Abstract
This study investigated how fabrication method (milling versus 3D printing) affects the water sorption and solubility of PMMA dental materials, and how surface characteristics affect hydrolytic stability. Fifty-six PMMA samples were divided into three groups fabricated from CAD/CAM milled discs (Group A: I-III) and four groups from 3D-printed resin (Group B: IV-VII), each subjected to distinct postprocessing protocols. Water sorption (wsp) and solubility (wsl) were measured after immersion in distilled water at 37 °C for 24, 48, and 72 h, and 7 and 14 days. Surface topography and nanoroughness were assessed using atomic force microscopy (AFM). Statistical descriptive analyses were followed by correlation analyses. Milled PMMA demonstrated significantly lower water sorption and negative solubility (mass loss), indicating material dissolution. In contrast, 3D-printed PMMA showed higher water sorption and positive solubility (mass gain), reflecting water incorporation and polymer swelling. The kinetic profiles differed: milled PMMA displayed a monophasic absorption curve, while 3D-printed PMMA exhibited a biphasic pattern with accelerated water uptake after 72 h. AFM analysis revealed that 3D-printed surfaces had significantly greater nanoroughness than milled surfaces. Strong positive correlations were observed between surface roughness parameters (Sa, Sy) and water sorption capacity. The fabrication method was found to influence the hydrolytic stability of PMMA dental materials. Milled PMMA demonstrated superior stability, with lower water uptake, smoother surfaces, and lower leaching solubility. In contrast, 3D-printed PMMA exhibited increased surface roughness and water sorption, attributed to its layered microstructure and nanoporosity. Surface topography emerged as a strong predictor of wsl, related to hydrolytic degradation. For clinical applications, milled PMMA is recommended for long-term use requiring durability, whereas 3D-printed PMMA may be appropriate for short-term applications with optimised postprocessing.