ABSTRACT
Small-angle and ultrasmall-angle neutron scattering (SANS and USANS) were used to characterize silica nanoparticle dispersion morphologies and the interphase in thermoset dimethacrylate polymer nanocomposites. Silica nanoparticle fillers were silanized with varying mass ratios of 3-methacryloxypropyltrimethoxysilane (MPTMS), a silane that interacts with the matrix through covalent and H-bonding, and n-octyltrimethoxysilane (OTMS), a silane that interacts through weak dispersion forces. Interphases with high OTMS mass fractions were found to be fractally rough with fractal dimensions, D(s), between 2.19 and 2.49. This roughness was associated with poor interfacial adhesion and inferior mechanical properties. Mean interparticle distances calculated for composites containing 10 mass % and 25 mass % silica suggest that the nanoparticles treated with more MPTMS than OTMS may be better dispersed than OTMS-rich nanoparticles. The results indicate that the covalent bonding and H-bonding of MPTMS-rich nanoparticles with the matrix are necessary for preparing well-dispersed nanocomposites. In addition, interphases containing equal masses of MPTMS and OTMS may yield composites with overall optimal properties. Finally, the combined SANS/USANS data could distinguish the differences, as a function of silane chemistry, in the nanoparticle/silane and silane/matrix interfaces that affect the overall mechanical properties of the composites.
Subject(s)
Dental Materials , Nanocomposites , Neutrons , Phase Transition , Scattering, Small Angle , Materials Testing , Nanocomposites/ultrastructure , Surface PropertiesABSTRACT
OBJECTIVES: The aim of this research was to better understand the relationships between interphase composition and the resultant mechanical properties of thermoset methacrylate nanocomposites, ultimately for the purpose of improving the properties of dental restorative materials through manipulation of the interphase. METHODS: Silica nanoparticles were silanized with three different silanes and blends of those silanes to generate six different interphase compositions. The silanes varied in their relative polarity, flexibility, and reactivity towards photo-polymerization. Composites containing 60% by mass of the silanized fillers were prepared and analyzed for uncured paste handling characteristics, vinyl conversion, biaxial flexure strength (BFS), modulus, and Knoop hardness. RESULTS: Dual silanization of the fillers improved the handling characteristics of the uncured composite pastes compared to those containing fillers silanized with 3-methacryloxypropyltrimethoxysilane. To obtain high BFS, functional groups reactive in free radical polymerization were needed in the composite interphase, but a high concentration of those groups was not necessary. Moduli were highest for composites with interphases that contained styrylethyltrimethoxysilane, a reactive aromatic silane. The hardness values of the composites with reactive interphases were all comparable. Methacrylate conversion was only modestly influenced by silane interphase composition. SIGNIFICANCE: This study suggests that dual silanization is a practical method for improving the handling characteristics of uncured dental restorative nanocomposites while maintaining or improving the mechanical properties of the cured composites.
Subject(s)
Composite Resins/chemistry , Dental Materials/chemistry , Methacrylates/chemistry , Nanocomposites/chemistry , Chemical Phenomena , Chemistry, Physical , Composite Resins/radiation effects , Dental Materials/radiation effects , Elasticity , Electrochemistry , Hardness , Humans , Light , Materials Testing , Methacrylates/radiation effects , Nanocomposites/radiation effects , Nanoparticles/chemistry , Nanoparticles/radiation effects , Pliability , Polymers/chemistry , Polymers/radiation effects , Silanes/chemistry , Silanes/radiation effects , Silicon Dioxide/chemistry , Silicon Dioxide/radiation effects , Stress, Mechanical , Structure-Activity Relationship , Vinyl Compounds/chemistry , Vinyl Compounds/radiation effectsABSTRACT
This study was designed to determine the effect of varying the chemistry of the interfacial phase on critical composite properties in dental nanocomposite materials. Silica nanoparticles were silanized with varying ratios of 3-methacryloxypropyltrimethoxysilane (MPTMS) and octyltrimethoxysilane (OTMS) while keeping the total amount of silane constant at 10% by mass fraction relative to the mass of filler. The silanized nanoparticles were mixed into a dimethacrylate resin (60% filler by mass fraction). The mechanical properties of the uncured pastes were assessed by compression testing between parallel plates. The composites were photo-cured and tested by biaxial flexure and three-point bend flexure testing. Fracture surfaces were analyzed by field-emission scanning electron microscopy (FE-SEM). At maximized filler mass fractions, the workabilities of the uncured pastes were better maintained as the fraction of OTMS in the interphase increased relative to MPTMS. The flexure strengths and moduli of the MPTMS silanized and dual silanized composites were similar but decreased as OTMS mass fractions in the silane mixture increased to 7.5% and 10%. FE-SEM images revealed evidence for phase separation in the composites containing silica silanized with high fractions of OTMS. Among the potential practical benefits of dual silanized nanoparticles are the improved workability of composite pastes with higher filler loadings that should lead to higher modulus composites with lower polymerization shrinkage.
