Key Engineering Materials Vols. 309-311

Abstract: This paper presents equipment for the measurement of initial as well as final setting times of calcium phosphate cements containing alkali to achieve higher solubility. Until now, the selfsetting process of cements also if alkali is integrated has been tested by using the “standard test method for time of setting of hydraulic-cement paste by Gillmore needles” in accordance to ASTM C 266 – 99. This procedure needs high man power and, furthermore, the results have been markedly influenced by individual experiences that are incorporated in the criterion “without appreciable indentation”.

Abstract: The objective of the paper is to investigate the mechanical and the handling properties of a novel injectable bone void filler based on calcium silicate. The orthopaedic cement based on calcium silicate was compared to a calcium phosphate cement, Norian SRS from Syntes Stratec, with regard to the working (ejection through 14 G needle) and setting time (Gillmore needles), Young’s modulus and the flexural (ASTM F-394) and compressive (ISO 9917) strength after storage in phosphate buffer saline at body temperature for time points from 1h up to 16 weeks. The calcium silicate cement is composed of a calcium silicate powder (grain size below 20 µm) that is mixed with a liquid (water and CaCl2) into a paste using a spatula and a mixing cup. The water to cement ratio used was about 0.5. The calcium silicate had a working time of 15 minutes and a setting time of 17 minutes compared to 5 and 10 minutes respectively for the calcium phosphate cement. The compressive strength was considerably higher for the calcium silicate cement (>100 MPa) compared to the calcium phosphate cement (>40 MPa). Regarding the flexural strength the calcium silicate cement had high values for up to 1 week (> 40 MPa) but it decreased to 25 MPa after 16 weeks. The phosphate cement had a constant flexural strength of about 25 MPa. The results show that calcium silicate cement has the mechanical and handling potential to be used as high strength bone void filler.

Abstract: The objective of this paper is to investigate and compare the in vitro bioactivity of three injectable cements for orthopaedic applications. The cements were all based on chemically bonded ceramics technology; calcium phosphate (Norian SRS), and experimental versions of calcium silicate and calcium aluminate cements. The cements were mixed with their respective liquids and were after setting stored in phosphate buffered saline at 37 °C for time periods of 1h, 24 h, 7 days and 30 days. After storage the samples were analysed with scanning electron microscopy (SEM), thin film X-Ray diffraction (TF-XRD) and energy dispersive spectroscopy (EDS) for the presence of possible apatite on the sample surface. The SEM and EDX analyses showed that surface films containing Ca and P (along with the other atoms present in the materials) were formed on all materials. Thus reactions with the storage medium had occurred. The TF-XRD analysis confirmed the presence of apatite for the calcium phosphate cement and the calcium aluminate cement. On the calcium silicate cement most of the surface zone seemed to be amorphous with only broad peaks corresponding to apatite. Thus all the tested materials showed signs of in vitro bioactivity.

Abstract: Time resolved infrared spectroscopy (FTIR) and isothermal differential scanning calorimetry (DSC) were used for the first time to monitor the chemical reaction in a fast setting brushite forming calcium phosphate cement. It was found that the reaction percentage at a given time was dependent on temperature and not powder to liquid (P/L) ratio. Both methods showed that there was, within the temperature range investigated, a single autocatalytic like setting reaction within the cement paste. Final conversion of the reactants was found to be unaffected by temperature and P/L ratio.

Abstract: This study investigated the influence of the addition of various proteins to the liquid phase (albumin, fibrinogen and foetal bovine serum (FBS)) on the mechanical strength and setting time of a brushite forming calcium phosphate cement. Additions of 1wt% protein to the liquid phase led to a deterioration in compressive strength of the set cement by up to 50%. The setting time was not affected by adding albumin and FBS but was increased by 50% with admixtures containing fibrinogen. The conversion of the reactants, β-tricalcium phosphate and monocalcium phosphate, to brushite was found to be unaffected by addition of up to 10wt% proteins.

Abstract: Cements were prepared by mixing the calcium phosphate (β-TCP) with phosphoric acid solution (2.6M) and chitosan solution (2.5% in acetic acid solution) that was added in different proportions, ranging from 1 to 50% of total acid solution amount. Observations using SEM showed that the used of chitosan increased the interconnectivity of grains in the final cement, although the mechanical resistance to compression decreased from approximately 3 to 1 MPa. Probably the chitosan macromolecule is able to form a more interconnected net.

Abstract: In this study, we have shown that by incorporating pyrophosphoric acid into a brushite cement system, it is possible to produce a cement that exhibits adhesive tensile strengths with cortical bone, alumina, sintered hydroxyapatite and 316L stainless steel of 700 kPa. To our knowledge, this is the first report of a calcium phosphate cement formulation that exhibits such adhesive properties without the addition of an organic additive. The production of a bond between medical prostheses and bone may further widen the field of application of calcium phosphate cements, additionally the adhesive nature of the calcium phosphate cement may be a desirable ‘handling characteristic’ during reconstructive surgery.

Abstract: Bajpai et al. originally reported the formation of cements by the mixture of carboxylic acids and β-tricalcium phosphate (β-TCP). In the current study, we report and contrast four such cement systems formed from mixing citric, malic, 2-oxoglutaric or phosphoric acid with β-TCP. Cements formed from malic or 2-oxoglutaric appeared to contain crystalline phases and were determined to contain brushite, β-TCP and unreacted acid. In contrast, cement formed with citric acid was poorly crystalline, containing little evidence of brushite formation and was unstable in water and therefore does not appear to be a feasible cement system.

Abstract: This study was to develop an injectable biocompatible and porous calcium phosphate collagen composite cement scaffold by in situ setting. TTCP was prepared as main material of the CPC powder, and the collagen solution was added into the phosphoric acid directly to form the liquid phase. The injectable time (tI), setting time (tS) and setting temperature (TS), along with the PH value were recorded during the setting process. The compressive strength, morphology and porosity were tested. With the increase of collagen, this novel CPC get a tI of 5mins to 8mins, tS of 20mins to 30mins, compressive strength from 1.5MPa to 4MPa, and the porosity from 40% to 60%. This study gave a possibility to form a porous scaffold of collagen/CPC composite with the nature of injectability and setting in situ.

Abstract: In preliminary ageing test, the cement using only calcium phosphate glass as power phase cracked with 1 day in simulated body fluid because of high dissolution rate of the cement. We added 30 wt% of either β-TCP or HA to 70 wt% calcium phosphate glass as powder phase to control the dissolution rate of the cement and performed in vitro ageing test in simulated body fluid by dynamic protocol as well as static protocol to confirm the possibility of controlling. Adding either β-TCP or HA to the cement increases the setting time and decreases the compressive strength. In dynamic assay, the pH of extract is maintained over 7. However, pH decreased to around 5 in static assay. Therefore, weight loss by static protocol continuously increased for 14 days, while weight loss by dynamic protocol almost saturated. In XRD patterns of ageing cements, CaO peaks appeared. CaO peak was maximized most lately in dynamic assay of the cement adding HA and within 7 days, the cement adding HA showed higher weight loss. It is indicated that CaO formed in surface of the cement hinder the dissolution of the cement. In addition, compressive strength increased when the CaO peak was maximized.