PALS probing of photopolymerization shrinkage in densely packed acrylate-type dental restorative composites.

BACKGROUND: Using positron annihilation lifetime spectroscopy (PALS), microstructural changes in commercial dental restorative composites under light-curing polymerization were identified as a modification in mixed positron/Ps trapping, where the decay of positronium (Ps; the bound state of positrons and electrons) is caused by free-volume holes mainly in the polymer matrix, and positron trapping is defined by interfacial free-volume holes in a mixed filler-polymer environment. In loosely packed composites with a filler content of <70-75%, this process was related to the conversion of Ps-to-positron trapping. OBJECTIVES: To disclose such peculiarities in densely packed composites using the example of he commercially available acrylate-based composite ESTA-3® (ESTA Ltd., Kiev, Ukraine), which boasts a polymerization volumetric shrinkage of only 1.5%. MATERIAL AND METHODS: ESTA­3® was used as a commercially available acrylate-based dental restorative composite. A fast-fast coincidence system of 230­ps resolution based on 2 photomultiplier tubes coupled to a BaF2 detector and ORTEC® electronics was used to register lifetime spectra in normal-measurement statistics. The raw PAL spectra were treated using x3-x2-CDA (coupling decomposition algorithm). RESULTS: The annihilation process in the densely packed dental restorative composites (DRCs), as exemplified by the commercially available acrylate-based composite ESTA­3®, is identified as mixed positron/ Ps trapping, where o-Ps decay is caused by free-volume holes in the polymer matrix and interfacial filler-polymer regions, and free positron annihilation is defined by free-volume holes between filler particles. The most adequate model-independent estimation of the polymerization volumetric shrinkage can be done using averaged positron annihilation lifetime. A meaningful description of the transformations in Psand positron-trapping sites under light curing can be developed on the basis of a semiempirical model exploring x3­x2­CDA. There is a strong monolithization of agglomerated filler nanoparticles in these composites, caused by the photo-induced disappearing of positron traps at the cost of Ps-decaying holes. CONCLUSIONS: Governing the polymerization void-evolution process in densely packed DRC ESTA­3® occurs mainly in the filler sub-system as positron-to-Ps trapping conversion, which is the reason for the low corresponding volumetric shrinkage.

Nanoscale Observation of Dehydration Process in PHEMA Hydrogel Structure.

One of the most important field of interest in respect to hydrogel materials is their capability to water storage. The problem mentioned above plays an important role regarding to diffusion of fluid media containing nanoparticles, what is very useful in biomedical applications, such as artificial polymeric implants, drug delivery systems or tissue engineering.In presented work, dehydration process in hydrogels used in ophthalmology as intraocular lenses was observed. Before measurements studied materials were immersed in deionized water and saline solution to obtain equilibrium swelling state. Studies of the dehydration process were carried out by use of gravimetric analysis, Fourier-Transform Infrared and Positron Annihilation Lifetime Spectroscopy. Obtained results revealed changes in hydrogen bonding structure and free volume holes induced by saline solution ingredients.

Light-Curing Volumetric Shrinkage in Dimethacrylate-Based Dental Composites by Nanoindentation and PAL Study.

Light-curing volumetric shrinkage in dimethacrylate-based dental resin composites Dipol® is examined through comprehensive kinetics research employing nanoindentation measurements and nanoscale atomic-deficient study with lifetime spectroscopy of annihilating positrons. Photopolymerization kinetics determined through nanoindentation testing is shown to be described via single-exponential relaxation function with character time constants reaching respectively 15.0 and 18.7 s for nanohardness and elastic modulus. Atomic-deficient characteristics of composites are extracted from positron lifetime spectra parameterized employing unconstrained x3-term fitting. The tested photopolymerization kinetics can be adequately reflected in time-dependent changes observed in average positron lifetime (with 17.9 s time constant) and fractional free volume of positronium traps (with 18.6 s time constant). This correlation proves that fragmentation of free-volume positronium-trapping sites accompanied by partial positronium-to-positron traps conversion determines the light-curing volumetric shrinkage in the studied composites.

Light-cured dimethacrylate dental restorative composites under a prism of annihilating positrons.

BACKGROUND: Breakthrough resolutions in current biopolymer engineering rely on reliable diagnostics of atomic-deficient spaces over the finest sub-nanometer length scales. One such diagnostic is positron annihilation lifetime spectroscopy, which probes space-time continuum relationships for the interaction between electrons and their antiparticle (positrons) in structural entities like free-volume defects, vacancies, vacancy-like clusters, interfacial voids and pores, etc. OBJECTIVES: This paper is intended to highlight the possibilities of positron annihilation lifetime spectroscopy as an informative instrumentation tool to parameterize free-volume evolution in light-cured dimethacrylate dental restorative composites exemplified by Charisma® (Heraeus Kulzer GmbH, Hanau, Germany) and Dipol® (Oksomat-AN Ltd, Kyiv, Ukraine). MATERIAL AND METHODS: The subjects of the study were the commercially available dimethacrylate-type dental restorative composites Charisma® and Dipol®. The analysis used a fast-fast coincidence system of 230 ps resolution based on 2 photomultiplier tubes coupled to BaF2 scintillator detectors and ORTEC® (ORTEC, Oak Ridge, USA) electronics to register lifetime spectra in normal-measurement statistics evolving ~1 million coincidences. RESULTS: The annihilation process in both composites is identified as mixed positron-Ps (positronium) trapping, where ortho-Ps decaying is caused entirely by free-volume holes in the polymer matrix, and the 2nd component is defined mainly by interfacial free-volume holes between filler nanoparticles and the surrounding polymer. The most appropriate model-independent estimation of photopolymerization volumetric shrinkage in dental restorative composites can be done using averaged positron annihilation lifetime. Partiallyconstrained x4-term analysis of lifetime spectra is less efficient, giving greater scatter of variance with an additional artifact of fixed shortest lifetime allowing unresolved mixing in the 2nd component. A meaningful phenomenological description of transformations in Ps and positron-trapping sites under light curing, which occurs more efficiently in Charisma® than in Dipol® nanocomposites, can be developed at the basis of a semi-empirical model exploring a x3-x2-coupling decomposition algorithm. CONCLUSIONS: A deep understanding of void-evolution processes in dimethacrylate dental composites employing positron annihilation lifetime spectroscopy makes it possible to diagnose, characterize and engineer novel biomaterials for advanced use in medical practice.

Free Volume Structure of Acrylic-Type Dental Nanocomposites Tested with Annihilating Positrons.

Positron annihilation spectroscopy in lifetime measuring mode exploring conventional fast-fast coincidence ORTEC system is employed to characterize free volume structure of commercially available acrylic-type dental restorative composite Charisma® (Heraeus Kulzer GmbH, Germany). The measured lifetime spectra for uncured and light-cured composites are reconstructed from unconstrained x3-term fitting and semi-empirical model exploring x3-x2-coupling decomposition algorithm. The governing channel of positron annihilation in the composites studied is ascribed to mixed positron-Ps trapping, where Ps decaying in the third component is caused entirely by input from free-volume holes in polymer matrix, while the second component is defined by free positron trapping in interfacial free-volume holes between filler nanoparticles and surrounded polymer matrix. Microstructure scenario of the photopolymerization shrinkage includes cross-linking of structural chains in polymer matrix followed by conversion of bound positron-electron (positronium) traps in positron-trapping interfacial free-volume voids in a vicinity of agglomerated filler nanoparticles.