Jacques Margerit

PHYSICAL PROPERTIES AND SELF-SETTING MECHANISM OF CALCIUM PHOSPHATE CEMENTS FROM CALCIUM BIS-DIHYDROGENOPHOSPHATE MONOHYDRATE AND CALCIUM OXIDE

An apatitic calcium phosphate cement was developed from calcium bis-dihydro-genophosphate monohydrate (or monocalcium phosphate monohydrate, MCPM) and calcium oxide (CaO). The powder had a Ca/P molar ratio of 1.67, and the liquid was either pure water or 0.25 M–1 M sodium phosphate buffer, pH 7.4. The influence of the powder-to-liquid (P/L) ratio on the setting time and the mechanical strength were studied. The best results were obtained for the 1 M phosphate buffer with a P/L ratio of 1.53; the setting time was 7 min and the compressive strength was 25 MPa after 24 h and 33 MPa after 11 d. The mechanism and kinetics of the setting reaction were investigated by X-ray diffraction, differential scanning calorimetry, 31P magic angle spinning–nuclear magnetic resonance and infrared spectrometry. The setting reaction was found to be biphasic: in the first step, during the mixing time, MCPM reacted with CaO immediately to give calcium hydrogenophosphate dihydrate (or dicalcium phosphate dihydrate, DCPD) which, in the second step, reacted more slowly with the remaining CaO to give hydroxyapatite. The conversion of the starting materials to hydroxyapatite was complete within 24 h when the liquid was water, but was slower and incomplete with the phosphate buffers. Of the starting materials, 30% remained after 3 d.

Confocal Raman microscopic analysis of the zirconia/feldspathic ceramic interface

OBJECTIVES Esthetic demands and biocompatibility have prompted the development of all-ceramic dental crowns. Yttria tetragonal zirconia polycrystalline (Y-TZP) framework material has the best mechanical properties compared to other all-ceramic systems, but the interface is the weakest component of core veneered restorations. Confocal Raman microscopy possibilities are used to ensure the understanding of the zirconia-feldspathic ceramic relationship, which is not well known. METHODS Bilayered zirconia (Vita In-Ceram(®) YZ) veneer (Vita VM(®)9) blocks were manufactured. Raman analyses were performed using two protocols: (1) single spectra, line scans and images on a sectioned and polished specimen and (2) in depth line scans on unprepared specimen. Single spectra, images and line scans provide information about the crystalline phases, their distribution and the existence of a possible diffusion at the Y-TZP/VM(®)9 interface, respectively. The elemental distribution of zirconium (Zr) and silicon (Si) around this interface were investigated using energy dispersive X-ray spectroscopy (EDS). RESULTS Raman single spectra embodied a unique spectrum (crystalline) on Y-TZP and two spectra (crystalline and amorphous) on VM(®)9; these spectra were clearly distinguished. Raman line scans showed a series of transition spectra across the interface from VM(®)9 to Y-TZP. It emphasized an interdiffusion zone, which was estimated at a maximum of 2 microns, found on 2d Raman images and confirmed by EDS. The elemental distribution with EDS showed a mutual diffusion of Zr and Si and was mainly dominated by Si diffusion in Y-TZP. SIGNIFICANCE Confocal Raman microscopy highlights an interdiffusion zone at the zirconia-feldspathic ceramic interface. The elemental transition layer is estimated and is supported by EDS analysis as a coupling technique.

pH-metric study of the setting reaction of monocalcium phosphate monohydrate/calcium oxide-based cements.

Hydraulic calcium phosphate cements (CPCs) that are used as osseous substitutes, set by an acid–base reaction between an acid calcium phosphate and a basic calcium salt (often a phosphate). In order to gain a better understanding of the setting of the monocalcium phosphate monohydrate–calcium oxide cement that we developed and in the aim to improve its mechanical properties, the setting reaction was studied by pH-metry. The two methods described in the literature were used. In the first, cement samples were prepared then crushed after different storage periods at 37 °C, 100% RH. The powder was then immersed in pure water with stirring and the pH was measured after equilibration. In the second technique, the starting materials were poured into water while stirring and the pH were followed over time. The two methods gave different results. The first procedure provided information concerning the pH of the surrounding liquid following the partial dissolution of the cement components, rather than any information about pH changes during setting. The second method is more appropriate to follow the pH variations during setting. In this second procedure, the effects of different parameters such as crushing time, stirring rate, liquid-to-powder (L/P) ratio and temperature were investigated. These parameters may impact substantially on the shape and position of the pH=f(t) curves. One or three pH jumps were observed during the setting depending on the composition of the liquid phase. The time at which these pH jumps occurred depended on the pH of the liquid phase, the concentration of the buffer, the crushing of starting materials, the L/P ratio and the temperature. Good linear correlations were obtained (i) between the time of the pH jumps and the L/P ratio and the temperature and (ii) between the time of the first pH jump and the compressive strength and the final setting time of the cements prepared with different liquid phases. It may be assumed in view of these correlations that the results obtained in dilute solution may be extrapolated to the conditions of cement sample preparation and that the mechanical properties of the cement are directly related to the phenomena that occur at the first pH jump which corresponds to precipitation of dicalcium phosphate dihydrate.

Study of a hydraulic calcium phosphate cement for dental applications

Calcium phosphate-based cements (CPCs) have attracted much interest because of their good osteoconductivity for bone reconstruction. We obtained CPCs by mixing calcium bis-dihydrogenophosphate monohydrate (MCPM) and calcium oxide with water or sodium phosphate buffers (NaP) as liquid phase. Cement samples with different calcium-to-phosphate ratios (Ca/P), liquid-to-powder ratios (L/P) and liquid phases were analyzed by X-rays diffraction (XRD), pH-metry, extensometry and calorimetry. Antibacterial activity on two bacterial strains (Streptococcus mutans, Lactobacillus acidophilus) and a polycontaminated bacterial inoculum was also studied using the agar diffusion method. The best mechanical properties (≈25 MPa) corresponded to Ca/P ratios between 1.67 and 2.5, a 1 M sodium phosphate buffer pH 7, as liquid phase and a L/P ratio of 0.6 ml g-1. The final setting time increased with the Ca/P ratio. The setting expansion, around 1–2%, depended on the Ca/P and L/P ratios. The inner temperature of the cements rose to 45° during setting then decreased rapidly. The injectability was 100% up to 3.5 min and then decreased. It increased with increasing the L/P ratio but to the detriment of the compressive strength and setting time. XRD analysis indicated that the setting reaction led to a mixture of calcium hydroxide and calcium-deficient hydroxyapatite even for a Ca/P ratio of 1.67. Consequently, the pH of the surrounding fluids rose to 11.5–12 during their dissolution. Bacterial growth inhibition was only clearly observed for Ca/P≥2. This bioactive calcium phosphate cement can potentially be employed for pulp capping and cavity lining as classical calcium hydroxide-based cements, but it is not usable, in the present formulation, for root canal filling because of its short setting time.

Chemical characterization of in vivo aged zinc phosphate dental cements

The chemical composition of zinc phosphate dental cements aged in vivo was studied. Twenty-seven samples aged 2 to 43 years were investigated using X-ray diffraction, infrared spectroscopy, 31P nuclear magnetic resonance spectroscopy, thermogravimetric analysis and differential scanning calorimetry. Evidence for the presence of zinc oxide, amorphous zinc phosphate, water of hydration and crystalline zinc phosphate tetrahydrate was found. The latter was identified as hopeite; it was present in 92% of the cements studied. No correlation with time concerning either the chemical structure of the components or their relative amounts was found. Zinc phosphate dental cements show very good chemical stability on long-term use.

Confocal Raman microscopy and SEM/EDS investigations of the interface between the zirconia core and veneering ceramic: the influence of a liner and regeneration firing

The aim of this study was to evaluate the changes in the transition layer at the interface between yttria partial stabilized tetragonal zirconia polycrystalline (Y-TZP) core and veneering feldspathic ceramic (VITA VM®9), under different manufacturing methods. Confocal Raman microscopy and energy dispersive X-ray spectroscopy (EDS) analyses were carried out on tapered veneered cross sections of the interface. For some samples, an additional firing of the core was used, as the application of an optional liner material between the core and veneer. Single Raman spectra were distinguishable between Y-TZP and the veneering materials. VM®9 and liner spectra were broadly superimposable. No substantial differences appeared in their chemical elemental composition. 2D Raman images and EDS analysis emphasized changes in the interdiffusion thickness; the additional firing of the core decreased the interdiffusion zone, and the highest firing temperature of the liner increased the interdiffusion zone. These results, which will help us understand the changes in this transition layer, are discussed.

Chemical characterization of in vivo aged zinc polycarboxylate dental cements.

The chemical composition of zinc polycarboxylate dental cements aged in vivo was studied. Thirty samples aged from one to 17 years were investigated using X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and differential scanning calorimetry. Evidence for the presence of zinc oxide, amorphous zinc polycarboxylate and water of hydration was found. No correlation with age concerning either the chemical structure of the components or their relative amounts was found. Zinc polycarboxylate dental cements show very good chemical stability on long-term use.

Chemical and structural changes in zinc polycarboxylate cements after immersion in dilute organic acid solutions

The behaviour of zinc polycarboxylate cements in contact with dilute aqueous solutions of organic acids at concentrations close to those existing in buccal medium, was studied. The organic acids were acetic, citric, tartaric and lactic acids, at 0.01 M and 0.001 M. The elution of zinc and magnesium was 10–1000 times greater in acid than in pure water, and correlated with the concentrations and the dissociation constants, pK1, of the acids tested. In all cases, important water losses were observed. In the 0.01 M acids, the cement structure collapsed to form a viscous, compact and homogeneous layer on the cement surface. In this layer, the polymeric carboxylic chains were regenerated from the zinc and magnesium polycarboxylate cement. Comparison with pure water showed that even the smallest concentration of the weak acids greatly modified the cement behaviour. This could explain the well-known differences in erosion processes between theoretical erosion predicted by standard specification tests and the in vivo situation.