Parag K. Shah

Role of filler and functional group conversion in the evolution of properties in polymeric dental restoratives

OBJECTIVES To examine effects of shrinkage and modulus on the dynamic development of shrinkage stress as a function of methacrylate conversion and filler loading in a model photocurable dimethacrylate-based resin with a silanized barium glass filler. METHODS BisGMA/TEGDMA samples with filler loading levels of 0-70wt% were evaluated. Irradiation times and intensities were varied to achieve a wide range of conversion. Shrinkage stress measurements were accompanied with real-time conversion monitoring, while shrinkage and modulus measurements were made at different static conversion points. RESULTS Shrinkage increased nearly linearly with respect to conversion, while for a given value of conversion, it decreased proportionally with increasing filler content. Modulus advanced in an exponential fashion with conversion and also increased incrementally with filler content; however, modulus values rose disproportionately rapidly for the highest filler loading. At either high or low filler loading levels, stress at limiting conversion, which was inversely proportional to the filler load, was high while at an intermediate filler content, a minimum in stress was observed due to the combined effects of filler based shrinkage reduction, restricted limiting conversion and only moderately enhanced modulus. The level of polymerization stress predicted from the conversion-indexed shrinkage and modulus measurements over-estimated the experimental stress states as modulus evolved due to system compliance that to some degree mimics the clinical situation presented by photocuring bonded composite restorations. Significance Measurement of monomer conversion provides a common basis by which different material properties can be rationally compared.

Ester-free thiol–ene dental restoratives—Part A: Resin development

OBJECTIVES To detail the development of ester-free thiol-ene dental resins with enhanced mechanical performance, limited potential for water uptake/leachables/degradation and low polymerization shrinkage stress. METHODS Thiol-terminated oligomers were prepared via a thiol-Michael reaction and a bulky tetra-allyl monomer containing urethane linkages was synthesized. The experimental oligomers and/or monomers were photopolymerized using visible light activation. Several thiol-ene formulations were investigated and their performance ranked by comparisons of the thermo-mechanical properties, polymerization shrinkage stress, water sorption/solubility, and reactivity with respect to a control comprising a conventional BisGMA/TEGDMA dental resin. RESULTS The ester-free thiol-ene formulations had significantly lower viscosities, water sorption and solubility than the BisGMA/TEGDMA control. Depending on the resin, the limiting functional conversions were equivalent to or greater than that of BisGMA/TEGDMA. At comparable conversions, lower shrinkage stress values were achieved by the thiol-ene systems. The polymerization shrinkage stress was dramatically reduced when the tetra-allyl monomer was used as the ene in ester-free thiol-ene mixtures. Although exhibiting lower Youngs modulus, flexural strength, and glass transition temperatures, the toughness values associated with thiol-ene resins were greater than that of the BisGMA/TEGDMA control. In addition, the thiol-ene polymerization resulted in highly uniform polymer networks as indicated by the narrow tan delta peak widths. SIGNIFICANCE Employing the developed thiol-ene resins in dental composites will reduce shrinkage stress and moisture absorption and form tougher materials. Furthermore, their low viscosities are expected to enable higher loadings of functionalized micro/nano-scale filler particles relevant for practical dental systems.

Evaluation of highly reactive mono-methacrylates as reactive diluents for BisGMA-based dental composites.

OBJECTIVES This study evaluates the performance of highly reactive novel monomethacrylates characterized by various secondary moieties as reactive diluent alternatives to TEGDMA in BisGMA filled dental resins. We hypothesize that these monomers improve material properties and kinetics over TEGDMA because of their unique polymerization behavior. METHODS The cure rates and final double bond conversion of the resins were measured using real-time FTIR spectroscopy. The glass transition temperature and storage modulus of the formed polymers were measured using dynamic mechanical analysis. Flexural modulus and flexural strength values were obtained using a three-point bending flexural test. RESULTS Polymerization kinetics and polymer mechanical properties were evaluated for the novel resin composites. It was observed that upon the use of novel monomethacrylates as reactive diluents, polymerization kinetics increased by up to 3-fold accompanied by increases in the extent of cure from 5% to 13% as compared to the BisGMA/TEGDMA control. Polymer composites formed from resins of BisGMA/novel monomethacrylates exhibited comparable T(g) values to the control, along with 27-37% reductions in the glass transition half widths indicating the formation of more homogeneous polymeric networks. The BisGMA/monomethacrylate formulations exhibited equivalent flexural modulus and flexural strength values relative to BisGMA/TEGDMA. SIGNIFICANCE Formulations containing novel monovinyl methacrylates exhibit dramatically increased curing rates while also exhibiting superior or at least comparable composite polymer mechanical properties. Thus, these types of materials are attractive for use as reactive diluent alternatives to TEGDMA in dental formulations.

Reduced shrinkage stress via photo-initiated copper(I)-catalyzed cycloaddition polymerizations of azide-alkyne resins

OBJECTIVES Polymerization shrinkage stress and factors involved in the stress development such as volumetric shrinkage and modulus were investigated in photo-CuAAC (photo-initiated copper(I)-catalyzed azide-alkyne cycloaddition) polymerization and compared with conventional BisGMA-based methacrylate polymerization for their use as alternative dental resins. METHODS Tri-functional alkyne and di-functional azide monomers were synthesized for photo-CuAAC polymerization. Conversion kinetics, stress development and polymerization shrinkage were determined with FTIR spectroscopy, tensometery, and with a linometer, respectively, for CuAAC and BisGMA-based monomer mixtures using a camphorquinone/amine visible light photoinitiator system. Thermo-mechanical properties for the cured polymer matrices were characterized by dynamic mechanical analysis and in three-point bending on a universal testing machine. Polymerization kinetics, polymerization shrinkage stress, dynamic volumetric shrinkage, glass transition temperature (Tg), flexural modulus, flexural strength, and flexural toughness were compared between the two different resin systems. RESULTS A glassy CuAAC polymer (Tg=62°C) exhibited 15-25% lower flexural modulus of 2.5±0.2GPa and flexural strength of 117±8MPa compared to BisGMA-based polymer (Tg=160°C) but showed considerably higher energy absorption around 7.1MJ×m-3 without fracture when strained to 11% via three-point bend compared to the flexural toughness of 2.7MJ×m-3 obtained from BisGMA-based polymer. In contrast to BisGMA-based polymers at 75% functional group conversion, the CuAAC polymerization developed approximately three times lower shrinkage stress with the potential to achieve quantitative conversion under ambient temperature photocuring conditions. Moreover, relatively equivalent dynamic volumetric shrinkage of around 6-7% was observed via both CuAAC and dimethacrylate polymerization, suggesting that the low shrinkage stress of CuAAC polymerization was due to delayed gelation along with slower rate of polymerization and the formation of a more compliant network structure. SIGNIFICANCE CuAAC crosslinked networks possessed high toughness and low polymerization shrinkage stress with quantitative conversion, which eliminated obstacles associated with BisGMA-based dental resins including limited conversion, unreacted extractable moieties, brittle failure, and high shrinkage stress.

Application of an addition–fragmentation-chain transfer monomer in di(meth)acrylate network formation to reduce polymerization shrinkage stress

A new addition-fragmentation chain transfer (AFT) capable moiety was incorporated into a dimethacrylate monomer that participated readily in network formation by copolymerizing with multifunctional methacrylates or acrylates. The process of AFT occurred simultaneously with photopolymerization of the AFT monomer (AFM) and other (meth)acrylate monomers leading to polymer stress relaxation via network reconfiguration. At low loading levels of the AFM, a significant reduction in shrinkage stress, especially for acrylate monomers, was observed with nominal effects on conversion. At higher loading levels of the AFM, the photopolymerization reaction kinetics and final double bond conversion were significantly lowered along with a delay in the gel-point conversion. Electron paramagnetic resonance studies during polymerization revealed the presence of a distinct radical species that was present in proportional quantities to the AFM content in the system. The lifetime and the character of the persistent radicals were altered due to the presence of the distinctive radical, in turn affecting the polymerization kinetics. With polymerization conducted at higher irradiance, the differential conversion between the control resin and samples with moderate AFM content was minimal, especially for the methacrylate-based formulations.

Simultaneous measurement of fluorescence, conversion and physical/mechanical properties for monitoring bulk and localized photopolymerization reactions in heterogeneous systems

An FT-NIR spectrometer, rheometer and fluorescence spectrophotometer were coupled for the real-time monitoring of polymerization reactions, allowing the simultaneous tracking of polymerization kinetics, storage modulus as well as fluorescence. In this study, a methacrylate functionalized dansyl chromophore (DANSMA) was synthesized and two different nanogels were made from urethane dimethacrylate and isobornyl methacrylate. Two series of resin formulations were prepared using the DANSMA probe, ethoxylated bisphenol A dimethacrylate as the matrix monomer, Irgacure® 651 as the initiator and the dispersed, monomer-swollen nanogels to give clear UV-curable resins. Placement of the fluorescent probe either throughout the resin or linked into the nanogel before its dispersion in the matrix provides a tool to study how the nanogel structure affects local network development by means of fluorescence from the DANSMA probe. We demonstrate the potential of this new technique using a composite as the two phase system (resin and polymerizable nanogel) including a dansyl derivative as a polymerizable probe to follow the reactions that are taking places in both phases.

Evaporation of low-volatility components in polymeric dental resins.

OBJECTIVES This study provides measurement of the volatility of selected photoinitiators and monomers used in dental adhesive resins. A detailed determination of the spatial and temporal character of camphorquinone (CQ) volatilization with respect to air flow conditions as well as media viscosity is assessed to gauge the effect of evaporative loss on the photopolymerization process and the photopolymers formed. METHODS Vapor pressures of materials are measured by thermogravimetric analysis. A quantitative model assuming one-dimensional Fickian diffusion with surface evaporation is presented and compared with measured photoinitiator volatilization from viscous and non-viscous resin samples, obtained by spectrophotometry and confocal microscopy. Model resins are prepared and subject to airthinning followed by photocuring, monitored in real-time by Fourier transform infrared spectrometry. RESULTS Vapor pressure measurements of the individual components of the adhesive resin span nearly four orders of magnitude, with the photoinitiator CQ near the middle (0.6Pa) and the monomer HEMA at the upper end (10Pa). We see depth-averaged CQ loss from non-viscous open films, while depthresolved measurements of viscous droplets show strong surface-localized CQ depletion. Good agreement is observed between measurements and the model. Finally, air-thinning of samples prepared with more-volatile photoinitiator and monomer is shown to cause longer induction times, slower early-stage polymerization rates and lower late-stage degree of conversion. SIGNIFICANCE Widely used compounds with vapor pressures as low as 0.6Pa (0.001Torr) undergo significant volatilization from samples ventilated under conditions generally representative to clinically used air-thinning procedures, with the potential to adversely affect the photopolymerization of both viscous and non-viscous resins. The inverse relationship between air-thinning and adhesive bond strength, observed elsewhere, may be partially caused by this same effect.