Interphase-Resolved Performance in PA6/TiO2 Nanocomposite Fibers: Four-Phase Geometry Linking Structure to Mechanical and UV Protection

Melt-spun PA6/TiO₂ fibers with TiO₂ modified by silane coupling agents KH550 and KH570 at 0, 1.6, and 4 wt% provide a practical testbed to address three fiber-centric gaps: transferable interphase quantification, interphase-resolved indications of compatibility, and a reproducible kinetics-structure-property link. This work proposes, for the first time at fiber scale, a four-phase partition into crystal (c), crystal-adjacent rigid amorphous fraction (RAF-c), interfacial rigid amorphous fraction (RAF-i), and mobile amorphous fraction (MAF), and extracts an interfacial triad consisting of the specific interfacial area (S_v), polymer-only RAF-i fraction expressed per composite volume (Γ_i), and interphase thickness (t_i) from SAXS invariants to establish a quantitative interphase-structure-property framework. A documented SAXS/DSC/WAXS workflow partitions the polymer into the above four components on a polymer-only basis. Upon filling, Γ_i increases while RAF-c decreases, leaving the total RAF approximately conserved. Under identical cooling, DSC shows the crystallization peak temperature is higher by 1.6-4.3 °C and has longer half-times, indicating enhanced heterogeneous nucleation together with growth are increasingly limited by interphase confinement. At 4 wt% loading, KH570-modified fibers versus KH550-modified fibers exhibit higher α-phase orientation (Hermans factor f(α): 0.697 vs. 0.414) but an ~89.4% lower α/γ ratio. At the macroscale, compared to pure (neat) PA6, 4 wt% KH550- and KH570-modified fibers show tenacity enhancements of ~9.5% and ~33.3%, with elongation decreased by ~31-68%. These trends reflect orientation-driven stiffening accompanied by a reduction in the mobile amorphous fraction and stronger interphase constraints on chain mobility. Knitted fabrics achieve a UV protection factor (UPF) of at least 50, whereas pure PA6 fabrics show only ~5.0, corresponding to ≥16-fold improvement. Taken together, the SAXS-derived descriptors (S_v, Γ_i, t_i) provide transferable interphase quantification and, together with WAXS and DSC, yield a reproducible link from interfacial geometry to kinetics, structure, and properties, revealing two limiting regimes-orientation-dominated and phase-fraction-dominated.