Fabrication of Wet-Spun Alginate/Halloysite Nanotube Composite Filaments with Tunable Morphology and Caffeine-Functionalized Nanotube Interfaces

Hybrid organic–inorganic composites based on biopolymers and nanoclays are attracting increasing interest for the development of functional materials in biomedical and agricultural applications. In this work, elongated alginate/halloysite nanotube (Alg/HNT) composite filaments were fabricated through a wet-spinning process assisted by syringe-based extrusion. Alg/HNT dispersions with different inorganic/organic ratios were first screened in terms of colloidal stability and injectability in order to identify suitable formulations for extrusion. The influence of key processing parameters, including the extrusion flow rate and calcium chloride concentration in the coagulation bath, was then systematically investigated to elucidate their effect on filament morphology and structure. Optical and scanning electron microscopy revealed that filament diameter can be tuned by varying the CaCl₂ concentration, while partial alignment of alginate chains along the extrusion direction was observed. Halloysite nanotubes were homogeneously distributed within the polymer matrix, mainly as micro-sized aggregates. Finally, the nanotubes were chemically functionalized with caffeine, as a model molecule, and incorporated into the alginate filaments, demonstrating the feasibility of introducing specific functionalities into wet-spun Alg/HNT composite fibers. These results establish a reproducible strategy for the fabrication of alginate/HNT filaments with tunable morphology and functionalizable nanotube interfaces, providing a versatile platform for the development of sustainable hybrid biopolymer materials.