E.A.P. De Maeyer

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 a-tricalcium phosphate containing 17 wt% β-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 technique, 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 a-tricalcium phosphate hydrolysis, giving as a product calcium-deficient hydroxyapatite, while β-tricalcium phosphate did not participate in the reaction; (2) the extent of conversion of a-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 Ringers 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.

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.

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°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.

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 Al 3+ ions. These results provide a fundamental basis for the explanation, prediction, and control of cement properties as a function of glass characteristics.

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 ῡAS 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 ῡAS and a general modification of the band profile. The results can be correlated with the x-ray diffraction characteristics of the glass. A decrease in the Si-O-Si angle could be caused by a decrease in the distortions in the (arrangement of the) SiO4 tetrahedra; the tetrahedra as well as their arrangement can be distorted.

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

Calcium phosphate cements based on powders containing α-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.

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 (26) 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 (26) decreases. These results can be related to the decreasing Si-Si distance in the glass network with increasing modifier radius.

The growth of non-stoichiometric apatites using the constant composition method.

The kinetics of the crystal growth of calcium-deficient hydroxyapatites with different stoichiometry (Ca5-μ(HPO4)μ(PO4)3-μ(OH)1-μ) have been investigated at 37°C using the constant composition method. The growth was performed in solutions supersaturated only with respect to Ca5(PO4)3(OH) (HAp) by inoculating with well-characterized seed crystals. The stoichiometry of the grown apatites was consistent with values of 0≤μ≤0.185. The deviation μ from HAp stoichiometry of the growing apatite increased with increasing supersaturation degree (S). The constant composition method also provides relevant information about the solubility behaviour of the growing phase with a definite composition. From the decrease of the normalized growth rate j with decreasing S, an estimate could be made of the composition of the solution for which the growth ceases. The determined solubility product of the grown apatite (4.28×10-54 M9) was higher than the value obtained by the equilibration of the seed material. The results were interpreted on the basis of differences in crystal lattice perfection.