Current dental resin undergoes phase separation into hydrophobic-rich and hydrophilic-rich phases during infiltration of the over-wet demineralized collagen matrix. Such phase separation undermines the integrity and durability of the bond at the composite/tooth interface. This study marks the first time that the polymerization kinetics of model hydrophilic-rich phase of dental adhesive has been determined. Samples were prepared by adding varying water content to neat resins made from 95 and 99wt% hydroxyethylmethacrylate (HEMA) and 5 and 1wt% (2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl1]-propane (BisGMA) prior to light curing. Viscosity of the formulations decreased with increased water content. The photo-polymerization kinetics study was carried out by time-resolved FTIR spectrum collector. All of the samples exhibited two-stage polymerization behavior which has not been reported previously for dental resin formulation. The lowest secondary rate maxima were observed for water content of 10-30%wt. Differential scanning calorimetry (DSC) showed two glass transition temperatures for the hydrophilic-rich phase of dental adhesive. The DSC results indicate that the heterogeneity within the final polymer structure decreased with increased water content. The results suggest a reaction mechanism involving both polymerization-induced phase separation (PIPs) and solvent-induced phase separation (SIPs) for the model hydrophilic-rich phase of dental resin.

The 2-fold objectives of this study were 1) to understand whether model hydrophobic-and hydrophilic-rich phase mimics of dentin adhesive polymerize similarly and 2) to determine which factor, the dimethacrylate component, bisphenol A glycerolate dimethacrylate (BisGMA) or photoinitiator concentration, has greater influence on the polymerization of the hydrophilic-rich phase mimic. Current dentin adhesives are sensitive to moisture, as evidenced by nanoleakage in the hybrid layer and phase separation into hydrophobic-and hydrophilic-rich phases. Phase separation leads to limited availability of the cross-linkable dimethacrylate monomer and hydrophobic photoinitiators within the hydrophilic-rich phase. Model hydrophobic-rich phase was prepared as a single-phase solution by adding maximum wt% deuterium oxide (D 2 O) to HEMA/BisGMA neat resins containing 45 wt% 2-hydroxyethyl methacrylate (HEMA). Mimics of the hydrophilicrich phase were prepared similarly but using HEMA/BisGMA neat resins containing 95, 99, 99.5, and 100 wt% HEMA. The hydrophilic-rich mimics were prepared with standard or reduced photoinitiator content. The photoinitiator systems were camphorquinone (CQ)/ethyl 4-(dimethylamino)benzoate (EDMAB) with or without [3-(3, 4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-2-hydroxypropyl]trimethylammonium chloride (QTX). The polymerization kinetics was monitored using a Fourier transform infrared spectrophotometer with a time-resolved collection mode. The hydrophobic-rich phase exhibited a significantly higher polymerization rate compared with the hydrophilic-rich phase. Postpolymerization resulting in the secondary rate maxima was observed for the hydrophilic-rich mimic. The hydrophilic-rich mimics with standard photoinitiator concentration but varying cross-linker (BisGMA) content showed postpolymerization and a substantial degree of conversion. In contrast, the corresponding formulations with reduced photoinitiator concentrations exhibited lower polymerization and inhibition/delay of postpolymerization within 2 h. Under conditions relevant to the wet, oral environment, photoinitiator content plays an important role in the polymerization of the hydrophilic-rich phase mimic. Since the hydrophilic-rich phase is primarily water and monomethacrylate monomer (e.g., HEMA as determined previously), substantial polymerization is important to limit the potential toxic response from HEMA leaching into the surrounding tissues.

The impact of light intensity on the degree of conversion (DC), rate of polymerization and network structure was investigated for hydrophobic and hydrophilic dental adhesive resins. Two and three component photoinitiating (PI) systems were used in this study. Low light intensities had a negative impact on the polymerization efficiency for the hydrophilic resin with 2 component PI system. Incorporation of iodonium salt in the hydrophilic resin significantly improved the polymerization efficiency of the HEMA/BisGMA system and led to a substantial DC, even at low light intensities. The results suggested that shorter polymer chains were formed in the presence of iodonium salt. It appears that there is little or no impact of light intensity on the polymer structure of the 2 component PI system. Light intensity has subtle impact on the polymer structure of the 3 component PI system. In the case of the hydrophobic resin, the polymer is so highly cross-linked that the presence of shorter chains for the 3 component PI system does not cause a decrease in the glass transition temperature (Tg) when compared to the 2 component PI system. For the hydrophilic resin, the presence of shorter polymer chains in the 3 component PI system reduces the Tg when compared with the corresponding 2 component PI system.

Water is ubiquitous in the mouths of healthy individuals and is a major interfering factor in the development of a durable seal between the tooth and composite restoration. Water leads to the formation of a variety of defects in dentin adhesives; these defects undermine the tooth-composite bond. Our group recently analyzed phase partitioning of dentin adhesives using high-performance liquid chromatography (HPLC). The concentration measurements provided by HPLC offered a more thorough representation of current adhesive performance and elucidated directions to be taken for further improvement. The sample preparation and instrument analysis using HPLC are, however, time-consuming and labor-intensive. The objective of this work was to develop a methodology for rapid, reliable, and accurate quantitative analysis of near-equilibrium phase partitioning in adhesives exposed to conditions simulating the wet oral environment. Analysis by Fourier transform infrared (FT-IR) spectroscopy in combination with multivariate statistical methods, including partial least squares (PLS) regression and principal component regression (PCR), were used for multivariate calibration to quantify the compositions in separated phases. Excellent predictions were achieved when either the hydrophobic-rich phase or the hydrophilic-rich phase mixtures were analyzed. These results indicate that FT-IR spectroscopy has excellent potential as a rapid method of detection and quantification of dentin adhesives that experience phase separation under conditions that simulate the wet oral environment.

The use of nanofillers to enhance the properties of fiber reinforced composites is limited due to the adverse effect on mechanical properties caused by agglomeration of these nanofillers in the matrix materials. In this study, graphene nanoflakes were functionalized with silane moiety to improve its dispersion, stability and bond strengths in the polymer matrices of the carbon fiber reinforced composites. Wet layup process was applied to incorporate graphene nanocomposites into the dry carbon fibers to make composite panels following the curing cycle of the epoxy and hardener. The impacts of the functionalized graphene on the mechanical and thermal properties of carbon reinforced composite were investigated in detail by tensile test, differential scanning calorimetry, dynamic mechanical analysis and scanning electron microscopy (SEM) analysis. It was observed that nanocomposites with 0.5 wt% silanized graphene exhibited maximum tensile strength and modulus of elasticity, indicating that 0.50 wt% silane functionalized graphene was the optimum nanofiller composition amongst the three different compositions investigated. The nanocomposites with 0.25 wt% and 0.50 wt% nanofillers showed improved ductility compared to the control sample. Based on the SEM studies on the crack zones, major morphological changes were observed after the salinization process. The interfacial interaction between epoxy and silane moiety of the graphene and reduction in the tendency to agglomerate could account for the improved properties of the nanocomposite observed here. Nanocomposites with silanized graphene showed overall higher glass transition temperature (Tg) and tensile strength than those with pristine graphene and control samples.