Ranganathan Parthasarathy

Quantitative analysis of aqueous phase composition of model dentin adhesives experiencing phase separation

There have been reports of the sensitivity of our current dentin adhesives to excess moisture, for example, water-blisters in adhesives placed on over-wet surfaces, and phase separation with concomitant limited infiltration of the critical dimethacrylate component into the demineralized dentin matrix. To determine quantitatively the hydrophobic/hydrophilic components in the aqueous phase when exposed to over-wet environments, model adhesives were mixed with 16, 33, and 50 wt % water to yield well-separated phases. Based upon high-performance liquid chromatography coupled with photodiode array detection, it was found that the amounts of hydrophobic BisGMA and hydrophobic initiators are less than 0.1 wt % in the aqueous phase. The amount of these compounds decreased with an increase in the initial water content. The major components of the aqueous phase were hydroxyethyl methacrylate (HEMA) and water, and the HEMA content ranged from 18.3 to 14.7 wt %. Different BisGMA homologues and the relative content of these homologues in the aqueous phase have been identified; however, the amount of crosslinkable BisGMA was minimal and, thus, could not help in the formation of a crosslinked polymer network in the aqueous phase. Without the protection afforded by a strong crosslinked network, the poorly photoreactive compounds of this aqueous phase could be leached easily. These results suggest that adhesive formulations should be designed to include hydrophilic multimethacrylate monomers and water compatible initiators.

Polymerization- and solvent-induced phase separation in hydrophilic-rich dentin adhesive mimic

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 99 wt.% hydroxyethylmethacrylate and 5 and 1 wt.% (2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl1]-propane prior to light curing. Viscosity of the formulations decreased with increased water content. The photopolymerization kinetics study was carried out with a time-resolved Fourier transform infrared spectrometer. 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 contents 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 increasing water content. The results suggest a reaction mechanism involving both polymerization-induced phase separation and solvent-induced phase separation for the model hydrophilic-rich phase of dental resin.

Ternary Phase Diagram of Model Dentin Adhesive Exposed to Over-wet Environments

When adhesives and/or composites are bonded to the tooth, water in the environment can interfere with proper interface formation. Formation of water blisters and phase separation at the adhesive/dentin interface have appeared as new types of bond defects. To better understand this problem, we determined the near-equilibrium partition of the hydrophobic/hydrophilic components when exposed to over-wet environments. Model methacrylate-based adhesives were mixed with different amounts of water to yield well-separated aqueous and resin phases. It was found that less than 0.1% BisGMA but nearly one-third of the HEMA diffused into the aqueous phase, leaving the remaining resin phase relatively hydrophobic. A partial phase diagram was created for the ternary BisGMA/HEMA/water system. All the experimental phase partitioning data were plotted, and the points lay on a binodal curve that separated the single-phase region from the two-phase region. We obtained the 3 tie lines by connecting the 2 points of each conjugate pair of the phase partitioning data from the 3 sets of tripartite mixtures. Information about solubility, water miscibility, distribution ratio, and phase partitioning behavior could be obtained quantitatively. This type of phase diagram will provide a more thorough understanding of current adhesive performance and elucidate directions for further improvement.

Polymerization Behavior of Hydrophilic-Rich Phase of Dentin Adhesive

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 (D2O) to HEMA/BisGMA neat resins containing 45 wt% 2-hydroxyethyl methacrylate (HEMA). Mimics of the hydrophilic-rich 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.

Mechanical properties of methacrylate‐based model dentin adhesives: Effect of loading rate and moisture exposure

The aim of this study is to investigate the mechanical behavior of model methacrylate-based dentin adhesives under conditions that simulate the wet oral environment. A series of monotonic and creep experiments were performed on rectangular beam samples of dentin adhesive in three-point bending configuration under different moisture conditions. The monotonic test results show a significant effect of loading rate on the failure strength and the linear limit (yield point) of the stress-strain response. In addition, these tests show that the failure strength is low, and the failure occurs at a smaller deformation when the test is performed under continuously changing moisture conditions. The creep test results show that under constant moisture conditions, the model dentin adhesives can have a viscoelastic response under certain low loading levels. However, when the moisture conditions vary under the same low loading levels, the dentin adhesives have an anomalous creep response accompanied by large secondary creep and high strain accumulation.

Viscoelastic properties of collagen–adhesive composites under water‐saturated and dry conditions

To investigate the time- and rate-dependent mechanical properties of collagen-adhesive composites, creep and monotonic experiments are performed under dry and wet conditions. The composites are prepared by infiltration of dentin adhesive into a demineralized bovine dentin. Experimental results show that for small stress level under dry conditions, both the composite and the neat adhesive have similar behavior. On the other hand, in wet conditions, the composites are significantly soft and weak compared to the neat adhesives. The behavior in the wet condition is found to be affected by the hydrophilicity of both the adhesive and the collagen. As the adhesive-collagen composites are a part of the complex construct that forms the adhesive-dentin interface, their presence will affect the overall performance of the restoration. We find that Kelvin-Voigt model with at least four elements is required to fit the creep compliance data, indicating that the adhesive-collagen composites are complex polymers with several characteristic time scales whose mechanical behavior will be significantly affected by loading rates and frequencies. Such mechanical properties have not been investigated widely for these types of materials. The derived model provides an additional advantage that it can be exploited to extract other viscoelastic properties which are, generally, time consuming to obtain experimentally. The calibrated model is utilized to obtain stress relaxation function, frequency-dependent storage and loss modulus, and rate-dependent elastic modulus.

Swelling equilibrium of dentin adhesive polymers formed on the water-adhesive phase boundary: experiments and micromechanical model.

During their application to the wet, oral environment, dentin adhesives can experience phase separation and composition change, which can compromise the quality of the hybrid layer formed at the dentin-adhesive interface. The chemical composition of polymer phases formed in the hybrid layer can be represented using a ternary water-adhesive phase diagram. In this paper, these polymer phases are characterized using a suite of mechanical tests and swelling experiments. The experimental results were evaluated using a granular micromechanics-based model incorporating poro-mechanical effects and polymer-solvent thermodynamics. The variation in the model parameters and model-predicted polymer properties was studied as a function of composition along the phase boundary. The resulting structure-property correlations provide insight into interactions occurring at the molecular level in the saturated polymer system. These correlations can be used for modeling the mechanical behavior of the hybrid layer, and are expected to aid in the design and improvement of water-compatible dentin adhesive polymers.

Micro-scale Analysis of Compositional and Mechanical Properties of Dentin Using Homotopic Measurements

High resolution techniques are being increasingly applied to image or measure biomaterial properties. Data interpretations from these measurements have to be performed carefully to extract meaningful information. Two aspects become significant when such techniques are used in a complementary manner. Firstly, the measurements have to be performed using a homotopic methodology such that property correlations or ‘data fusion’ considers the same material volume. Secondly, appropriate mathematical models must be applied to interpret the data in terms of material properties since the high resolution technique seldom measure the properties directly. In this paper, we have described the application of scanning acoustic and scanning electron microscopy to measure the mechanical and the compositional properties of primary tooth dentin using a homotopic methodology. We have then utilized a homogenization technique in order to understand the variation in the measured elastic moduli.

Dentin/Adhesive Interface in Teeth

Clinical studies have demonstrated an alarmingly high failure rate for posterior composite dental restorations. The premature failure of moderate-to-large composite restorations can be traced to a breakdown of the bond at the tooth surface/composite material interface and increased levels of cariogenic bacteria at the perimeter of these materials. In this chapter, we discuss the dentin/adhesive bond, with a focus on the failure of current adhesives to consistently seal and adhere to the dentin. The concept of forming a resin-reinforced hybrid layer for improved adhesion is presented. The complex role of water in dentin/adhesive bonding is then described. Finally, mechanisms leading to mechanical property changes at the interface are discussed.

Poromechanics Parameters of Fluid-Saturated Chemically Active Fibrous Media Derived from a Micromechanical Approach

The authors have derived macroscale poromechanics parameters for chemically active saturated fibrous media by combining microstructure-based homogenization with Hills volume averaging. The stress-strain relationship of the dry fibrous media is first obtained by considering the fiber behavior. The constitutive relationships applicable to saturated media are then derived in the poromechanics framework using Hills Lemmas. The advantage of this approach is that the resultant continuum model assumes a form suited to study porous materials, while retaining the effect of discrete fiber deformation. As a result, the model is able to predict the influence of microscale phenomena such as fiber buckling on the overall behavior, and in particular, on the poromechanics constants. The significance of the approach is demonstrated using the effect of drainage and fiber nonlinearity on monotonic compressive stress-strain behavior. The model predictions conform to the experimental observations for articular cartilage. The method can potentially be extended to other porous materials such as bone, clays, foams, and concrete.