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The liquid-to-crystal transformation proceeds steadily in the temperature range of the overlap of both rate curves. Tammann rate curve representations: a small top vs. Shaded area indicates overlap range. Get the full book here. The conference chairs were M. Pascual and A. The home page of the event is still available here. The conference venue was the Auditorium in the Parador de Segovia. Previous versions have been held in. Nagaoka, Japan T. Komatsu, A. Sakamoto Goslar, Germany J.

Zanotto Jackson Hole, Wyoming U. Davis Sheffield, England P. James Vaduz, Liechtenstein W. Over the years, these bi- or triennial meetings have established a strong international reputation for disseminating the state-of-the-art in crystallization research, from fundamental aspects to innovative glass-ceramic products.

The Segovia meeting covered the areas of simulation and theory, formation, structure, properties, and applications of crystallized glasses presented in 57 lectures including 11 invited talks and 76 posters. Schmelzer, Rostock University Germany A. Jianrong, Zhejiang University China H.

Awardees S. Shigematsu, S. Sakka, T. Liquid phase sintering, Cullity B D. Elements of X-ray facsimile ed. Newyork: Plenum press diffraction. Reading, M A: Addison- Wesley; p. Fundamentals of ceramics, Kittel C. Wiley: New York; chapter 2 8. Kokubo, T. Shigematsu, M. Nagashima, Tashiro, M. Nakamura, T. The Yamamuro, and T.

Apatite— effect of substrate temperature on the and wollostonite- containing glass Structural and some physical properties ceramics for prosthetic applications. Investigations on chemical bath 9. Holeand, W. Vogel, K. Journal of biomedical films. Mater Chem Phys, —96 materials research.

Related Papers. By Baskaran V. Bioactive Glass-ceramics: Processing, Properties and Applications. By Maziar Montazerian. History and trends of bioactive glass-ceramics. By sayed kenawy. Download pdf. Remember me on this computer. Moreover, the review papers cited above tend to deliberately omit the several disadvantages of high alkali-containing BGs [ 67 , 68 , 69 , 70 , 72 , 73 , 76 , 77 , ]. The leaching of high alkali contents induces in vitro cytotoxicity effects in cell culture media and in the living tissues around the implant due to the high local pH environment [ 67 , 76 , 77 , , ].

Such high pH environment favours the formation of HCA, but is likely to give false positive bioactivity results in SBF, while being unfavourable for homeostasis [ 76 ]. Excessive changes in the medium pH can inhibit osteoblast activity and cause cell necrosis or apoptosis [ 76 , ].

Therefore, the pertinence of the continuous research activities focused on high alkali-containing bioactive glasses is highly questionable. As reviewed above, such glass compositions hardly can meet the most salient features of an ideal bioactive glass, concerning not only the in vitro and in vivo performances, but also the thermal, physicochemical properties, and processing ability, which include [ ]:. Fast biomineralisation rate in vitro with the formation of a hydroxyl carbonated apatite HCA ;.

Osteoinductive properties—recruiting immature cells and stimulating them to develop into pre-osteoblasts, which are essential in any bone healing process;. Osseointegration—stable anchorage of an implant achieved by direct bone-to-implant contact. For implant coatings, good matching of the coefficients of thermal expansion of the coating glass and the metallic substrate for a strong adhesion between applied films and metallic implants;.

Solving this complex challenge for multifunctional bioactive glasses with well-balanced properties requires new and smart approaches, which have been pursued by Ferreira et al. Significant improvements in the overall properties were achieved using bioactive glass and glass-ceramic compositions with low alkali contents in the SiO 2 —Al 2 O 3 —B 2 O 3 —MgO—CaO—Na 2 O—F system [ 27 , , , , , , , , ].

These materials exhibited good sintering ability and excellent performances in vitro [ 27 , , , , , ] and in vivo [ ]. They were also used in the formulation of injectable devices [ , ]. However, when sodium oxide was gradually added to partially replace MgO in a series of glasses prepared by the melt quenching technique with compositions expressed as These results suggested that alkali-free compositions could be a better bet to explore. The attempts made in this direction will be reviewed in the next section. The most salient features desired for bioactive glasses as listed above can be obtained while totally excluding the alkalis and by a rational combination of all the remaining pertinent glass components, as has been plenteously demonstrated by Ferreira et al.

Following a completely different concept, the alkali-free bioactive glass compositions were based upon the compositions of minerals that are biocompatible and bioactive, such as diopside, fluorapatite, wollastonite, and tricalcium phosphate, in different combinations and proportions.

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The emphasis in this section is particularly put on alkali-free bioactive glasses and glass-ceramics as a smart way to overcome all the drawbacks mentioned above for high alkali containing compositions, as summarised elsewhere [ ]. Amorphous glasses could be obtained only for compositions up to 40 wt. Silicon was predominantly present as a Q 2 Si species, while phosphorus was found in an orthophosphate-type environment in all the investigated glasses.

The in vitro cellular responses to glass-ceramics showed good cell viability and the significant stimulation of osteoblastic differentiation, suggesting the possible use of the glass-ceramics for bone regeneration [ ]. It was shown that irrespective of the mean particle size, the bioglass exhibited good sintering ability. Neck formation and other morphological changes observed by HT-SEM were initially driven by surface diffusion at temperatures apparently below T g but without noticeable macroscopic shrinkage.

With temperatures increasing above T g , the particles formed individual spherical droplets, which then merged into larger liquid droplets, which were signs of their excellent sintering ability. The content of residual glassy phase tended to increase as the mean particle size increased. The aim of adding W was to further improve the sintering ability that was investigated by differential thermal analysis DTA.

Glasses and glass ceramics for medical applications

The glass-ceramics W—W exhibited the higher amounts of residual glassy phase that favoured bioactivity. P 2 O 5 system, combined in different proportions [ , , , , ]. Graphical representation of the alkali-free bioactive glass compositions investigated [ , , , , ]. Table 11 provides the compositional details of the most interesting BGs in this ternary system. The glass-forming ability and stability of these glasses strongly depended on the composition and the cooling rate.

Fluorapatite-richer compositions were less prone to glass formation and underwent fast crystallisation, even upon quenching the melts in cold water to obtain the glass frits black symbols. Among the diopside-richer compositions, some enabled obtaining amorphous frits, but the bulk glasses cast on metal plates tended to partially crystallise, especially in the parts further from the metal plates that cooled more slowly white core symbols , while others enabled obtaining amorphous materials grey symbols.

These last ones were the most interesting compositions from the processing viewpoint. The silicate network consisted predominantly of Q 2 Si units, while phosphorus tends to remain in an orthophosphate Q 0 environment, which is a common feature to all the designed alkali-free formulations. Some of the investigated glasses exhibit HCA formation on their surface within one to 12 hours of their immersion in SBF solution [ ]. The alkaline phosphatase activity and osteogenic differentiation using rat bone marrow mesenchymal stem cells seeded on sintered glass powder compacts revealed that the tested compositions are ideal potential candidates for applications in bone tissue engineering.

These features are essential for the fabrication of mechanically strong bioactive glass scaffolds for bone regeneration. Printable inks containing 47 vol. The fully densified filaments obtained upon sintering conferred to the scaffolds compressive strength values that were higher in comparison to cancellous bone. The addition of bioglass was found to decrease the elastic gradient and yield stress if two scaffolds of the same density are compared. Such problems could only be overcome using carboxymethylcellulose CMC as a single multifunctional dispersant, binder, gelation agent processing additive, enabling obtaining aqueous suspensions with 45 vol.

Further, the addition of strontium led to a sevenfold decrease in chemical degradation of glasses in Tris—HCl and citric acid buffer. Di was crystallised as the dominant phase, and FA was also formed as the secondary phase. The flexural strength values of GCs varied between 98— MPa.

The large amounts of residual glassy phase, along with the good flexural strength, proved the potential of the developed GCs for the scaffold fabrication in bone tissue engineering. The foremost studies on Sr-containing bioactive glasses were published in by Galliano et al. The authors were not yet sure about their biocompatibility. The subject did not attract further attention for more than one decade, but the interest in Sr-doped bioactive glasses was rejuvenated as deduced from a series of Sr-containing bioactive glass compositions patented by Hill and Stevens [ ] and Jallot et al.

These studies demonstrated the benefits of Sr-doping bioactive glass for their in vitro performance. Recently, Hill and Stevens [ ] patented a series of strontium-containing bioactive glass compositions, among which a glass with wt. The other parallel work [ ] aimed at investigating the influence of the partial replacement of MgO by ZnO on the structure, sintering ability, crystallisation behaviour, and bioactivity.

The ZnO content was revealed to play an essential role in the in vitro bioactivity. The detailed compositions are reported in Table The relevant structural properties, which were assessed by molecular dynamics simulations in combination with solid-state NMR spectroscopy were well correlated to the degradation behaviour, in vitro bioactivity, osteoblast proliferation, and alleviation of the oxidative stress levels exerted on the human osteosarcoma MG63 cell line.

A dose-dependent cytoprotective effect of glasses with respect to the concentrations of zinc and strontium released was observed, enhancing the cell viability and negating the effect of oxidative stress induced by the addition of H 2 O 2 to the cell culture medium. The most promising bioactive glass compositions Di to Di reported in Table 13 were further investigated for the in vitro performance using human mesenchymal stem cells hMSCs.

Significant statistical increases in the metabolic activity of hMSCs when compared to the control were observed for Di and Di glasses under both basal and osteogenic conditions [ ]. All of the investigated glasses underwent considerably lower weight losses in Tris—HCl in comparison to that of 45S5 Bioglass, but exhibited enhanced in vitro biomineralisation activity expressed by the formation of an HCA surface layer over seven days of soaking in SBF.

The aim was to evaluate and compare their abilities to stimulate human mesenchymal stem cells hMSCs differentiation into osteoblasts. Nowadays, the international market for osseous implants and endoprostheses is dominated by the medical devices fabricated from titanium Ti or its medical-grade superalloys. Respectable financial analysis agencies forecast an outstanding growth of the implants market, in the response to the increasing health and societal needs [ , , ].

In spite of their proven biocompatibility and excellent mechanical performance, the metallic implantable devices entail long healing periods, as they lack innate bioactive properties, and thereby do not possess the ability to induce a fast bonding with bone tissue. No commercially ready for clinical use bioactive glass implant coatings yet exist, to the best of our knowledge. The benefits that could emerge from the delineation of an implant coating design based on bioactive compounds that are superior to HA i.

Consequently, a wide palette of deposition methods [ ] has been explored over the years to achieve this conceptual desiderate i. Thereby, in this short section, the authors aim to complete the whole picture, and briefly present the results achieved in the realm of bioactive silica-based glass SBG thin films synthesised by ion-beam and radio-frequency magnetron sputtering, offering a flavour of their future potential.

The sputtering method is a prominent member of the physical vapour deposition PVD family, and is currently expansively used in the semiconductor and decorative industries. Its simple process relies on the expulsion of atoms from a target by bombardment with energetic ions typically argon. The positively charged gas ions are attracted to the negative biased cathode target at very high speeds, resulting in the ejection of atoms, which are deposited in form of a film on a substrate conveniently positioned in the vicinity of the target. The ion-beam variant possesses the advantage that some of the deposition variables i.

Furthermore, the absence of plasma between the substrate and the target present in the case of magnetron sputtering permits the deposition of films onto materials that are highly sensitive to temperature. However, ion-beam sputtering yields reduced deposition rates with good uniformity only on constricted substrate areas, which does not make it very attractive for large-scale applications. To date, only two attempts to prepare SBG glass films by ion-beam sputtering have been recorded. Films with thicknesses in the range of 0.

A good degree of substrate coverage was attained only for the thicker films. The most promising results have been achieved for the SBG-coated polymeric substrates, as indicated by the in vivo tests performed on animal model Sprague—Dawley rats. The tissue adhesion of collagen to the SBG coating surface was observed. The second topical study followed 20 years later, with Wang et al.

The dense and homogenous coatings had excellent bonding strength no delamination being observed by performing scratch tests at a load of gf and induced the proliferation of MC3T3-E1 mouse osteoblast cells. In magnetron sputtering, the gun cathode design uses magnetic fields to trap the stray electrons in the vicinity of cathode target surface, which disallows these particles to bombard and heat with possible damages the growing film.

Simultaneously, the ionisation probability of the neutral working gas molecules is augmented by several orders of magnitude, having as an effect a more stable plasma and greater number of available bombarding ions, and thus, a significant improvement of the sputtering yield [ ]. Furthermore, radio-frequency magnetron sputtering RF-MS has a series of other remarkable advantages, including: high purity, excellent adherence, uniformity in both thickness and composition on large-area substrates dependent only on the magnetron gun size , compactness, ability of facile engineering of film properties by variation of the process parameters working pressure, electric power, target-to-substrate separation distance, substrate temperature, working gas composition , or the possibility of coating complex-shaped objects if adopting planetary rotation holders [ , , ].

The demonstrated ability of RF-MS to surpass technological barriers and be scaled up with ease to an industrial level as shown in the optoelectronics industry [ , ] should increase its desirability in the biomedical field also. Following this peripheral attempt, there can be identified in the main scientific data bases e. Recently, Stuart et al. Remarkable biomineralisation capabilities i. Kokubo in the early s now part of the ISO bioactivity testing protocol [ , ] and ii inorganic—organic media with increasing degrees of biomimicry, reproducing the human intercellular environment with higher fidelity [ ].

SBG films have shown as well to have excellent cytocompatibility with various cell lines: rat bone marrow [ ], SAOS-2 human osteoblast [ ], primary human osteoblast [ ], 3T3 mouse fibroblast [ ], human dental pulp stem [ ], HUVEC-Hs27 human umbilical vein endothelial [ ], and human mesenchymal stem cells [ ]. The ability of SBG RF-MS films to either i promote the proliferation and differentiation of osteoblast cells [ ] or ii conserve an undifferentiated phenotype of stem cells, while enabling a good cellular adhesion and proliferation [ ], has been reported.

In Ref. Contradictory biological results have been obtained. The S53P4 addition to hydroxyapatite dental implant coatings resulted in inferior in vivo performances [ ], while in the case of iliac implants coatings, the S53P4 incorporation into hydroxyapatite led to an enhanced in vivo biological behaviour [ ], with respect to the pure hydroxyapatite control.

However, no pure SBG control coating has been included in the experimental groups, due to the authors fearing the possible low adherence strength of the SBG films [ ]. Indeed, one obstacle in the fabrication of mechanically reliable SBG coatings for implant applications was the significant mismatch between the coefficients of thermal expansion CTE of classical SBG systems i. However, as a consequence of the inexplicable application of post-deposition thermal treatments at extreme temperatures i. Ten years later, Stan et al.

By using SBG systems with i high silica content [ ] or ii moderate silica content and low alkali concentration [ , ], and thereby lower CTE values i. These values are similar to the ones obtained for plasma spray coatings with thicknesses of the tens or even hundreds of micrometres [ , ]. These progresses encouraged the application of such optimised RF-MS regimes for the coating with SBG layers of real dental implant fixtures [ ]. Noteworthy, it was recently shown that one can take advantage of the RF-MS film growth mechanisms i. While RF-MS possesses a large number of advantages, it has also been criticised for its presumed inability to congruently reproduce with ease the composition of complex materials, including SBGs and PBGs, since the lighter species are more readily ejected from the target surface.

However, by the variation of the main RF-MS deposition parameters sputtering pressure, working atmosphere, target powder density, target-to-substrate separation distance , one can modify the composition and structure of films starting from a single target, in the pursuit of improved mechanical and biological performances [ , , , , , , , , , ]. In conclusion, the RF-MS technique can be considered a genuine alternative for the biofunctionalisation of the next generation of osseous implants and endoprostheses. The path towards the manufacture of mechanically reliable SBG implant coatings has now been reopened by the recent delineation of SBG compositional systems, eliciting both low CTEs and unaltered biological properties.

His discoveries inspired many other studies with different perspectives. The pertinence in further exploring this perspective is quite questionable, as the degree of novelty is not clear, and it seems to go beyond science and towards advertisement. However, numerous available literature reports about bioactive glasses and glass ceramics provide plenty of evidence that high alkali-containing bioactive glasses present several main limitations, as have been detailed and reviewed in the sections above, including the abstract.

Another completely different perspective is behind an increasing number of other studies that have aimed at tackling the specific problems posed or left unsolved by high alkali-containing bioactive glass compositions and emphasising the demonstrated advantages of using alkali-free or low alkali-containing bioactive glass compositions. From sections 3. Their 10 most important advantages are summarised in Section 3.

Unfortunately, due mostly to artificial market barriers, the process by which new biomedical devices reach the market is cumbersome and discouraging, even when there is enough evidence about the comparative advantages offered by the new materials or devices in comparison to those being commercialised. Its superior overall properties suggest excellent promise for biomedical applications in dentistry, orthopaedics, maxillofacial surgeries, scaffolds fabrication for bone regeneration and tissue engineering, and as coating material for the surface functionalisation of metallic or ceramic implants.

They also distributed specific review tasks among themselves and the remaining authors A. He also elaborated the figures related to the respective sections. Both also agreed concerning the details of the Graphical Abstract. All authors revised the paper critically for intellectual content and approved the final version.

All authors agree to be accountable for the work and to ensure that any questions relating to the accuracy and integrity of the paper are investigated and properly resolved. National Center for Biotechnology Information , U. Journal List Materials Basel v.

Materials Basel. Published online Dec Hugo R. Find articles by Hugo R. Find articles by Anuraag Gaddam. Find articles by Avito Rebelo. Find articles by Daniela Brazete. George E. Author information Article notes Copyright and License information Disclaimer. Received Nov 10; Accepted Dec 6. This article has been cited by other articles in PMC. Keywords: bioactive glasses, alkali-free, scaffolds fabrication, additive manufacturing techniques, bone regeneration, tissue engineering. Background: Nature, Structure, and Chemistry of Glasses 1.

The Nature of Glasses Glasses have been used by mankind for thousands of years in multiple forms and applications. Glass Structure One of the earliest consideration of the glass structure was proposed by Zachariasen in his classic paper [ 8 ]. Open in a separate window. Figure 1. Figure 2. Borate Glasses B 2 O 3 is one of the most important glass-forming oxides due to its higher field strength, lower cation size, small heat of fusion, and trivalent nature of B. Mixed Glass Former Systems Many glass compositions are based on more than one former oxide, such as borosilicates, borophosphates, or phosphosilicates, for instance.

Probing the Structure The structure of a glass could be quantified by the pair distribution function PDF or radial distribution function RDF , given by g r , which is related to the probability of finding another atom at a distance r from a central atom. Glass-Ceramics: Between Glasses and Crystalline Materials Glass-ceramics GCs were discovered in the midth century, and can be considered as a combination of a glass with a ceramic [ 47 ].

Bioactive Glasses and Glass-Ceramics The progressive aging of world population, coupled with an increasing incidence of skeletal diseases, is a main driving force stimulating the increasing research efforts put forward developing new implantable materials. The formation of an HCA layer occurs according to the followed sequence of reactions, as proposed by Hench [ 64 ]: 1. Bioactive Glasses in Numbers The number of papers published per year in the field has noticeably increased especially since the beginning of the s.

Table 1 Publications by access type. Figure 3. Table 2 Subject areas found in query A. Table 3 Subject areas found in query B. Table 4 Types of documents. Table 5 Source titles with bucketing regarding the number of publications for A query.

Research 4 4 1. Table 6 Affiliations organised after bucketing by number of publications. Table 7 Publications per country, population in , gross domestic product GDP reference to , in 10 12 USD , number of publications NP per million of habitants, and the ratio of number of publications per respective GDP. Glass Structure, Dissolution Behaviour, and Bioactivity The chemical durability of glass is a crucial property for bioactivity, because the dissolution rate must be compatible with the cellular processes and with the rate of new bone formation.

A New Biocompatible and Antibacterial Phosphate Free Glass-Ceramic for Medical Applications

Thermodynamics and Kinetics of Dissolution In contrast to glasses for most other applications, which are expected to have low dissolutions rates to minimise the corrosion, bioactive glasses require specific dissolution rates to tune the in vitro and in vivo performances. Figure 4. The Effects of Adding Other Components to the Na 2 O—CaO—SiO 2 Glass System Most of the bioactive glass compositions that have been developed so far typically belong to the ternary Na 2 O—CaO—SiO 2 system, which is essentially the same compositional system adopted for common glasses such as windows, food and beverage containers, decorative tableware, etc.

Ion-Doped Bioactive Glasses The physical and functional properties and the in vitro and in vivo performances of bioactive glasses can be modified and improved with the incorporation of doping oxides in trace amounts e. Below are listed examples pointing out the biological role and the effect of some ions on glass bioactivity: 1.

As reviewed above, such glass compositions hardly can meet the most salient features of an ideal bioactive glass, concerning not only the in vitro and in vivo performances, but also the thermal, physicochemical properties, and processing ability, which include [ ]: 1. Alkali-Free Bioactive Glasses The most salient features desired for bioactive glasses as listed above can be obtained while totally excluding the alkalis and by a rational combination of all the remaining pertinent glass components, as has been plenteously demonstrated by Ferreira et al. Figure 5. Sputtered Bioglass Thin Films: A Reliable Biofunctionalization Option for Implantology Nowadays, the international market for osseous implants and endoprostheses is dominated by the medical devices fabricated from titanium Ti or its medical-grade superalloys.

Author Contributions H. Conflicts of Interest The authors declare no conflicts of interest. References 1. Gutzow I. Springer; Berlin, Germany: Doremus R. Glass Science. Paul A. Chemistry of Glasses.

1. Background: Nature, Structure, and Chemistry of Glasses

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Bioactive Glass and Glass Ceramics

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  • Next-generation glass research;
  • Glasses and glass ceramics for medical applications;
  • TC07: Crystallisation & GCs.

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Inhaltsverzeichnis

Characterization of glass corrosion and durability. An Introduction to Bioceramics. Review of bioactive glass: From Hench to hybrids. Acta Biomater. Sepulveda P. In vitro dissolution of melt-derived 45S5 and sol-gel derived 58S bioactive glasses. Vogel M. In vivo comparison of bioactive glass particles in rabbits. Clupper D. Crystallization kinetics of tape cast bioactive glass 45S5. Chen Q. Boccaccini A. Faraday Discuss.

Lefebvre L. Sintering behaviour of 45S5 bioactive glass. Bretcanu O. Huang R. A two-scale model for simultaneous sintering and crystallization of glass-ceramic scaffolds for tissue engineering. Kirsten A. Bioactive and thermally compatible glass coating on zirconia dental implants. Wallace K. Influence of sodium oxide content on bioactive glass properties. Kansal I. Structure, biodegradation behavior and cytotoxicity of alkali-containing alkaline-earth phosphosilicate glasses.

Cannillo V. Production of Bioglass 45S5-Polycaprolactone composite scaffolds via salt-leaching. Fabbri P. Highly porous polycaprolactoneS5 Bioglass scaffolds for bone tissue engineering. Rottensteiner U. Materials Basel ; 7 — Meng D. Tetracycline-encapsulated P 3HB microsphere-coated 45S5 Bioglass-based scaffolds for bone tissue engineering. Ball J. Biocompatibility evaluation of porous ceria foams for orthopedic tissue engineering. Part A. Rivadeneira J. Alno N. De Development of a three-dimensional model for rapid evaluation of bone substitutes in vitro: Effect of the 45S5 bioglass.

Zhang Y. Cytocompatibility of two porous bioactive glass-ceramic in vitro. West China J.

Biomedical Glasses

Biocompatible evaluation of barium titanate foamed ceramic structures for orthopedic applications. Ferreira J. Is the ubiquitous presence of barium carbonate responsible for the poor aqueous processing ability of barium titanate? Phelan D. Is hypokalaemia the cause of paralysis in barium poisoning?

Chaudhary S. Indian Assoc. Pryce R. Dissolution characteristics of bioactive glasses. Key Eng. In vitro evaluation of 45S5 Bioglass-derived glass-ceramic scaffolds coated with carbon nanotubes. Biocompatibility of submicron Bioglass V powders obtained by a top-down approach. Part B Appl. Santhiya D. Santocildes-romero M. The osteogenic response of mesenchymal stromal cells to strontium-substituted bioactive glasses. Tissue Eng. Three-dimensional bioactive glass implants fabricated by rapid prototyping based on CO 2 laser cladding. Bellucci D. Bioactive glass-based composites for the production of dense sintered bodies and porous scaffolds.

Sol-gel derived bioactive glasses with low tendency to crystallize: Synthesis, post-sintering bioactivity and possible application for the production of porous scaffolds. Murphy S. The effect of ionic dissolution products of Ca-Sr-Na-Zn-Si bioactive glass on in vitro cytocompatibility. Biomimetic coating on bioactive glass-derived scaffolds mimicking bone tissue.

Philippart A.