Tubular Nanoclay-Enhanced Calcium Phosphate Mineralization and Assembly to Impart High Stiffness and Antimicrobial Properties

Achieving superior mechanical properties of composite materials in artificially engineered materials is a great challenge due to technical bottlenecks in the size and morphological modulation of inorganic nanominerals. Hence, a “bioprocess-inspired fabrication” is proposed to create multilayered organic–inorganic columnar structures. The sequential assembly of halloysite nanotubes (HNTs), polyelectrolytes (PAAs), and calcium phosphates (CaPs) results in organic–inorganic structures. PAA plays a crucial role in controlling the formation of CaP, guiding it into amorphous particles with smaller nanosizes. The introduction of HNT induces the assembly and maturation of CaP–PAA, leading to the formation of a highly crystalline hydroxyapatite. Poly(vinyl alcohol) was then woven into HNT-encapsulated hydroxyapatite nanorods, resulting in composite materials with basic hierarchical structures across multiple scales. The fabricated composite exhibits exceptional hardness (4.27 ± 0.33 GPa) and flexural strength (101.25 ± 1.72 MPa), surpassing those of most previously developed biological hard tissue materials. Additionally, the composite demonstrates effective antibacterial properties and corrosion resistance, attributed to the dense crystalline phase of CaP. This innovative approach showcases the potential of clay minerals, particularly HNT, in the advancement of biomaterial design. The outstanding mechanical and antimicrobial properties of clay-based composites make them a promising candidate for applications in hard tissue repair, offering versatility in biomedicine and engineering.