title: Rheological and mechanical properties and interfacial stress development of composite cements modified with thio-urethane oligomers.
abstract: Thio-urethane oligomers have been shown to reduce stress and increase toughness in highly filled composite materials. This study evaluated the influence of thio-urethane backbone structure on rheological and mechanical properties of resin cements modified with a fixed concentration of the oligomers.
  
  
  
  Thio-urethane oligomers (TU) were synthesized by combining thiols - pentaerythritol tetra-3-mercaptopropionate (PETMP) or trimethylol-tris-3-mercaptopropionate (TMP) - with isocyanates - 1,6-hexanediol-diissocyante (HDDI) (aliphatic) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (BDI) (aromatic) or dicyclohexylmethane 4,4'-diisocyanate (HMDI) (cyclic), at 1:2 isocyanate:thiol, leaving pendant thiols. 20wt% TU were added to BisGMA-UDMA-TEGDMA (5:3:2). 60wt% silanated inorganic fillers were added. Near-IR was used to follow methacrylate conversion and rate of polymerization ( [Formula: see text] ). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM, and toughness), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). PS was measured on the Bioman. Viscosity (V) and gel-points (defined as the crossover between storage and loss shear moduli (G'/G″)) were obtained with rheometry. Glass transition temperature (Tg), cross-link density and homogeneity of the network were obtained with dynamic mechanical analysis. Film-thickness was evaluated according to ISO 4049.
  
  
  
  DC and mechanical properties increased and [Formula: see text] and PS decreased with the addition of TUs. Gelation (G'/G″) was delayed and DC at G'/G″ increased in TU groups. Tg and cross-link density dropped in TU groups, while oligomers let to more homogenous networks. An increase in V was observed, with no effect on film-thickness. Significant reductions in PS were achieved at the same time conversion and mechanical properties increased.
  
  
  
  The addition of thio-urethane oligomers proved successful in improving several key properties of resin cements, without disrupting the procedures dentists use to polymerize the material. This approach has potential to be translated to commercial materials very readily.
authors.affiliation: Department of Restorative Dentistry, Division of Biomaterials and Biomechanics, School of Dentistry, Oregon Health and Science University, 2730 SW Moody Ave, Portland, OR 97201, USA; Department of Prosthodontics and Dental Materials, School of Dentistry, Meridional Faculty, Av. Senador Pinheiro, 304, Passo Fundo, RS 99070-220, Brazil.
authors.forename: Ataís
authors.initials: A
authors.lastname: Bacchi
authors.affiliation: Department of Restorative Dentistry, Division of Biomaterials and Biomechanics, School of Dentistry, Oregon Health and Science University, 2730 SW Moody Ave, Portland, OR 97201, USA. Electronic address: pfeiferc@ohsu.edu.
authors.forename: Carmem S
authors.initials: CS
authors.lastname: Pfeifer
mesh_terms: D003188:Composite Resins; D055119:Elastic Modulus; D006018:Glycols; D008422:Materials Testing; D008689:Methacrylates; D018583:Pliability; D013314:Stress, Mechanical; D014520:Urethane
chemical_list: D003188:Composite Resins; D006018:Glycols; D008689:Methacrylates; D014520:Urethane; C027765:hexamethylene glycol
keywords: Dynamic mechanical analysis; Mechanical strength; Polymerization stress; Resin cements; Rheological properties; Thio-urethane oligomers