Hard-Particle Surface Stabilization and Data-Driven Wear Prediction in TiB2-Reinforced Heat-Polymerized PMMA Denture Base Composites

Abstract

Poly(methyl methacrylate) (PMMA) remains a clinically important denture base polymer because of its favorable processability, aesthetics, repairability and long-term prosthodontic use; however, its limited surface hardness and susceptibility to sliding-induced degradation constrain surface durability. This study establishes the structure-chemistry-microstructure-tribology relationships and composition-window predictive behavior of heat-polymerized PMMA reinforced with titanium diboride (TiB2). PMMA/TiB2 composites containing 1, 3 and 5 wt.% TiB2 were prepared and compared with unreinforced PMMA. X-ray diffraction confirmed preservation of the broad amorphous/semi-amorphous PMMA response, while TiB2-related crystalline features became increasingly detectable with reinforcement content. ATR-FTIR showed retention of the characteristic C-H, ester C=O and C-O/C-O-C vibrations. SEM/EDS demonstrated progressively greater particle-related surface contrast and local Ti/B-associated elemental signatures. Vickers microhardness increased from 20.0 +/- 0.7 to 35.0 +/- 1.39 HV0.03, corresponding to a 75.0% improvement at 5 wt.% TiB2. After 1000 m of dry sliding, total mass loss decreased from 32.4 +/- 0.5 to 14.9 +/- 0.4 mg (54.0% reduction), overall coefficient of friction decreased from 0.58 to 0.35, and representative wear-track width decreased from 481.4 to 101.8 & micro;m. A parsimonious distance-composition interaction model retained strong grouped leave-one-composition-out performance for cumulative wear (R2 = 0.9622; RMSE = 1.53 mg), while a linear composition model provided the most robust hardness prediction (R2 = 0.9317; RMSE = 1.50 HV0.03). More complex nonlinear models did not improve prediction for held-out compositions. Within the investigated 0-5 wt.% window, 5 wt.% TiB2 provided the most effective combination of matrix preservation, surface hardening, wear suppression and frictional stabilization.