Key Engineering Materials Vols. 309-311

Abstract: The feasibility of processing glass-ceramics using the layer manufacturing technique, selective laser sintering (SLS), to produce parts with suitable biological and mechanical properties for use in bone replacement applications, has been investigated. Glass-ceramics derived from glasses based on several different systems have been considered. Initial experiments using an apatite-mullite glass-ceramic (4.5SiO2⋅3Al203⋅1.6P2O5⋅3CaO⋅2CaF2) demonstrated the ability to process glass-ceramic materials using this technique, creating parts with a strength similar to that of cancellous bone, and a porous structure that was shown in vivo to be suitable for the ingrowth of bone. Concerns over the inability of the apatite-mullite material to form an apatite layer on its surface when soaked in a simulated body fluid (SBF) has led to the development of Al2O3-free glasses based on the systems (50-x)CaO⋅45SiO2⋅5P2O5⋅xCaF2 and (48-x)CaO⋅45SiO2⋅5P2O5⋅2CaF2⋅xNa2O. These materials have demonstrated good in vitro bioactivity, and therefore have good potential as candidates for processing by an indirect SLS method for the production of custom-made bone implants.

Abstract: Novel fluorcanasite based glass-ceramics were produced by controlled two stage heattreatment of as-cast glasses. Castability of parent glasses was determined using a graduated spiral cast piece. Fluorcanasite glasses were also cast to form complex shapes using the lost wax casting technique. Gypsum and phosphate bonded investments were used to investigate their effect on the casting process, cast surface crystallinity and biocompatibility. The stoichiometric composition had the greatest castability but the other two modified compositions also had good castability. X-ray diffraction showed similar bulk crystallisation for each glass irrespective of the investment material. However, some differences in surface crystallisation in the presence of different investment materials were detected. Discs cast using gypsum bonded investment showed greater in vitro biocompatibility than equivalent discs cast using phosphate bonded investment under the conditions used. Gypsum and phosphate bonded investments could both be successfully used for the lost wax casting of these novel fluorcanasite glasses.

Abstract: Self-setting paste model in bioactive glass systems was investigated. Particulate glasses based on the systems CaO-SiO2-P2O5 and Na2O-CaO-SiO2 were combined with sodium phosphate solution to constitute paste models. Setting behavior of these pastes, i.e., workability and setting within 30 min were obtained by controlled composition-mass conditions. Specifically, it was found that the setting behavior could be controlled by glass compositions as well as mixing ratios of solids and solutions. These suggest new concept of bioactive cement for various biomedical applications.

Abstract: This work reports the structure of two glass ceramics prepared in the calcium phosphate system, MK5B and MT13B, using 31P MAS-NMR technique. The results obtained showed that the network of MK5B consisted mainly of Q1 and Q2 groups. Besides these two groups, MT13B material also present Q3 units. The Qn groups detected in both glass ceramics seem to be correlated to the crystalline phases present in their microstructure.

Abstract: Strontium is one of the most common substituents in apatite crystals. The presence and behavior of Sr in apatite-group phases are of considerable significance in biology. The present paper investigates the substitution of strontium for calcium in a glass-ceramic of the following composition 4.5SiO23Al2O31.5P2O54CaO1CaF2. The glasses were characterized using Differential Thermal Analysis (DTA), X-ray powder diffraction (XRD), neutron diffraction (ND) and 19F Resonance Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR). The all calcium glass crystallized to calcium fluorapatite (Ca5(PO4)3F). Substituting strontium partially for calcium resulted in the formation of a mixed strontium/calcium fluorapatites. In contrast complete substitution resulted in the formation of strontium fluorapatite. MAS-NMR showed the the F to be present as F-Ca(3) representing a fluoride ion surrounded by three Ca2+ ions in the all calcium glass and was present as F-Sr(3) in the all strontium glass. In the mixed glasses fluorine was present as FCa( 3), F-Ca(2)Sr, F-CaSr(2) and F-Sr(3). Ca had a higher tendency to occupy the F-M(3) sites than Sr which may reflect the higher charge to size ratio of Ca2+ relative to Sr2+ and its greater affinity for F- ions.

Abstract: Apatite-mullite glass-ceramics have been developed based on SiO2-Al2O3-P2O5-CaOCaF2 glasses. The glasses crystallise to form fluorapatite (FAP) and mullite with an appropriate heat treatment. The crystallisation mechanism has been thought to occur via a prior amorphous phase separation. The aim of this study was to carry out real time neutron diffraction of apatite-mullite glass-ceramics in order to develop an understanding of the crystal growth and crystal dissolution phenomena in the temperature regime between 550 and 1200oC. The results show that during the initial stages of fluorapatite crystallisation pronounced line broadening was observed indicating crystallisation on a nanoscale. Mullite starts to crystallise once there is insufficient charge balancing cations in the glass to maintain aluminium in a four fold coordination state. As a result of this work it is suggested that the mechanism of crystal growth of FAP is thought to involve the dissolution of smaller FAP crystals during the crystal growth temperature followed by re-crystallisation of FAP on the remaining larger crystallites during cooling.

Abstract: Bioactive glasses have attracted considerable interest in recent years. In this work, Differential Thermal Analysis (DTA) measurements were performed on bulk and powdered samples of the SiO2-Na2O-CaO-P2O5 glass system, in order to study the particle size effect on the crystal growth and nucleation process. A shift of the crystallization peak to lower temperatures and deconvolution of a slightly asymmetric crystallization peak into two separate peaks were observed with decreasing particle size. The bioactive behavior -through the process of immersion SBF- of the specific glass is studied as a function of particle size. A better bioactive response was observed increasing particle size until a specific size, further increase leading in no further improvement in the bioactive behavior.

Abstract: CaO-SiO2 gels for bioactive organic-inorganic composites were prepared from tetraethoxysilane (TEOS) and calcium nitrate tetrahydrate (Ca(NO3)2⋅4H2O) by a sol-gel method with the addition of polyethylene glycol (PEG) and methacryloxypropyltrimethoxysilane (MPS). The effects of PEG and MPS on morphology and bioactivity of the gel were investigated. The samples with the nominal compositions of Ca(NO3)2:TEOS:MPS = 30:70:0 and 30:63:7 (in molar ratio) were prepared with or without coexistence of PEG at a molar ratio of (TEOS+MPS):PEG = 70:0.16. Spherical powders were obtained regardless of the addition of MPS after removal of PEG by washing, whereas the samples prepared without PEG gave crack-free bulk bodies. Incorporation of MPS was confirmed form the results of Fourier transform infrared spectroscopy (FT-IR). All the samples, regardless of addition of PEG and MPS, formed apatite on their surfaces in simulated body fluid (SBF), when washing time was 3 h during the preparation. These results show that the bioactive spherical powder of CaO-SiO2 gel modified with MPS can be obtained by the present method. It is expected to induce the increase of the chemical bonding with surrounding organic matrix when it was used as fillers for composite materials.

Abstract: The purpose of this study is to investigate the crystallization behavior and in-vitro bioactivity character of glass ceramics having 3:7 weight ratio of flourapatite (Ca5(PO4)3F) to potassium mica (K2Mg3AlSi3O10F2) as a function of titania addition, and compare the morphology of hydroxycarbonateapatite (HCA) layer formation depending on titania addition on ceramic composition. It is observed from microstructural investigations that there is no morphology change occurred on precipitated HCA layer depending on nucleating agent in glass-ceramics. TF-XRD analysis indicates that after precipitation of initial particulates, crystallization proceeds and crystallization of precipitated HCA phase increases by increasing the time. It is observed that Ca, P ion variation in solution has two stage in terms of precipitation’ first stage represents formation of amorphous HCA and the second stage is related with crystallization. FTIR analysis strongly supports TF-XRD analysis as well.

Abstract: In this study; in-vitro bioactivity characterization of machinable glass-ceramics having 85 wt% sodium mica (NaMg3AlSi3O10F2) and 15 wt% fluoroapatite has been carried out. Two different heat treatment procedures are applied to the machinable glass-ceramics. The first one is nucleation at 610°C for 2 hours and crystallization at 1000°C for 3 hours and the second is nucleation at 610°C for 2 hours and crystallization at 1000°C for 4 hours. It is observed that increasing the crystallization time to 4 hours resulted in the increasing the formation of hydroxyapatite layer on surface. According to the microstructural investigations, the morphology of the precipitated crystals are different. In addition, the speed of the precipitation of hydroxyapatite is higher in glass-ceramic B than A. Thin film XRD analysis supports these results.