Improved PIXE analysis of micro- and trace elements in dental composites

Due to the interactions occurring at the solid-solid and solid-liquid interfaces of a tooth's filling, the mineral elements of the restorative composite may induce a complex response of the organism. To study such problems, sensitive surface trace element analysis is required. Particle-induced X-ray emission (PIXE) has a detection limit one order of magnitude lower than XRF and has been used for hard dental tissues, but not yet for dental composites. We evaluated the potential of PIXE in a study of ten types of composites used in restorative dentistry, some of them with two color shades each. The samples were prepared as described for XRF. The measurements were performed with 3 MeV protons from a van de Graaff tandem linear accelerator, using a hyper pure Ge detector and collecting the spectra for 1.5-4 hours. The spectra were processed with the program Leone. The proton route in the sample calculated with the Trim program (∼ 50-100 μm) exceeded the size of mineral particles (0.02-30 μm), thus granularity did not affect the analysis. The PIXE analysis detected Z ≥ 19 elements in all composites, and Z≥14 elements in only one low Z material. PIXE detected generally the same dominant elements, but many more trace elements than XRF. Thus both Charisma (Kulzer) and Pekafill (Bayer) contained Ba as the major element, but trace elements were Ni, Zn, In, in the first, and Fe, Cu, Zn, Sr, Ag in the second. In other glass- and ceramics-based materials we found: Ca, Zr, Ba, Yb and traces of Sr, In, and possibly Ti in Tetric Ceram and in Ariston (both from Vivadent); Ca, Zr, Ba, Hf, possibly Mn, and traces of Ni, Ho, Ti, Fe, Cr in Valux Plus (3M Dental); Sr, Ba (major), K, Fe, Mn (minor), and traces of Ni, Zn, In, in F2000 Compomer (3M Dental); Ba (major) and traces of Fe, Ni, Sr in Surefil (Dentsply). In quartz-based materials we detected: Si, Ca, Ti, Fe and traces of K, Cl, Cr, Ni, Cu, Zn in Evicrol (Spofa); low and trace levels of Ca, Ti, Cr, Mn, Fe, Cu in Alphaplast (DGM) and Concise (3M Dental). Color shades were dependent on the ratio (Fe, Ni)/Cu/(Ti, Cr) in Evicrol; but they were composition-invariant in Tetric Ceram, Valux Plus and Surefil. Some traces were impurities (as Sr accompanying Ba and Ca); they may influence the properties of nanoparticles in the materials. The ability of PIXE for trace detection in dental composites was due both to better sensitivity and to careful analysis of spectra. However, spectral overlap caused a degree of uncertainty on some trace elements. Caution is necessary to avoid trace contamination of samples. The method could serve also in new materials development and in forensic expertise. (authors)