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Volume 116
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Structural regulation of polylactic acid porous microspheres by different porogens
Ni Su, Hong Yin, Shenfeng Yuan, Zhirong Chen, Qilei Zhang *
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310058, China
10.1016/j.partic.2026.06.031
Volume 116, September 2026, Pages 411-423
Received 31 January 2026, Revised 14 May 2026, Accepted 22 June 2026, Available online 4 July 2026, Version of Record 15 July 2026.
E-mail: zql@zju.edu.cn
Highlights

• Solution-penetrating and gas-foaming porogens for PDLLA microspheres were compared.

• Electrolyte porogens offered excellent tunability for pore size and porosity.

• NaHCO3 and NH4HCO3 created large interconnected cavities within microspheres.


Abstract

This study systematically compared the regulatory effects of solution-penetrating (NaCl, NaAc, sucrose, MgSO4) and gas-foaming porogens (NaHCO3, NH4HCO3) on the structure of poly (D, L-lactic acid) (PDLLA) porous microspheres prepared via double emulsion-solvent evaporation. The results demonstrated that solution-penetrating porogens affected the particle size of the microspheres, and the largest particle sizes (65–74 μm) were achieved when using MgSO4 or sucrose as porogens. Moreover, the non-electrolyte sucrose returned more well-structured microspheres with a narrower particle size distribution (span values of 0.829–0.776). Meanwhile, electrolyte porogens performed better in tailoring pore-structure parameters such as pore size and porosity. Parameters such as pore volume, pore size, and porosity increased with the increase of porogen concentration, while bulk density and specific surface area gradually decreased. Gas-foaming porogens could form large interconnected cavities but reduced the uniformity of the microspheres under acid induction. This study found that the pore-forming results of gas-foaming porogens bear certain similarities to those of the solution-penetration mechanism. This is because the foaming agents also possess salt ion characteristics, so their action does not rely solely on the bubbling effect but, to some extent, depends on the osmotic pressure of the ions, which provides theoretical and practical guidance for the controllable preparation of PDLLA porous microspheres.

Graphical abstract
Keywords
Porogen; Polylactic acid; Porous microspheres; Solution penetration; Gas foaming
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