Promoting Effect of Synergetic Nucleating Agent on Crystallization Behavior of Polylactic Acid
Yongxiang Hu
School of Materials Science and Engineering, Shandong University of Technology, Zibo, China
Contribution: Data curation (lead), Formal analysis (lead), Investigation (lead), Project administration (lead), Resources (equal), Software (equal), Supervision (equal), Visualization (equal), Writing - original draft (lead)
Search for more papers by this authorCorresponding Author
Hongwang Shen
School of Materials Science and Engineering, Shandong University of Technology, Zibo, China
Correspondence:
Hongwang Shen ([email protected])
Lina Zhang ([email protected])
Guannan Ju ([email protected])
Contribution: Conceptualization (lead), Data curation (lead), Formal analysis (lead), Funding acquisition (lead), Project administration (lead), Resources (lead), Validation (lead), Visualization (lead), Writing - original draft (lead), Writing - review & editing (lead)
Search for more papers by this authorHuali Ni
Shandong Hua Zhilin Pharmaceutical Co. Ltd, Zibo, China
Contribution: Project administration (equal), Resources (equal), Software (equal)
Search for more papers by this authorYuanbiao Liu
School of Materials Science and Engineering, Shandong University of Technology, Zibo, China
Contribution: Resources (equal), Software (lead)
Search for more papers by this authorCorresponding Author
Lina Zhang
College of Pharmacy, Hebei Medical University, Shijiazhuang, Hebei, People's Republic of China
Correspondence:
Hongwang Shen ([email protected])
Lina Zhang ([email protected])
Guannan Ju ([email protected])
Contribution: Resources (lead), Software (equal)
Search for more papers by this authorCorresponding Author
Guannan Ju
School of Materials Science and Engineering, Shandong University of Technology, Zibo, China
Correspondence:
Hongwang Shen ([email protected])
Lina Zhang ([email protected])
Guannan Ju ([email protected])
Contribution: Resources (equal), Software (lead), Validation (equal), Writing - review & editing (equal)
Search for more papers by this authorYongxiang Hu
School of Materials Science and Engineering, Shandong University of Technology, Zibo, China
Contribution: Data curation (lead), Formal analysis (lead), Investigation (lead), Project administration (lead), Resources (equal), Software (equal), Supervision (equal), Visualization (equal), Writing - original draft (lead)
Search for more papers by this authorCorresponding Author
Hongwang Shen
School of Materials Science and Engineering, Shandong University of Technology, Zibo, China
Correspondence:
Hongwang Shen ([email protected])
Lina Zhang ([email protected])
Guannan Ju ([email protected])
Contribution: Conceptualization (lead), Data curation (lead), Formal analysis (lead), Funding acquisition (lead), Project administration (lead), Resources (lead), Validation (lead), Visualization (lead), Writing - original draft (lead), Writing - review & editing (lead)
Search for more papers by this authorHuali Ni
Shandong Hua Zhilin Pharmaceutical Co. Ltd, Zibo, China
Contribution: Project administration (equal), Resources (equal), Software (equal)
Search for more papers by this authorYuanbiao Liu
School of Materials Science and Engineering, Shandong University of Technology, Zibo, China
Contribution: Resources (equal), Software (lead)
Search for more papers by this authorCorresponding Author
Lina Zhang
College of Pharmacy, Hebei Medical University, Shijiazhuang, Hebei, People's Republic of China
Correspondence:
Hongwang Shen ([email protected])
Lina Zhang ([email protected])
Guannan Ju ([email protected])
Contribution: Resources (lead), Software (equal)
Search for more papers by this authorCorresponding Author
Guannan Ju
School of Materials Science and Engineering, Shandong University of Technology, Zibo, China
Correspondence:
Hongwang Shen ([email protected])
Lina Zhang ([email protected])
Guannan Ju ([email protected])
Contribution: Resources (equal), Software (lead), Validation (equal), Writing - review & editing (equal)
Search for more papers by this authorFunding: This study was supported by the Natural Science Foundation of Shandong Province, ZR2023QE032 and Innovation Ability Improvement Project of Science and Technology SMEs in Shandong Province, 2022TSGC1166.
ABSTRACT
Modulating the crystallization behavior of polylactic acid (PLA) is significant for expanding its application range. In this article, a synergetic nucleating agent of talc and D-sorbitol combination is incorporated into PLA via melt blending to enhance the crystallization of PLA. Then, differential scanning calorimetry (DSC) is employed to study the nonisothermal and isothermal crystallization behaviors, and the analysis of isothermal crystallization kinetics is carried out according to the Avrami equation, which has confirmed that the synergetic nucleating agent can promote the increase of the crystallinity from 3.5% to 43.8% and enhance the crystallization rate. Meanwhile, the analysis of Lauritzen–Hoffman's secondary nucleation theory reveals an obvious decline in the nucleation constant and fold surface free energy of PLA chains, which means a superior nucleating efficiency. Furthermore, the results of polarized optical microscopy (POM) demonstrated that the addition of the synergetic nucleating agent resulted in a greater number of spherical crystals with smaller sizes simultaneously visible in the field of view, indicating the synergetic nucleating agent promotion effect on PLA crystallization.
Conflicts of Interest
The authors declare no conflicts of interest.
Open Research
Data Availability Statement
The raw/processed data required to reproduce these findings cannot be shared at this time due to legal or ethical reasons.
Supporting Information
| Filename | Description |
|---|---|
| app56796-sup-0001-supinfo.docxWord 2007 document , 2 MB |
Data S1. Supporting Information. |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1 M. MacLeod, H. P. H. Arp, M. B. Tekman, and A. Jahnke, “The Global Threat From Plastic Pollution,” Science 373 (2021): 61–65.
- 2 G. Yin and X. Yang, “Biodegradable Polymers: A Cure for the Planet, But a Long Way to Go,” Journal of Polymer Research 27 (2020): 38.
- 3 P. Saini, M. Arora, and M. R. Kumar, “Poly(Lactic Acid) Blends in Biomedical Applications,” Advanced Drug Delivery Reviews 107 (2016): 47–59.
- 4 J. Tang, J. Li, G. Li, et al., “Spermidine-Mediated Poly(Lactic-co-Glycolic Acid) Nanoparticles Containing Fluorofenidone for the Treatment of Idiopathic Pulmonary Fibrosis,” International Journal of Nanomedicine 12 (2017): 6687–6704.
- 5 P. C. Dartora, M. Rosa Loureiro, and M. M. Camargo Forte, “Crystallization Kinetics and Morphology of Poly(Lactic Acid) With Polysaccharide as Nucleating Agent,” Journal of Thermal Analysis and Calorimetry 134 (2018): 1705–1713.
- 6 H. Fang, Y. Zhang, J. Bai, and Z. Wang, “Shear-Induced Nucleation and Morphological Evolution for Bimodal Long Chain Branched Polylactide,” Macromolecules 46 (2013): 6555–6565.
- 7 V. Jost, “Packaging Related Properties of Commercially Available Biopolymers—An Overview of the Status Quo,” Express Polymer Letters 12 (2018): 429–435.
- 8 S. Saeidlou, M. A. Huneault, H. Li, and C. B. Park, “Poly(Lactic Acid) Crystallization,” Progress in Polymer Science 37 (2012): 1657–1677.
- 9 Z. Liu, X. Li, W. Dai, J.-J. Liu, and M.-J. Lin, “Naphthalenediimide and Perylenediimide Based Donor-Acceptor Crystalline Hybrid Materials: Structures and Applications,” Coordination Chemistry Reviews 526 (2025): 216350.
- 10 P. Tiwary and M. Kontopoulou, “Tuning the Rheological, Thermal, and Solid-State Properties of Branched PLA by Free-Radical-Mediated Reactive Extrusion,” ACS Sustainable Chemistry & Engineering 6 (2018): 2197–2206.
- 11 A. Greco and F. Ferrari, “Thermal Behavior of PLA Plasticized by Commercial and Cardanol-Derived Plasticizers and the Effect on the Mechanical Properties,” Journal of Thermal Analysis and Calorimetry 146 (2020): 131–141.
- 12
P. Jariyasakoolroj, N. Rojanaton, and L. Jarupan, “Crystallization Behavior of Plasticized Poly(Lactide) Film by Poly(l-Lactic Acid)-Poly(Ethylene Glycol)-Poly(l-Lactic Acid) Triblock Copolymer,” Polymer Bulletin 77 (2019): 2309.
10.1007/s00289-019-02862-4 Google Scholar
- 13 S. Deng, J. Yao, H. Bai, H. Xiu, Q. Zhang, and Q. Fu, “A Generalizable Strategy Toward Highly Tough and Heat-Resistant Stereocomplex-Type Polylactide/Elastomer Blends With Substantially Enhanced Melt Processability,” Polymer 224 (2021): 123736.
- 14 H. Park and C. Hong, “Relationship Between the Stereocomplex Crystallization Behavior and Mechanical Properties of PLLA/PDLA Blends,” Polymers 2021 (1851): 13.
- 15 M. Razavi and S. Wang, “Why Is Crystalline Poly(Lactic Acid) Brittle at Room Temperature?,” Macromolecules 52 (2019): 5429–5441.
- 16 H. Li and M. A. Huneault, “Effect of Nucleation and Plasticization on the Crystallization of Poly(Lactic Acid),” Polymer 48 (2007): 6855–6866.
- 17 K. Okada, K. Watanabe, T. Urushihara, A. Toda, and M. Hikosaka, “Role of Epitaxy of Nucleating Agent (NA) in Nucleation Mechanism of Polymers,” Polymer 48 (2007): 401–408.
- 18 S. Yoshimoto, T. Ueda, K. Yamanaka, A. Kawaguchi, E. Tobita, and T. Haruna, “Epitaxial Act of Sodium 2,2′-Methylene-Bis-(4,6-di-t-Butylphenylene)phosphate on Isotactic Polypropylene,” Polymer 42 (2001): 9627–9631.
- 19 A. M. Harris and E. C. Lee, “Improving Mechanical Performance of Injection Molded PLA by Controlling Crystallinity,” Journal of Applied Polymer Science 107 (2007): 2246.
- 20 F. Yu, T. Liu, X. Zhao, X. Yu, A. Lu, and J. Wang, “Effects of Talc on the Mechanical and Thermal Properties of Polylactide,” Journal of Applied Polymer Science 125 (2012): E99–E109.
- 21 Y. Cai and L. Zhao, “Investigation on the Modification of N,N′-Adipic Bis(Benzoic Acid) Dihydrazide on Poly(l-Lactic Acid),” Polymer Bulletin 76 (2019): 2295–2310.
- 22 M. Pluta, J. Bojda, T. Makowski, et al., “Significant Modification of the Surface Morphology of Polylactide (PLA) and PLA-Halloysite Nanocomposites in the Presence of N,N'-Ethylenebis(Stearamide) Upon Thermal Treatment,” Express Polymer Letters 14 (2020): 1155–1168.
- 23 S. Boyacioglu, M. Kodal, and G. Ozkoc, “A Comprehensive Study on Shape Memory Behavior of PEG Plasticized PLA/TPU Bio-Blends,” European Polymer Journal 122 (2020): 109372.
- 24 A. R. M. Costa, C. B. B. Luna, E. P. Nascimento, et al., “Tailoring PLA/ABS Blends Compatibilized With SEBS-g-MA Through Annealing Heat Treatment,” Polymers 15 (2023): 3434.
- 25 T. Song, M. Liu, J. Tian, S. W. Wang, and Q. Li, “Effect of PLA/TiO2/Lg Filler Competition and Synergy on Crystallization Behavior, Mechanics and Functionality of Composite Foaming Materials,” Polymer 271 (2023): 125797.
- 26 A. Kovalcik, R. A. Pérez-Camargo, C. Fürst, P. Kucharczyk, and A. J. Müller, “Nucleating Efficiency and Thermal Stability of Industrial Non-Purified Lignins and Ultrafine Talc in Poly(Lactic Acid) (PLA),” Polymer Degradation and Stability 142 (2017): 244–254.
- 27
R. Somsunan and N. Mainoiy, “Isothermal and Non-Isothermal Crystallization Kinetics of PLA/PBS Blends With Talc as Nucleating Agent,” Journal of Thermal Analysis and Calorimetry 139 (2019): 1941.
10.1007/s10973-019-08631-9 Google Scholar
- 28 X. Zhang, B. Yang, B. Fan, H. Sun, and H. Zhang, “Enhanced Nonisothermal Crystallization and Heat Resistance of Poly(l-Lactic Acid) by D-Sorbitol as a Homogeneous Nucleating Agent,” ACS Macro Letters 10 (2021): 154–160.
- 29 B. Yang and X. Wan, “Trace Sorbitol-Modified Nano-Silica: Towards Nano-Nucleation for Poly(L-Lactic Acid),” International Journal of Biological Macromolecules 274 (2024): 133236.
- 30 H. Liu, J. Hu, Y. Zhang, J. Zhao, X. Wang, and J. Song, “A Dual Role of D-Sorbitol in Crystallizing and Processing Poly(Lactic Acid),” Journal of Polymer Research 30 (2023): 102.
- 31
A. T. Lorenzo, M. L. Arnal, J. Albuerne, and A. J. Müller, “DSC Isothermal Polymer Crystallization Kinetics Measurements and the Use of the Avrami Equation to Fit the Data: Guidelines to Avoid Common Problems,” Polymer Testing 26 (2006): 222–231.
10.1016/j.polymertesting.2006.10.005 Google Scholar
- 32 M. Yasuniwa, S. Tsubakihara, K. Iura, Y. Ono, Y. Dan, and K. Takahashi, “Crystallization Behavior of Poly(l-Lactic Acid),” Polymer 47 (2006): 7554–7563.
- 33 H. Shen, Y. Hu, Z. Lin, F. Meng, and G. Ju, “Mechanical Properties, Crystallization Behaviors and Phase Morphologies of PLA/GTR Blends by Reactive Compatibilization,” Materials 15 (2022): 7095.
- 34 J. E. Schawe, P. Pötschke, and I. Alig, “Nucleation Efficiency of Fillers in Polymer Crystallization Studied by Fast Scanning Calorimetry: Carbon Nanotubes in Polypropylene,” Polymer 116 (2017): 160–172.
- 35 R. Nasseri, C. Moresoli, A. Yu, Z. Yuan, and C. C. Xu, “Effect of Interphase Properties on Isothermal and Non-Isothermal Crystallization Behavior of Poly(Lactic Acid)/Acetylated Starch Blends,” ACS Omega 7 (2022): 27851–27863.
- 36 M. B. Alanalp, B. Ozdemir, M. Nofar, and A. Durmus, “Isothermal and Non-Isothermal Cold Crystallization Kinetics of Polylactide/Cellulose Nanocrystal (PLA/CNC) Nanocomposites,” Journal of Thermal Analysis and Calorimetry 147 (2022): 14211–14227.
- 37 S. Jain, M. M. Reddy, A. K. Mohanty, M. Misra, and A. K. Ghosh, “A New Biodegradable Flexible Composite Sheet From Poly(Lactic Acid)/poly(ε-Caprolactone) Blends and Micro-Talc,” Macromolecular Materials and Engineering 295 (2010): 750–762.
- 38 T. Tábi, I. Sajó, F. Szabó, A. Luyt, and J. Kovács, “Crystalline Structure of Annealed Polylactic Acid and Its Relation to Processing,” Express Polymer Letters 4 (2010): 659–668.
- 39 C. Zhou, H. Li, W. Zhang, et al., “Thermal Strain-Induced Cold Crystallization of Amorphous Poly(Lactic Acid),” CrystEngComm 18 (2016): 3237–3246.
- 40 N. Petchwattana and B. Narupai, “Synergistic Effect of Talc and Titanium Dioxide on Poly(Lactic Acid) Crystallization: An Investigation on the Injection Molding Cycle Time Reduction,” Journal of Polymers and the Environment 27 (2019): 837–846.
- 41 H. Shi, X. Chen, W. Chen, et al., “Crystallization Behavior, Heat Resistance, and Mechanical Performances of PLLA/myo-Inositol Blends,” Journal of Applied Polymer Science 134 (2017): 44732.
- 42 T. Tábi, S. Hajba, and J. G. Kovács, “Effect of Crystalline Forms (α′ and α) of Poly(Lactic Acid) on Its Mechanical, Thermo-Mechanical, Heat Deflection Temperature and Creep Properties,” European Polymer Journal 82 (2016): 232–243.
- 43 H. Wen, Y. Wang, D. Wang, et al., “Evaluation of Relationship Between Crystallization Structure and Thermal-Mechanical Performance of PLA With MCC Addition,” ChemistrySelect 4 (2019): 10174–10180.
- 44
B. Daniele, B. Sergio, and F. Alberto, “Crystallization Kinetics of Poly(Lactic Acid)-Talc Composites,” Express Polymer Letters 5 (2011): 849–858.
10.3144/expresspolymlett.2011.84 Google Scholar
- 45 G. S. Deshmukh, D. R. Peshwe, S. U. Pathak, and J. D. Ekhe, “Nonisothermal Crystallization Kinetics and Melting Behavior of Poly(Butylene Terephthalate) (PBT) Composites Based on Different Types of Functional Fillers,” Thermochimica Acta 581 (2014): 41–53.
- 46
Z. Meng, L. Yang, W. Geng, Y. Yao, X. Wang, and Y. Liu, “Kinetic Study on the Isothermal and Nonisothermal Crystallization of Monoglyceride Organogels,” The Scientific World Journal 2014 (2014): 1.
10.1155/2014/521047 Google Scholar
- 47 N. Bosq and D. Aht-Ong, “Isothermal and Non-Isothermal Crystallization Kinetics of Poly(Butylene Succinate) With Nanoprecipitated Calcium Carbonate as Nucleating Agent,” Journal of Thermal Analysis and Calorimetry 132 (2018): 233–249.
- 48 K. M. Seven, J. M. Cogen, and J. F. Gilchrist, “Nucleating Agents for High-Density Polyethylene-A Review,” Polymer Engineering and Science 56 (2016): 541–554.
- 49 X. Shi, G. Zhang, T. Phuong, and A. Lazzeri, “Synergistic Effects of Nucleating Agents and Plasticizers on the Crystallization Behavior of Poly(Lactic Acid),” Molecules 20 (2015): 1579–1593.
- 50 J. D. Hoffman and R. L. Miller, “Kinetic of Crystallization From the Melt and Chain Folding in Polyethylene Fractions Revisited: Theory and Experiment,” Polymer 38 (1997): 3151–3212.
- 51
R. Patwa, A. Kumar, and V. Katiyar, “Crystallization Kinetics, Morphology, and Hydrolytic Degradation of Novel Bio-Based Poly(Lactic Acid)/Crystalline Silk Nano-Discs Nanobiocomposites,” Journal of Applied Polymer Science 135 (2017): 46590.
10.1002/app.46590 Google Scholar
- 52 B. S. Hsiao, “Polymer Crystallization: The Development of Crystalline Order in Thermoplastic Polymers by Jerold M. Schultz (University of Delaware),” Journal of the American Chemical Society 124 (2002): 7251–7252.
- 53 A. Gupta, W. Simmons, G. T. Schueneman, and E. A. Mintz, “Lignin-Coated Cellulose Nanocrystals as Promising Nucleating Agent for Poly(Lactic Acid),” Journal of Thermal Analysis and Calorimetry 126 (2016): 1243–1251.
- 54 C. M. Clarkson, S. M. E. A. Azrak, G. T. Schueneman, J. F. Snyder, and J. P. Youngblood, “Crystallization Kinetics and Morphology of Small Concentrations of Cellulose Nanofibrils (CNFs) and Cellulose Nanocrystals (CNCs) Melt-Compounded Into Poly(Lactic Acid) (PLA) With Plasticizer,” Polymer 187 (2020): 122101.
- 55 A. Shakoor and N. Thomas, “Talc as a Nucleating Agent and Reinforcing Filler in Poly(Lactic Acid) Composites,” Polymer Engineering and Science 54 (2014): 64–70.
- 56 S. A. Arvidson, K. C. Wong, R. E. Gorga, and S. A. Khan, “Structure, Molecular Orientation, and Resultant Mechanical Properties in Core/Sheath Poly(Lactic Acid)/Polypropylene Composites,” Polymer 53 (2012): 791–800.
- 57 A. Kowalewska and M. Nowacka, “Supramolecular Interactions in Hybrid Polylactide Blends—The Structures, Mechanisms and Properties,” Molecules 25 (2020): 3351.
- 58 Y. Lin, K. Zhang, Z. Dong, L. Dong, and Y. Li, “Study of Hydrogen-Bonded Blend of Polylactide With Biodegradable Hyperbranched Poly(Ester Amide),” Macromolecules 40 (2007): 6257–6267.
- 59 B. Yang, B. Fan, H. Wang, and Y. Ma, “Analyzing Isothermal Crystallization of Poly(Lactic Acid)/polyol Systems: Correlated DSC and Simulation Studies,” Polymer 297 (2024): 126843.
