Addition of CaF2 to a silicate bioactive glass favours formation of fluorapatite, which is less soluble in acidic environment than hydroxyapatite. However, excess CaF2 in the glass is problematic, owing to the formation of crystalline calcium fluoride rather than fluorapatite on immersion. In this paper we investigate chloride as an alternative to fluoride in bioactive silicate glasses and in particular their bioactivity for the first time. Meltderived bioactive glasses based on SiO2-P2O5-CaO-CaCl2 with varying CaCl2 contents were synthesised and characterised by DSC. Chemical analysis of the chloride content was performed by using an ion selective electrode. Glass density was determined using Helium Pycnometry. The glass bioactivity was investigated in Tris buffer. Ion release measurements were carried out by using ICP-OES. The chemical analysis results indicated that the majority of the chloride is retained in the Q2 type silicate glasses during synthesis. Tg and glass density reduced with increasing CaCl2 content. Apatite-like phase formation was confirmed by FITR, XRD and 31P MAS-NMR. The results of the in vitro studies demonstrated that the chloride containing bioactive glasses are highly degradable and form apatite-like phase within three hours in Tris buffer and, therefore, are certainly suitable for use in remineralising toothpastes. The dissolution rate of the glass was found to increase with CaCl2 content. Faster dissolving bioactive glasses may be attractive for more resorbable bone grafts and scaffolds.

Apatite glass‐ceramics are attractive for medical and dental applications, and fluorapatite glass‐ceramics based on aluminosilicate glasses have been extensively studied. This study is the first study of chlorapatite glass‐ceramics based on calcium chloride‐containing Q2 bioactive phosphosilicate glasses. The crystallization behavior of oxychloride glasses is examined and compared with mixed oxychloride/fluoride and oxyfluoride glasses. The glass transition temperature decreased for all three series with increasing halogen content. On increasing the halogen content, there was an increasing tendency of the glasses to crystallize. The halogen‐free glass surface crystallized to pseudowollastonite and an apatite. On incorporating a halide, the glasses exhibited largely bulk crystallization to a haloapatite. In the case of chloride, the glasses crystallized to chlorapatite. This is the first time to our knowledge that chlorapatite has been shown to crystallize from a glass. Chlorapatite is very attractive for medical applications because it converts to hydroxyapatite the mineral phase of tooth and bone on immersion in water.

Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl. The CaCl has been added to the calcium metasilicate composition (CaO·SiO). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl has been successfully incorporated into these silicate glasses without the occurrence of crystallization. Si MAS-NMR spectra showed the silicon being present mainly as a Q silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl content, the T reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl content. However, both linear regressions revealed a breakpoint at a CaCl content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl crystallized to wollastonite, whilst the compositions with CaCl content equal to or greater than 19.2 mol% are thought to crystallize to CaCl. In practice, the crystallization of CaCl could not occur until the crystallization temperature fell below the melting point of CaCl. The implications of the results along with the high chloride retention are discussed.

There are numerous over-the-counter (OTC) and professionally applied (in-office) products and techniques currently available for the treatment of dentine hypersensitivity (DH), but more recently, the use of bioactive glasses in toothpaste formulations have been advocated as a possible solution to managing DH. Aim. The aim of the present study, therefore, was to compare several bioactive glass formulations to investigate their effectiveness in an established in vitro model. Materials and Methods. A 45S5 glass was synthesized in the laboratory together with several other glass formulations: (1) a mixed glass (fluoride and chloride), (2) BioMinF, (3) a chloride glass, and (4) an amorphous chloride glass. The glass powders were formulated into five different toothpaste formulations. Dentine discs were sectioned from extracted human teeth and prepared for the investigation by removing the cutting debris (smear layer) following sectioning using a 6% citric acid solution for 2 minutes. Each disc was halved to provide test and control halves for comparison following the brushing of the five toothpaste formulations onto the test halves for each toothpaste group. Following the toothpaste application, the test discs were immersed in either artificial saliva or exposed to an acid challenge. Results. The dentine samples were analyzed using scanning electron microscopy (SEM), and observation of the SEM images indicated that there was good surface coverage following artificial saliva immersion. Furthermore, although the acid challenge removed the hydroxyapatite layer on the dentine surface for most of the samples, except for the amorphous chloride glass, there was evidence of tubular occlusion in the dentine tubules. Conclusions. The conclusions from the study would suggest that the inclusion of bioactive glass into a toothpaste formulation may be an effective approach to treat DH.

Oxyhalide-containing silicate glasses have been receiving increasing attention in recent years due to their extensive medical and dental applications. This manuscript reports the first detailed structural investigation using MD simulations in the context of chloride- and mixed-fluoride/chloride-containing phospho-silicate bioactive glasses. It is shown that adding fluoride, chloride, and mixed fluoride and chloride has not altered the Q silicate distribution and phosphorus speciation significantly in all of the glasses investigated. The Q silicon species is the predominant species with smaller and nearly equal proportions of Q and Q species, whereas phosphorus is largely present as orthophosphate Q units. No Si-F/Cl and P-F/Cl bonds have been observed at room temperature. Both F and Cl anions are present as F-Ca(n) and Cl-Ca(n). MD simulations also indicate opposite effects of fluoride and chloride on the crystallization ability of the glasses. The environment of Cl in chloride-containing glass series is quite different from the chlorapatite and CaCl crystals, and a significant structural reorganization is required to observe the appearance of the crystal nuclei. Instead, the environment of fluoride ions in the glasses is quite similar to that present in the FAP and CaF crystals and thus F-containing glasses manifest a high crystallization tendency. Moreover, in the mixed-fluoride/chloride-containing glasses, fluorine tends to surround phosphate, whereas chloride moves toward the silicate network. Finally, it was observed that a good correlation exists between the glass transition temperature and the overall strength of the glass network quantified by the F factor.

No abstract

The addition of chlorine into a bioactive glass composition is expected to reduce its abrasiveness and increase its bioactivity, which is important for dental applications such as toothpastes. There is a lack of information and understanding regarding the structural role of chlorine in chlorine-containing bioactive silicate glasses. This has prompted classical core-shell model molecular dynamics simulations of (50 - x/2)CaO-(50 - x/2)SiO-xCaCl glasses to be performed, where x ranges from x = 0.0 to 43.1 mol % CaCl. These ternary glasses are advantageous for a fundamental study because they do not have additional network formers (e.g., phosphorus pentoxide) or modifiers (e.g., sodium) typically found in bioactive glass compositions. The (50 - x/2)CaO-(50 - x/2)SiO-xCaCl glasses were seen to become phase-separated around the x = 16.1 mol % CaCl composition, and chlorine predominantly coordinated with calcium. These findings provide a solid foundation for further computational modeling work on more complex chlorine-containing bioactive glass compositions.

Recently, the porous bioactive glasses have attracted a lot of attention for use as scaffolds for tissue engineering bone, such glasses include the high phosphate, strontium containing glass (Stronbone P TM). However, the previous studies suggest that strontium can have a detrimental effect on the ability of apatite-like phase formation of the glass. The previously studied high phosphate all Sr glass showed an unidentified phase rather than an apatite-like phase upon immersion. Octa-calcium phosphate (OCP) is believed to be a precursor phase to apatite, however octastrontium phosphate does not exist. Fluoride is known to knock out the OCP formation and promotes fluorapatite formation. This work presents the incorporation of a small amount of fluoride into calcium/strontium bioactive glasses. Differential 2 scanning calorimetry was used to estimate the glass thermal properties. All of the studied glass compositions were subjected to bioactivity studies in Tris buffer (pH=7.4) for up to 21 days. The initial glasses and the resultant precipitates were analysed using fourier transform infra red spectroscopy, X-ray diffraction and magic angle spinning-nuclear magnetic resonance. The findings showed that all the fluoride containing glasses were amorphous and there was a marked increase in the rate of apatite formation in vitro compared to the equivalent fluoride free glasses, particularly for the all strontium containing glass. This indicates that the presence of fluoride affects the pathway of apatite formation, forming fluorapatite directly instead of via the transformation from OCP to hydroxyapatite. Therefore, fluoride may have potential future clinical applications as an additive to increase apatite formation.