F. C. M. Driessens

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 mineral solubility of human tooth roots

Whole roots of molars that had never been exposed to the mouth were exposed to calcium and phosphate-containing buffer solutions with discrete values of pIOHA [i.e. -log(a10Ca2+ X a6PO4(3-) X a2OH-)] at various pH. From densitometric measurements on contact-microradiographs of transverse sections of the roots the rate of demineralization (Vdem) was calculated. Vdem changed non-linearly as a function of pIOHA and became zero at a pIOHA-value of 105.3 +/- 0.4; this is substantially lower than the corresponding value of 118 +/- 1 for enamel. Thus root mineral is more soluble than enamel mineral. The critical pH for root caries appears to be about 6.7, provided that the plaque fluid follows about the same pH-pIOHA- pathway as acidified saliva.

Evaluation of calcium phosphates and experimental calcium phosphate bone cements using osteogenic cultures

In this study, rat bone marrow cells (RBM) were used to evaluate two biodegradable calcium phosphate bone cements and bioactive calcium phosphate ceramics. The substances investigated were: two novel calcium phosphate cements, Biocement F and Biocement H, tricalcium phosphate (TCP), surface-modified alpha-tricalcium phosphate [TCP (s)] and a rapid resorbable calcium phosphate ceramic consisting of CaKPO(4) (sample code R5). RBM cells were cultured on disc-shaped test substrates for 14 days. The culture medium was changed daily and also examined for calcium, phosphate, and potassium concentrations. Specimens were evaluated using light microscopy, and morphometry of the cell-covered substrate surface, scanning electron microscopy, and energy dispersive X-ray analysis and morphometry of the cell-covered substrate surface. Areas of mineralization were identified by tetracyline labeling. Except for R 5, rat bone-marrow cells attached and grew on all substrate surfaces. Of the different calcium phosphate materials tested, TCP and TCP (s) facilitated osteoblast growth and extracellular matrix elaboration to the highest degree, followed by Biocements H and F. The inhibition of cell growth encountered with R 5 seems to be related to its high phosphate and potassium ion release.

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.

The Vulnerability of Unexposed Human Dental Roots to Demineralization

Crowns and roots of human molars, the roots from which had not been exposed to the oral environment, were exposed for 0, 3.5, 7, and 14 days to buffer solutions which were undersaturated or supersaturated with respect to hydroxyapatite. Densitometric measurements on contact-microradiograms of transverse sections of the crowns and of the cervical parts of the roots yielded plots of the mineral content as a function of the distance to the outer surface. From these plots, the rate of demineralization was calculated. It was found that the mineral of the roots dissolved even in buffer solutions which were supersaturated with respect to hydroxyapatite. Comparison of the results obtained from the crowns with those from the roots showed that the root hard tissues were more vulnerable to demineralization than was the dental enamel.

Characterization of Bone Cements

Properties of acrylic bone cements during and after curing were determined for three brands of bone cement. Curing time and consistency were chosen for the characterization of the handling and working behavior of these materials. The performance of bone cements after curing may be related amongst other things to the following properties: water resorption, solubility/disintegration, flexural modulus of elasticity, yield stress, proportional limit, flexural strength and impact strength. Methods to determine these handling and material properties are described. The influence of radiopacifying and antibiotic additives on these properties is evaluated as well as the influence of porosity on flexural strength and impact strength. The results indicate that considerable differences in the handling properties occur. The material properties of the three brands tested do not show marked differences. Radiopacifying and antibiotic additives appear to have a negative effect on material properties; the effect of porosity as it develops during curing under simulated clinical conditions is more pronounced.

In vivo behaviour of three calcium phosphate cements and a magnesium phosphate cement

Three types of calcium phosphate cements and one magnesium phosphate cement were implanted subcutaneously in rats under exclusion of direct cellular contact. Retrieval times were either 1, 2, 4 or 8 weeks. Before and after retrieval the compressive strength, the diametral tensile strength, the quantitative chemical composition, the qualitative phase composition, the FTIR spectrum and the microstructure were determined. The three calcium phosphate cements maintained their strength during implantation. The phase DCPD was completely transformed into a Na- and CO3-containing apatite, the phases DCP and CDHA only partially. It could not be ruled out that OCP is also transformed into a bone-mineral-like apatite to a certain extent. That this latter process occurs much faster during the turn-over of living bone, is probably due to the very small crystal size of the OCP particles in bone.

Production of calcium phosphate coatings on Ti6Al4V obtained by Nd:yttrium–aluminum–garnet laser cladding

Among the various techniques that have been investigated to produce Hydroxyapatite (HA) coatings in order to promote fixation and osteointegration of cementless prosthesis, the plasma spray (PS) technique is the most popular method commercially in use. PS presents some disadvantages such as the poor coating-to-substrate adhesion, low mechanical strength, and brittleness of the coating. In order to overcome the drawbacks of plasma spraying, an approach on how to bind HA to the Ti alloy will be introduced in this work, using a well-known technique in the metallurgical field: laser surface cladding. Different techniques were applied to characterize the coated samples, including x-ray diffraction, scanning electron microscopy, and energy dispersive x-ray analysis.

Biodegradation of four calcium phosphate ceramics;in vivo rates and tissue interactions

To prevent exposure of artificial tooth root implants, a resorbable root implant may be developed, that in time will resorb in a vertical direction at the same rate as the alveolar ridge does after the loss of the natural teeth. Implants of four calcium phosphates: rhenanite, β-tricalcium phosphate, hydroxylapatite and magnesium-whitlockite were measured duringin vivo resorption and their interactions with the surrounding tissues at experimental periods of 6 weeks and 3 months were investigated. It was shown that a sequence of progressive resorptionin vitro does not correlate with the resorption rates found in thisin vivo experiment.In vivo hydroxylapatite was found to be less resorbable than magnesium-whitlockite and rhenanite less resorbable than β-tricalcium phosphate. Tissue interactions showed that resorption of the calcium phosphates was positively related to the number of osteoclast-like cells and did not completely correlate with the resorption measurements insofar that most rhenanite implants showed a more reactive peri-implant with the largest number of osteoclast-like cells, strongly affecting the implant surface. In contrast, two rhenanite implants showed intimate contact with bone after initial resorption. Because of this divergent reaction with rhenanite, furtherin vivo investigation on this material is proposed.