym. Sci. Polym. Phys. Ed. 1973 , 11 , 2185−2197..

McAliley, J. H.; Bruce, D. A. Development of force field parameters for molecular simulation of polylactide. J. Chem. Theory Comput. 2011 , 7 , 3756−3767..

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