Review of the Integration of Fused Filament Fabrication with Complementary Methods for Fabricating Hierarchical Porous Polymer Structures

Hierarchically porous polymers can unite macro-scale architected voids with micro-scale pores, enabling unique combinations of low density, high surface area, and controlled transport properties that are difficult to achieve with traditional methods. This review outlines the current advancements in creating such multiscale architectures using fused filament fabrication (FFF), the most widely used polymer additive manufacturing technique. Unlike earlier reviews that consider lattice architectures and foaming chemistries separately, this work integrates both within a single analysis. It begins with an overview of FFF fundamentals and how process parameters affect macropore formation. Design strategies for achieving macroporosity (≳100 µm) with a single thermoplastic are presented and categorized: 2D infill patterns, strut-based lattices, triply periodic minimal surfaces (TPMS), and Voronoi structures, along with functionally graded approaches. The discussion then shifts to functional filaments incorporating chemical or physical blowing agents, thermally expandable or hollow microspheres, and sacrificial porogens, which create microporosity (≲100 µm) either in situ or through post-processing. Each material approach is connected to case studies that demonstrate its application. A comparative analysis highlights the advantages of each method. Key challenges such as viscosity control, thermal gradient management, dimensional instability during foaming, environmental concerns, and the absence of standardized porosity measurement techniques are addressed. Finally, emerging solutions and future directions are explored. Overall, this review provides a comprehensive perspective on strategies that enhance FFF’s capability to fabricate hierarchically porous polymer structures.