The Ca/P range of nanoapatitic calcium phosphate cements.

Nanoapatites are apatites consisting of nanometer size crystals. The commercial calcium phosphate cements set by the precipitation of nanoapatitic calcium phosphates in the range 1.5 < or = Ca/P < 1.8. In this study it is shown that a continuum of nanoapatites can precipitate in the range 0.8 < Ca/P< or = 1.5. In order to be formed these nanoapatites need to incorporate K+ ions. In addition they can incorporate some Na+ ions. Upon immersion in aqueous solutions these nanoapatites loose phosphate, K+ and Na+ so that in an open system they are transformed into calcium deficient hydroxyapatite Ca9(HPO4)(PO4)5OH within about 2 months.

Infrared spectrometric study of acid-degradable glasses.

The composition of glasses used in glass-ionomer cements affects their leaching behavior and hence the properties of the cement. The aim of this study was to correlate the composition and leaching behavior of these glasses with their infrared absorption characteristics. The wavenumber of the absorption band of the Si-O asymmetric stretching vibration shifts to a higher value with decreasing content of mono- and bivalent cations in the glass. This effect can be ascribed to the influence of these extraneous ions on the glass network order and connectivity. Preferential leaching of these ions induces an increase of asymmetric stretching vibration and a general modification of the band profile. The results can be correlated with the x-ray diffraction characteristics of the glass.

X-ray diffraction study of acid-degradable glasses.

The composition of the degradable glasses used in commercial dental glass-ionomer cements determines their leaching behavior and hence the properties of the cement. The objective of the present study was to assess if the composition and leaching in acetic acid solutions are reflected in the x-ray diffraction characteristics of these glasses. The position (2theta) of the maximum of the first sharp diffraction peak shifts to higher diffraction angles with increasing number and ionic radius of mono- and bivalent cations in the glass. Upon acid-leaching, these ions are preferentially leached out, so that (2theta) decreases. These results can be related to the decreasing Si-Si distance in the glass network with increasing modifier radius.

X-ray diffractometric determination of crystalline phase content in bioactive glasses.

A rapid routine determination of the content of crystalline CaF(2) and Al(2)O(3) inclusions in bioactive glass ceramics is performed using X-ray diffractometry with a standard addition technique. Multiple ratio analysis, even using peaks with different broadenings, indicates that differences in crystallite properties (e.g., crystal imperfection, particle size and morphology, preferred orientation) between the unknown sample and standard do not bias the result. In this respect, an exact match between their crystallographic integrities does not seem to be required for a reliable estimation of the crystalline content with a relative standard deviation of 7%.

Fluoride release from glass ionomer activated with fluoride solutions.

The mechanism of the fluoride release from glass-ionomer cements (GICs) is not yet completely understood, due to the complexity of these systems. The objective of the present study was to investigate the fluoride and alkali metal ion release from a relatively simple GIC formulation with fluoride- and alkali metal-free glass and activated with a NaF or KF solution. The set formulations were eluted during 168 days in water at 37 degrees C. The cumulative fluoride release was the result of an initial high release that ceased after some time and a prolonged but slow release, both of which increased with increasing fluoride concentrations in the activating solution, independently of the type of alkali metal. Maturation prior to elution decreased the fluoride and slowed the alkali metal release. The release of these ions was not (completely) correlated. The results suggest that the release process is due not only to a loss of relatively loosely bound fluoride in the cement matrix, but also to the release of fluoride which becomes strongly bound during the setting reaction and induces a long-term release.

Fluoride release of polyacid-modified composite resins with and without bonding agents.

OBJECTIVES: The aim of this study was to investigate the influence of the proprietary bonding agents Hytac OSB (OSB) (Espe), Prime&Bond 2.1 (PB) (Dentsply DeTrey) and Syntac Single Component (SSC) (Vivadent) on the fluoride release of the corresponding polyacid-modified composite resins Hytac (HTC), Dyract AP (DAP) and Compoglass F (CGF), respectively. METHODS: Ten cylindrical specimens (6mm diameter and 3mm thick) of each polyacid-modified composite were prepared according to the manufacturers' instructions: five with bonding agent applied and five without bonding agent as a control. The specimens were immersed individually in 10ml ultra-pure water at 37 degrees C immediately after light-curing of the polyacid-modified composite resins. Over 140 days, the water was regularly renewed and the fluoride concentration eluted during each period was determined with a combined fluoride ion selective electrode. RESULTS: The fluoride release decreases according to the sequence: CGF>DAP>HTC. The bonding agent significantly reduces the fluoride released by DAP and CGF, respectively, by a factor 2-3 and +/-1.4. For HTC, the bonding agent reduces the fluoride released initially by a factor of +/-2, but the difference between the fluoride release with and without bonding agent becomes insignificant after approximately 3 weeks. SIGNIFICANCE: It can be concluded that the use of bonding agent can significantly reduce fluoride release of polyacid-modified composite resins in the long-term, and especially in the short-term. The decrease in fluoride release might reduce the material's potential to prevent recurrent caries.

Effect of a neutral citrate solution on the fluoride release of resin-modified glass ionomer and polyacid-modified composite resin cements.

The effect of 0.01 mol/l citrate solution at pH = 7 on the fluoride release is compared for the resin-modified glass ionomer cements (RM-GIC) GC Lining LC, PhotacBond, Vitremer and Vitrebond and for the polyacid-modified composite resins (PAM-C) Variglass and Dyract by means of the six-month fluoride release profiles at 37 degrees C. The fluoride release of both RM-GIC and PAM-C increases in the neutral citrate solution as compared to water, which can be explained by the ability of citrate to complex metal ions and hence to degrade the glass as well as the polysalt matrix of the cement. Although RM-GIC release more fluoride than PAM-C in water as well as in citrate solution, the relative increase in fluoride release upon immersion in citrate solution is most pronounced for PAM-C. Whereas for the latter citrate affects both the short-term and long-term fluoride release, for RM-GIC only the long-term fluoride release is affected. This suggests that the action of citrate increases with decreasing importance of the polysalt formation in the hardening of the material. This could be explained on the basis of the difference in the chemical properties of the cement matrix.

Conversion of octacalcium phosphate in calcium phosphate cements.

This study investigated the in vitro conversion reaction in calcium phosphate cements (CPCs) containing octacalcium phosphate (OCP) as one of the reagents. OCP is known to be a precursor for apatite formation in vivo. The reaction products were characterized using infrared spectroscopy and X-ray diffraction. Although the conversion of OCP into hydroxyapatite is thermodynamically favorable, OCP only yields apatite formation in CPC provided it is combined with a highly soluble Ca(2+) and OH(-) releasing reaction partner. In this respect, tetracalcium phosphate is a promising compound. Adding small amounts of monocalcium phosphate monohydrate can stimulate the setting through intermediate brushite formation. The preparation method of OCP might drastically affect the performance of the cement. The reaction path of the setting of these CPC probably does not conform to the singular point principle described in the literature, and an in situ hydrolysis of OCP to apatite is conceivable. Simulation of apatite formation using OCP as the precursor and/or seed in CPC might be beneficial for some biomedical applications.

Effect of maturation on the fluoride release of resin-modified glass ionomer and polyacid-modified composite resin cements.

The effect of an early water contact on the fluoride release is studied for the resin-modified glass ionomer cements (RM-GIC) GC Lining LC, PhotacBond, Vitremer and Vitrebond and for the polyacid-modified composite resins (PAM-C) Variglass and Dyract. Six months fluoride release profiles were determined in regularly renewed water (37 degrees C), for the products directly after light curing and after 24 h maturation in a humid atmosphere (85% RH). ANOVA shows that both the short-term and the long-term fluoride release of a RM-GIC are influenced by this maturation. This indicates that direct water contact for this material should be avoided. For the RM-GIC a correlation is found between the initial fluoride release process and the long-term process. For the PAM-C materials, no differences in the fluoride release are found as a function of maturation, indicating that early water contact has no effect. The amounts of fluoride released by PAM-C are low compared to RM-GIC, which can affect their caries preventive potential. The results are explained on the basis of the setting reaction of both types of materials.

Fluoride release profiles of mature restorative glass ionomer cements after fluoride application.

This study investigates the fluoridation of four conventional glass ionomer cements (GIC) (ChemFil Superior encapsulated, Fuji Cap II, Ketac-Fil and Hi Dense) and three resin-modified GIC (RM-GIC) (Fuji II LC encapsulated, Photac-Fil and Vitremer). The fluoride release of matured restorative GIC was measured as a function of time, after four repeated fluoridations in a 2% NaF aqueous solution for 1 h. This release was corrected for the intrinsic release as determined with a control group. It was demonstrated that application of fluoride is capable of recharging GIC but the subsequent high fluoride release only lasts for one or a few days. Moreover, the fluoride release behaviour depends on the cement formulation. Comparable to the intrinsic release, the net fluoride release after fluoridation is composed of a short- and a long-term process, the former being predominant after fluoridation. The total amount of fluoride released according to the short-term process increases with consecutive fluoridations. This is especially pronounced for the RM-GIC, who exhibit a relatively slow release after fluoridation as compared to the conventional GIC. An explanation for these results is suggested on the basis of the physicochemistry of the setting reaction of the cements and of the fluoridation process.

Effect of temperature and immersion on the setting of some calcium phosphate cements.

Calcium phosphate cements based on powders containing alpha-Ca3(PO4)2 and aqueous solutions containing Na2HPO4 as accelerator were used to determine the effects of accelerator concentration, temperature and immersion on the setting time. Increases in accelerator concentration and temperature increased the rate of setting, but immersion had a retarding effect. These results were used to design a method whereby a syringe filled with cement paste can be kept ready for injection of the paste into the implantation site for a long time, whereas setting of the cement paste in the body takes place in a short time.

Stoichiometry of the leaching process of fluoride-containing aluminosilicate glass-ionomer glasses.

Dental glass-ionomer cements (GIC) set by an acid-base reaction between a polyalkenoic acid and an ion-leachable glass. The exact relationship between the glass composition and the setting and final properties of GIC is not yet fully elucidated. As part of a systematic study of this relationship, we studied the leaching stoichiometry of glasses used in commercial formulations to correlate the glass composition with its leaching properties. The leaching experiments were performed in acetic acid solutions at pH = 3.4 by means of a pH-stat method. After predetermined time intervals, the suspension was filtered and the filtrate was analyzed for the glass constituents. The usefulness of the pH-stat method for the determination of glass reactivity was corroborated. The deviation of the leaching stoichiometry with respect to the pure glass stoichiometry decreased with increasing relative content of mono- and bivalent glass network dwellers and modifiers. Indications were found that the latter can be leached out independently and preferentially, while the leaching of network dwellers is coupled with the aluminum release. The F content as well as the reactivity of the glass affect the amount of fluoride available for release from a set GIC. It could be concluded that the leaching stoichiometry of GIC glasses can be correlated with their absolute and relative composition.

Reactivity of fluoride-containing calcium aluminosilicate glasses used in dental glass-ionomer cements.

The glass component critically determines the properties of glass-ionomer cements (GIC). However, the exact relationship between the composition of the glass and these properties is not yet fully understood. To investigate this relationship, we studied the reactivity of glasses used in commercial GIC in acetic acid solutions, using a pH-stat method. Qualitative differences in the leaching behavior of these glasses can be explained by different pre-treatments. Acid-washing and silanization modify the surfaces of the glass particles, thus inducing a delay of the leaching process, whereas untreated glasses exhibit a fast initial leaching, but their acid reactivity slows very soon. Quantitative differences in acid reactivity can be correlated with the mean chemical composition of the glasses. In this respect, the leaching tends to increase with an increasing ratio of network-dwelling cations to Al3+ ions. These results provide a fundamental basis for the explanation, prediction, and control of cement properties as a function of glass characteristics.

Fluoride release process of (resin-modified) glass-ionomer cements versus (polyacid-modified) composite resins.

The fluoride release of conventional and resin-modified glass-ionomers is reviewed and compared to that of fluoride-releasing (polyacid-modified) composite resins. Each formulation displays a typical fluoride release profile. The cumulative amount of fluoride released is described by [F]c = [F](I)t/(t + t1/2) + beta square root t for glass ionomers whether resin-modified or not, whereas for composite resins this quantity is given by [F]c = [F](I)t/(t + t1/2) + alpha t. Both equations indicate that two kinetic processes are responsible for the fluoride release profiles. The kinetic parameters [F](I), t1/2, beta and alpha depend on the formulation. On the basis of the exchange characteristics for fluoride, an attempt is made to explain the mechanisms responsible for these fluoride release processes.

Setting reaction and hardening of an apatitic calcium phosphate cement.

The combination of self-setting and biocompatibility makes calcium phosphate cements potentially useful materials for a variety of dental applications. The objective of this study was to investigate the setting and hardening mechanisms of a cement-type reaction leading to the formation of calcium-deficient hydroxyapatite at low temperature. Reactants used were alpha-tricalcium phosphate containing 17 wt% beta-tricalcium phosphate, and 2 wt% of precipitated hydroxyapatite as solid phase and an aqueous solution 2.5 wt% of disodium hydrogen phosphate as liquid phase. The transformation of the mixture was stopped at selected times by a freeze-drying techniques, so that the cement properties at various stages could be studied by means of x-ray diffraction, infrared spectroscopy, and scanning electron microscopy. Also, the compressive strength of the cement was measured as a function of time. The results showed that: (1) the cement setting was the result of the alpha-tricalcium phosphate hydrolysis, giving as a product calcium-deficient hydroxyapatite, while beta-tricalcium phosphate did not participate in the reaction; (2) the extent of conversion of alpha-TCP was nearly 80% after 24 hr; (3) both the extent of conversion and the compressive strength increased initially linearly with time, subsequently reaching a saturation level, with a strong correlation observed between them, indicating that the microstructural changes taking place as the setting reaction proceeded were responsible for the mechanical behavior of the cement; and (4) the microstructure of the set cement consisted of clusters of big plates with radial or parallel orientations in a matrix of small plate-like crystals.

Kinetic study of the setting reaction of a calcium phosphate bone cement.

The setting reaction of a calcium phosphate bone cement consisting of a mixture of 63.2 wt % alpha-tertiary calcium phosphate (TCP)[alpha-Ca3(PO4)2], 27.7 wt % dicalcium phosphate (DCP) (CaHPO4), and 9.1 wt % of precipitated hydroxyapatite [(PHA) used as seed material] was investigated. The cement samples were prepared at a liquid-to-powder ratio of: L/P = 0.30 ml/g. Bi-distilled water was used as liquid solution. After mixing the powder and liquid, some samples were molded and aged in Ringer's solution at 37 degrees C. At fixed time intervals they were unmolded and then immediately frozen in liquid nitrogen at a temperature of TN = -196 degrees C, lyofilized, and examined by X-ray diffraction as powder samples. The compressive strength versus time was also measured in setting samples of this calcium phosphate bone cement. The crystal entanglement morphology was examined by scanning electron microscopy. The results showed that: 1) alpha-TCP reacted to a calcium-deficient hydroxyapatite (CDHA), Ca9(HPO4)(PO4)5O H, whereas DCP did not react significantly; 2) the reaction was nearly finished within 32 h, during which both the reaction percentage and the compressive strength increased versus time, with a strong correlation between them; and 3) the calcium phosphate bone cement showed in general a structure of groups of interconnected large plates distributed among agglomerations of small crystal plates arranged in very dense packings.

Fluoride release profiles of restorative glass ionomer formulations.

OBJECTIVES: The amounts of fluoride released by different glass ionomer formulations were compared on the basis of individual fluoride release profiles in order to derive the effect of the physical and chemical formulation on the fluoride release process. METHODS: The fluoride release profiles of each of five specimens of ten glass ionomer cements setting by an acid-base reaction were investigated. The profiles were obtained by determining the amount of fluoride released [F] after equilibrating the samples at 37 degrees C in distilled water for 140 d. The [[F],t]-profiles were compared with a Multivariate Data Analysis on the basis of a Principal Component Analysis. RESULTS: The Multivariate Data Analysis reveals that eight of the ten glass ionomers can be classified into four distinct groups. When the cumulative amount of fluoride released by each sample, [F]c, is calculated and fitted as a function of time, a regression analysis (r > 0.99) reveals that [F]c for all samples is most adequately represented by [F]c = ([F]l x t)/(t + t1/2) + beta x square root of t, indicating that two kinetic processes are responsible for the fluoride release profiles. SIGNIFICANCE: A comparison of the parameters of this equation shows that the physicochemical rationale for the classification of the glass ionomers conforms to differences in the kinetics of these processes which are determined by the qualitative and quantitative chemical composition as well as by the presentation (hand-mixed vs. capsules) of the glass ionomer. From the classification, it becomes apparent that different formulations can result in the same fluoride release profiles.

Spectrum decomposition through maximum likelihood common factor analysis of the EPR spectra of Na+ containing carbonated apatites dried at 400 degrees C.

X-irradiated carbonated apatites precipitated from aqueous solutions and dried at 400 degrees C until constant weight are investigated with electron paramagnetic resonance (EPR). The carbonate content of the samples studied ranges from 8.12 to 21.0 wt%. The observed multicomponent EPR spectra are analyzed with maximum likelihood common factor analysis (MLCFA), a multivariate statistical technique. Once the correct number of constituents are determined and the factor spectra estimated by MLCFA, a minimization procedure is performed in order to transform the abstract factor spectra linearly into an equal number of real EPR powder spectra. The spin hamiltonian parameters of the component spectra thus obtained are used to characterize and identify the different paramagnetic radicals. A comparison with values from the literature is made. A spectrum decomposition study of all the observed multicomponent EPR spectra in terms of the isolated constituents is successfully performed as a function of the carbonate content of the samples.