Thermal behaviour and excess entropy of bioactive glasses and Zn-doped glasses

Bioactive glasses prepared in SiO₂–CaO–Na₂O and P₂O₅ system are used as biomaterials in orthopaedic and maxillofacial surgery. Zn presents high physiological interest. It enhances physiological effects of implanted biomaterials. In this work, the thermal characteristics (T _g, T _c and T _f) of pure bioactive glass elaborated with different amounts of CaO, Na₂O in pure glass and with different amounts of introduced Zn in glass (ranging from 0.1 to 10 in mass%), were studied. The excess entropy was calculated for different compounds. Glasses were prepared by the melting process. The thermal behaviour of obtained bioactive glasses was determined using differential thermal analysis. Therefore, the glass transition (T _g), the crystallization (T _c) and the melting temperatures (T _f) were revealed. Moreover, according to Dietzel formula, the thermal stability (TS) of the studied bioactive glasses has been calculated. The first results concerning the impact of different oxides, revealed a decrease of the TS, T _g, T _c and T _f when the SiO₂/CaO increases and revealed an increase of these thermal characteristics when the SiO₂/Na₂O and CaO/Na₂O ratios increase. Introducing Zn into the bioactive glasses induces a decrease of T _f and an increase of TS. Contrary to crystals, prepared glasses have entropy different to zero at T = 0 K and vary versus T _f. The excess entropy of pure glasses and Zn-doped glasses were calculated. The significant variations were registered.     

Thermal analysis of gel-derived bioactive phospho-silicate glasses

Thermal reactions of model phospho-silicate gels of simple composition has been studied. The investigations demonstrate that the kind of compounds introducing P₂O₅ into the gel silicate network, H₃PO₄, PO(OC₂H₅)₃, POCl₃ influence the course and temperature and the xerogel formation. The amount of interstitial water and xerogel porosity is dependent on the cations, amorphous structure modifiers (Ca, Na) used. Thermal analysis curves appear the convenient carriers of informations about the processes in gel pores and the formation of xerogel and glass. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structural characterization of bioactive glasses by solid state NMR

Nuclear magnetic resonance (NMR) spectroscopy offers an element-selective, inherently quantitative and experimentally very flexible approach for the structural elucidation of non-crystalline materials. The present review introduces the basic concepts of this technique, highlighting the use of advanced NMR methodology for characterizing short- and intermediate range order in bioactive glass systems. The current state of the literature in this field is summarized in a comprehensive manner. NMR can give clear-cut and quantitative answers about the extent of network polymerization, the spatial distribution of the network former and network modifier species, and the structural roles of Group III elements introduced into these networks. These results facilitate our understanding of the influence of bioglass compositions upon the dissolution kinetics and bioactivities of these glasses. A particular mission of this review is to highlight the utility of non-routine, more advanced experimentation, in the hope of their increased usage and circulation in future applications.

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The main six nuclear isotopes used in obtaining high-resolution magic-angle spinning NMR spectra for the structural characterization of bioactive glasses

     

Structural effects of phosphorus inclusion in bioactive silicate glasses

Molecular dynamics simulations of four bioactive silicate glasses containing between 0 (P0) and 12 (P12) mol % P2O5 have been carried out in order to elucidate the structural role of phosphorus in these materials. In particular, we have focused on structural features which can have a direct role in the bioactive mechanism of dissolution and bone bonding. The higher affinity of modifier Na and Ca cations for coordinating phosphate rather than silicate, together with the formation of P-O-Si linkages, lead to increasing repolymerization of the silicate network with increasing P2O5 content, which in principle would represent a negative effect of P inclusion on the glass bioactivity. However, this effect is counterbalanced by the concomitant increase in the amount of free orthophosphate groups, whose fast release is deemed to enhance the bioactivity. The strong affinity of the orthophosphates for calcium ions leads to a clear tendency toward separation of silicate-rich and phosphate-rich phases for the P12 composition. Although this could reduce the bioactivity in the case of P12, in general, the favorable balance between the effects mentioned above should result in a positive effect of partial Si --> P substitution on the glass bioactivity.     

Design and preparation of bioactive glasses with hierarchical pore networks

Hierarchically giant-, macro-, and meso-porous 3D bioactive glass scaffolds with good bone-forming bioactivity in vitro were synthesized by using a combination of sol-gel, double polymers templating, and rapid prototyping techniques.     

Excess entropy and thermal behavior of Cu- and Ti-doped bioactive glasses

Bioactive glasses belong to the ceramic family. They are good materials for implantation due to their excellent capacities to create an intimate bond with bones. Copper is known for its anti-inflammatory, antibacterial, and antifungal properties. Titanium is biocompatible and resistant to corrosion. These chemical elements can be introduced in bioactive glasses to provide a wide variety of uses and to enhance the physiological properties of implanted biomaterials. In this work, bioactive glasses doped with different contents of copper and titanium were synthesized by the melting method. The purpose is to study the effect of doping metal element on the thermal characteristics (T _g, T _c, and T _f). The results revealed that the increase of the content of copper and titanium in the glass matrix decreases the melting temperature and induces an increase of the thermal stability. The excess entropies of pure and doped glasses were calculated. Obtained results highlighted the decrease of the excess entropy with the increase of metal elements contents.     

Crystallization kinetics of bioactive glasses in the ZnO-Na2O-CaO-SiO2 system

The crystallization kinetics of Na(2)O.CaO.2SiO(2) (x = 0) and 0.68ZnO.Na(2)O.CaO.2SiO(2) (x = 0.68, where x is the ZnO stoichiometric coefficient in the glass formula) bioactive glasses have been studied using both nonisothermal and isothermal methods. The results obtained from isothermal XRPD analyses have showed that the first glass crystallizes into the isochemical Na(2)CaSi(2)O(6) phase, whereas the Na(2)ZnSiO(4) crystalline phase is obtained from the Zn-rich glass, in addition to Na(2)CaSi(2)O(6). The activation energy (Ea) for the crystallization of the Na(2)O.CaO.2SiO(2) glass is 193 +/- 10 and 203 +/- 5 kJ/mol from the isothermal in situ XRPD and nonisothermal DSC experiments, respectively. The Avrami exponent n determined from the isothermal method is 1 at low temperature (530 degrees C), and its value increases linearly with temperature increase up to 2 at 607 degrees C. For the crystallization of Na(2)CaSi(2)O(6) from the Zn-containing glass, higher values of both the crystallization temperature (667 and 661 degrees C) and Ea (223 +/- 10 and 211 +/- 5 kJ/mol) have been found from the isothermal and nonisothermal methods, respectively. The Na(2)ZnSiO(4) crystalline phase crystallizes at lower temperature with respect to Na(2)CaSi(2)O(6), and the Ea value is 266 +/- 20 and 245 +/- 15 kJ/mol from the isothermal and nonisothermal methods, respectively. The results of this work show that the addition of Zn favors the crystallization from the glass at lower temperature with respect to the Zn-free glass. In fact, it causes an increase of Ea for the Na diffusion process, determined using MD simulations, and consequently an overall increase of Ea for the crystallization process of Na(2)CaSi(2)O(6). Our results show good agreement between the Ea and n values obtained with the two different methods and confirm the reliability of the nonisothermal method applied to kinetic crystallization of glassy systems. This study allows the determination of the temperature stability field of the crystalline phases with the view of creating a different glass ceramic useful in the field of bioactive materials.     

Carbonate formation and decomposition on atomic oxygen precovered Au(111)

Experimental results supported by density functional theory calculations show carbonate formation and reaction on atomic oxygen precovered Au(111). Oxygen mixing is observed in temperature-programmed desorption measurements when a Au(111) precovered with 16O is exposed to isotopically labeled CO2 (C18O2). The presence of 16O18O is attributed to surface carbonate formation and decomposition at surface temperatures ranging from 77-400 K and initial oxygen coverages ranging from 0.18-2.1 ML. A reaction probability on the order of 10(-4) and an activation energy of -0.15+/- 0.08 eV are estimated for this reaction.     

Determination of avrami parameters of hydroxyapatite and β-wollastonite in bioactive phosphor—Silica glasses

The properties of biologically active glasses in the system SiO₂?P₂O₅?MgO?CaO were studied. Crystalline hydroxyapatite (HA) and β-wollastonite (β-W) were used after heat treatment (1100°C). The influence of the glass particle size (0.071–2.5 mm) and of glass powder (d ₅₀=15.1 μm) on the behaviour of the products during differential thermal analysis was followed. These analyses indicated that the β-W probably originates from surface nucleation, and HA from bulk nucleation. The differentiation was confirmed by calculation of the Avrami parameters (n) with the Pi-loyan-Borchardt analytical method. For HA and β-W, the calculated values ofn were 2.96 and 1.91. The surface-nucleated glasses exhibited predominant bidimensional crystal growth.     

Synthesis of hierarchically porous bioactive glasses using natural plants as template for bone tissue regeneration

A series of highly ordered hierarchically porous silica and bio-glasses materials with macropore size of 8?C1,000???m and mesopore size of 3.1?C5.6?nm have been synthesized using six plant based materials as templates. However, the as-obtained porous structure was reported for the first time with interconnected 3D macropore up to 1,000???m. The porous silica materials were used as the host for drug loading and release, which showed a good sustained delivery function. The as-synthesized bio-glasses materials indicated the highly bioactive capability in the bone regeneration. This method can be utilized to synthesize other multi-porous bioactive glasses using different plants as templates for bone tissue repairing.     

Thermal evolution of ladder-like silsesquioxanes during formation of black glasses

Heat capacity of single-crystal samples of five chalcogenides (LiInS₂, LiInSe₂, LiGaS₂, LiGaSe₂, and LiGaTe₂) was measured with DSC in a temperature range from 180 to 460 K. The data for LiInS₂ and LiInSe₂ were compared with the literature data and shown to agree with the results of adiabatic calorimetry (Gmelin and Hönle in Thermochimica Acta 269: 575–590, 1995) better than with other DSC data (Kühn et al. in Cryst Res Technol 22: 265–269, 1987). Besides, the high-temperature fitting polynomial for C _P(T) published about 30 years ago for LiInS₂ is wrong. LiGaS₂, LiGaSe₂, and LiGaTe₂ were measured for the first time.     

Elucidation of the structural role of fluorine in potentially bioactive glasses by experimental and computational investigation

Glasses belonging to the Na(2)O-CaO-P(2)O(5)-SiO(2) system and modified by CaF(2) substitution for CaO and Na(2)O alternatively, were synthesized and characterized experimentally and computationally. The results of molecular dynamics simulations show that fluorine is almost exclusively bonded to modifier cations (Ca and Na) with coordination number close to 4. A similar mean coordination number value is found in the crystal phases obtained by means of thermal treatment at fixed temperature. Addition of fluorine increases the polymerization of silicate tetrahedra by removing modifiers from the siliceous matrix. No appreciable amount of Si-F bonds are detected.     

Shear band formation and mode II fracture of polymeric glasses

Mode I and II fracture studies were performed from quasistatic to low velocity impact rates on polymethyl methacrylate (PMMA) and polycarbonate (PC). Mode II tests used an angled double‐edge notched specimen loaded in compression. The shear banding response of PMMA is shown to be highly sensitive to rate, with diffuse shear bands forming at low rates and sharp distinct shear bands forming at high rates. As the rate increases, shear deformation becomes more localized to the point where Mode II fracture occurs. PC is much less rate dependent and stable shear band propagation is observed over the range of rates studied with lesser amounts of localization. A new theory is formulated relating orientation in a shear band to intrinsic material properties obtained from true‐stress true‐strain tests. In a qualitative sense the theory predicts the high rate sensitivity of PMMA. A kinematic limit for orientation within a shear band is also derived based on entanglement network parameters. Mode II fracture in PMMA is shown to occur at this kinematic limit. For the case of PC, the maximum impact rates were not high enough to reach the kinematic limit. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Synthesis and characterization of europium-containing luminescent bioactive glasses and evaluation of in vitro bioactivity and cytotoxicity

Luminescent europium-containing bioactive glasses (EuBG) based on the 58 %SiO₂–33 %CaO–9 %P₂O₅ (in mass, %) system were synthesized using sol–gel technique by adding Eu₂O₃ in silica network. The structural, textural and optical properties, as well as in vitro bioactivity and biocompatibility of the material were characterized using various methods. The results show that all the Eu-containing bioactive glass materials exhibit an amorphous structure, large specific surface area, relatively uniform pore size distribution and high in vitro bioactivity, similar to the conventional sol–gel bioactive glass. More importantly, the addition of Eu₂O₃ endow the material with a luminescent property even after immersion in aqueous solution and the luminescent intensity increases with the increase of Eu₂O₃ content. The cytotoxicity assay indicates that pure EuBG extract significantly inhibit the growth of rat marrow mesenchymal stem cells (rMSCs), while 25 % concentration of the extract diluted by culture medium could significantly improve the proliferation of rMSCs in comparison with pure medium. According to the above results, the material presents excellent apatite-forming activity, luminescent property and biocompatibility, demonstrating their potential applications in the fields of bone regeneration and drug delivery system.     

Effect of gamma-rays on the formation of color centers in copper-containing lead borate glasses

Absorption bands in the range of 350–950 nm, induced in copper-containing lead borate glasses by -rays were identified and characterized. The effect of irradiation dose, copper oxide and lead oxide contents on the intensity and position of the induced absorption bands were also considered. Several induced absorption bands were observed. At least two bands in the ranges of 740–780 and 850–870 nm could be identified. They are suggested to be associated with induced Cu⁽²⁺⁾ ions. The band in the 800–830 nm (1.6 eV) range is ascribed to the Pb⁽³⁺⁾ ion, whereas others in the ranges of 600–630 and 650–730 nm are associated with the intrinsic defects formed in the base glass.     

m-Terphenyl thiols: rigid and bulky molecules for the formation of bioactive self-assembled monolayers on gold

The m-terphenyl 4-mercaptomethyl-2,6-diphenylbenzoic acid (3), was prepared and shown to form omega-carboxyl terminated self-assembled monolayers (SAMs) on gold with high surface pKa(10.1 +/- 0.2) and low density favourable for the binding of biological macromolecules.     

Glass formation and properties of Ge-Te-BiI3 far infrared transmitting chalcohalide glasses

A novel series of Ge-Te-BiI(3) chalcogenide glasses were prepared by traditional melt-quenching method and the glass-forming region was determined. Properties measurements including density, Vis-NIR and infrared (IR) transmission spectra with FTIR, XRD, DSC were adopted to analyze the composition, structure and performance of the Ge-Te-BiI3 glass system. Based on the metallization criterion and band gap energy theory, the relationships between energy gap, metallization criterion and glass composition was investigated. The results show that with the addition of BiI3, the glasses-forming ability and thermal stability are improved. The values of energy band gap and metallization criterion are within the range of 0.627-0.343 eV and 0.177-0.131, respectively. These series of glasses have wide optical transmission window from 2.2 to 25 μm and can offer an alternative solution for far infrared transmitting applications.