Effect of MgO addition on the crystallization and in vitro bioactivity of glass ceramics in the CaO–MgO–SiO2–P2O5 system

CaO–MgO–SiO₂–P₂O₅ glass ceramics were successfully prepared by sintering the sol–gel-derived powders. The effects of MgO addition on the samples crystallization and structure were investigated by means of differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). In addition, samples degradation and in vitro bioactivity assays were also evaluated. With more MgO addition, the glass ceramics crystallization kinetics under non-isothermal conditions changed from bulk crystallization to surface crystallization, and new crystal phases of Ca₂MgSi₂O₇ and SiO₂ were induced. In addition, it is observed that with increasing MgO concentration, the glass ceramics degradability gradually decreased and the formation of apatite was delayed.     

In vitro characterisation of plasma-sprayed apatite/wollastonite glass–ceramic biocoatings on titanium alloys

Some ceramics have the ability to form direct bonds with surrounding tissues when implanted in the body. Among bioactive ceramics, the apatite/wollastonite (A/W) glass–ceramic, containing apatite and wollastonite crystals in the glassy matrix, has been largely studied because of good bioactivity and used in some fields of medicine, especially in orthopaedics and dentistry. However, medical applications of bioceramics are limited to non-load bearing applications because of their poor mechanical properties. In this study, A/W powders, obtained from industrial and high grade quality raw materials, were thermally sprayed by APS (atmospheric plasma spraying) on Ti–6Al–4V substrates, in order to combine the good bioactivity of the bioceramic and the good mechanical strength of the titanium alloy base material. The microstructure and the resulting properties were evaluated depending on processing parameters and post-processing thermal treatments. The morphology and the microstructure of the coatings were observed by SEM and the phase composition was examined by X-ray diffraction. The bioactivity of the coatings was evaluated by soaking the samples in a simulated body fluid (SBF) for 1, 2 and 5 weeks. The bioactive behaviour was then correlated with the thermal treatments and the presence of impurities (in particular Al₂O₃) in the coatings.     

Studies of Bone-Bonding Ability and Antibacterial Properties of Ag<Superscript>+</Superscript>, Cu<Superscript>2+</Superscript> or Zn<Superscript>2+</Superscript> ions Doping within Hench’s Bioglass and Glass-Ceramic Derivatives

Derived Hench’s bioglasses with specific ionic dopants Ag⁺, Cu²⁺, or Zn²⁺ have been prepared. The bone-boding ability or bioactivity behavior for the prepared glasses and their glass-ceramic derivatives has been investigated after immersion in phosphate solution for two weeks. Collective Fourier transform infrared absorption spectra (FTIR) and scanning electron microscopic (SEM) studies were conducted in order to study the in-vitro bioactivity behavior. X-ray diffraction (XRD) analysis was carried out to identify the crystallized phases upon thermal heat treatment through a two-step regime. The glasses and their glass-ceramic derivatives were tested to study their antibacterial or antifungal efficiency responding to the doped metal ions. FTIR spectra revealed the generation of two split peaks at about 560 and 605 cm^?1, after immersion in (0.2 M) sodium phosphate solution (Na₃PO₄), signifying the formation of a crystalline calcium phosphate phase, leading to hydroxyapatite formation. SEM examinations show characteristic rounded or nodular microcrystals for hydroxyapatite which support the FTIR data. X-ray diffraction analysis indicated crystallization of the main soda-lime silicate phase (1Na₂O.2CaO.3SiO₂) besides a secondary silicon phosphate phase (SiO₂.P₂O₅) in the studied glass ceramics. The route of crystallization is discussed on the basis of the presence of 6% P₂O_5; which facilitates the formation of phase separation and voluminous bulk crystallization of the main soda-lime silicate phase. The introduction of dopants is identified to cause no changes in the precipitated phases, with only minor changes in the percent of the crystalline phases. Experimental data indicate that the glass-ceramic samples are effective in bioactivity and antimicrobial efficiency.     

Sealing Glass‐Ceramics with Near‐Linear Thermal Strain,Part II: Sequence of Crystallization and Phase Stability

The sequence of crystallization in a recrystallizable lithium silicate sealing glass‐ceramic Li₂O–SiO₂–Al₂O₃–K₂O–B₂O₃–P₂O₅–ZnO was analyzed by in situ high‐temperature X‐ray diffraction (HTXRD). Glass‐ceramic specimens have been subjected to a two‐stage heat‐treatment schedule, including rapid cooling from sealing temperature to a first hold temperature 650°C, followed by heating to a second hold temperature of 810°C. Notable growth and saturation of Quartz was observed at 650°C (first hold). Cristobalite crystallized at the second hold temperature of 810°C, growing from the residual glass rather than converting from the Quartz. The coexistence of quartz and cristobalite resulted in a glass‐ceramic having a near‐linear thermal strain, as opposed to the highly nonlinear glass‐ceramic where the cristobalite is the dominant silica crystalline phase. HTXRD was also performed to analyze the inversion and phase stability of the two types of fully crystallized glass‐ceramics. While the inversion in cristobalite resembles the character of a first‐order displacive phase transformation, i.e., step changes in lattice parameters and thermal hysteresis in the transition temperature, the inversion in quartz appears more diffuse and occurs over a much broader temperature range. Localized tensile stresses on quartz and possible solid‐solution effects have been attributed to the transition behavior of quartz crystals embedded in the glass‐ceramics.     

Reduction‐Induced Inward Diffusion and Crystal Growth on the Surfaces of Iron‐Bearing Silicate Glasses

We investigate the sodium inward diffusion (i.e., sodium diffusion from surface toward interior) in iron containing alkaline‐earth silicate glasses under reducing conditions around T_g and the induced surface crystallization. The surface crystallization is caused by formation of a silicate‐gel layer first and then the growth of silica crystals on the glass surface. The type of alkaline‐earth cations has a strong impact on both the glass transition and the surface crystallization. In the Mg‐containing glass, a quartz layer forms on the glass surface. This could be attributed to the fact that Mg²⁺ ions have stronger bonds to oxygen and lower coordination number (4–5) than Ca²⁺, Sr²⁺, and Ba²⁺ ions. In contrast, a cristobalite layer forms in Ca‐, Sr‐, and Ba‐containing glasses.     

Phase evolution and photoluminescence in Er3+ doped glass ceramics containing lutetium oxyfluoride nanocrystals

Crystalline phase evolution through merely adjusting composition was achieved in silicate glass ceramics containing Lu_nO_n-1F_n+2 (n = 5–10) nanocrystals. Orthorhombic or cubic phase nanocrystals were precipitated in the aluminosilicate glass matrix after thermal treatment together with varying the Na₂O/NaF ratio. Oxyfluoride nanocrystals with quasi-spherical shape show homogenous and dense distribution in glass matrix by transmission electron microscopy measurement. Intense upconversion and mid-infrared emissions were realized in these glass ceramics compared to the precursor glass, and the emission spectral shapes, relative emission intensity and fluorescence decay curves of Er³⁺ in cubic LuOF embedded samples exhibit remarkable differences due to the crystal phase dependent effect in glass ceramics. These results indicate that the crystallization and luminescence properties of oxyfluoride glass ceramics could be modified through the alteration of glass composition, which could be used for the development of novel glass ceramics and design of luminescent properties.     

Characterization and in vitro-bioactivity of natural hydroxyapatite based bio-glass–ceramics synthesized by thermal plasma processing

Natural bovine hydroxyapatite/SiO₂–CaO–MgO glass–ceramics were produced using the transferred arc plasma (TAP) processing method. Homogeneous mixtures of HA/25 wt% SiO₂–CaO–MgO and HA/50 wt% SiO₂–CaO–MgO batches obtained by dry mixing the respective compositions in a ball mill were processed in argon plasma using the TAP torch at 5 kW for 1, 2 and 3 min, respectively. The synthesized glass–ceramic samples were studied for phase composition, microstructure and bioactivity. The phase study of the synthesized glass–ceramics revealed the formation of calcium phosphate silicate with traces of calcium silicate. The structural study by SEM revealed that the prepared samples possessed smooth glassy surface morphology. The in vitro-bioactivity of the TAP synthesized glass–ceramics was examined in simulated body fluid (SBF). The SBF test results confirmed the development of crystalline carbonated apatite phase after 12 days of immersion. The cytocompatibility was evaluated through human fibroblast cell proliferation. The fibroblasts culture results showed that the sample was non-toxic and promoted cell growth.     

Crystallization process of thermally treated vitrified EAFD waste

Electric arc furnace dust (EAFD) powder was mixed and vitrified with 55% SiO₂, 10% Na₂CO₃ and 35% CaCO₃ raw materials. The resulting glass was thermally treated at the same temperature at different annealing times. The process towards crystallization of the glass–ceramics produced, as a function of annealing time, was examined by means of optical microscopy, electron microscopy techniques and X-ray diffraction. While at small crystallization times wollastonite was the only crystalline phase separated from the amorphous matrix, as the time of crystallization increased crystals of diopside emanating from wollastonite were also observed. The emergence of diopside crystals was attributed to the tendency of the metallic elements of EAFD, incorporated in the wollastonite structure, to move towards the neighbouring glass matrix causing local maxima of concentration in the vicinity of wollastonite crystals. This diffusive motion of the metallic elements of EAFD, such as Fe, Zn, was found to follow the 2nd Fick law and plays a crucial role in the stability region of the crystallized structures of the system.     

Phase formation during crystallization of a Li2O-Al2O3-SiO2 glass with ZrO2 as nucleating agent – An X-ray diffraction and (S)TEM-study

Glass ceramics based on the system Li₂O/Al₂O₃/SiO₂ (LAS) often show a coefficient of thermal expansion close to zero. Although these glass-ceramics are of high economic importance, the fundamentals of the crystallization process are still not fully understood. In this paper, the effect of ZrO₂ addition as a sole nucleation agent on the crystallization of the LAS glass is described predominantly using transmission electron microscopy and X-ray diffraction. The composition of the studied green glass was close to that of the commercially available Robax™ glass (Schott AG), which, however, contained both, ZrO₂ and TiO₂ as nucleating agents. It was found that during thermal treatment, in a first step, already at temperatures around 10–20 K below the glass transition temperature, T_g, ZrO₂ nanocrystals with sizes in the range from 5 to 15 nm were precipitated. The next crystalline phase that forms during the crystallization process was LAS with a structure similar to the hexagonal high temperature phase of quartz. These crystals were much larger than the ZrO₂ crystals. If thermal treatment was carried out at higher temperatures, a dense network of LAS crystals was formed. Differently shaped crystals in samples with different thermal history were visualized, and an enrichment of Ba and Sb in the residual glass phase in the late stages of thermal treatment was found. Also, an enrichment of aluminum around the ZrO₂ crystals was evident, which is a hint at a preceding droplet phase separation from which the ZrO₂ crystals were precipitated. The crystallization is notably different from that of mixed ZrO₂/TiO₂ nucleating agents used in commercial lithium alumosilicate glass ceramics.     

Crystallization and luminescence properties of Eu<Superscript>2+</Superscript> doped diopside glass ceramics

Eu²⁺ doped glass ceramics have been prepared and characterized. The crystallization and optical properties of the glass ceramics were studied by XRD, SEM, and fluorescence spectra. The precipitated crystalline phase in the glass ceramics was prismatic diopside (CaMgSi₂O₆) and plate-like cristobalite (β-SiO₂). As the heat treatment time increases, the content of crystals increases gradually. Fluorescence measurements showed that Eu²⁺ ions entered into the diopside crystalline phase and induced a much stronger emission in the glass ceramics than that in the corresponding glass. With increase of Eu²⁺ content, concentration quenching was observed.     

Structural and optical properties of Ho2TeO6 micro-crystals embedded in tellurite matrix

In the present work, Ho³⁺ doped tellurite glasses and glass ceramics have been explored. Micro-sized Ho₂TeO₆ crystals have been successfully prepared in TeO₂ matrix using two step heat treatment method. Structural, thermal and optical properties have been investigated using different characterization techniques. Variations in above mentioned properties were observed to improve when these crystals grew in TeO₂ matrix. We have reported several anti-Stokes and Stokes emissions extended from UV to NIR region on excitation with 532 and 976 nm laser radiations. The unique structure of Ho₂TeO₆ crystal was expected to play a crucial role in enhancement of the optical properties of glass ceramics.     

Thermal and physical characterisation of apatite/wollastonite bioactive glass–ceramics

Glass–ceramics, containing apatite and wollastonite (A/W) crystals in the MgO–CaO–SiO₂–P₂O₅ glassy matrix, show the ability to form tight chemical bonds with living tissues when implanted in the body, as demonstrated by Kokubo and co-workers. However, the medical applications are mainly limited to non-load bearing conditions because of their poor mechanical properties. To overcome this drawback, a coating of the A/W glass–ceramic could be deposited onto a titanium substrate, in order to combine the good bioactivity of the bioceramic and the good mechanical strength of the titanium alloy base material. In this study, A/W powders obtained from commercial raw materials were thermally sprayed by APS (atmospheric plasma spraying) on Ti–6Al–4V substrates. Since in the as-sprayed conditions the coating microstructure was defective because of pores and cracks, thermal treatments on A/W plasma-sprayed coatings were conducted to enhance the coating microstructure. In order to gain a deeper insight, A/W bulk and sintered samples of the same composition were prepared and subjected to the same thermal treatments. In addition, the crystallisation behaviour of A/W bioactive glass–ceramic was investigated. The frits thermal behaviour was characterised by means of hot stage measurements and DTA analysis. DTA analysis on the A/W base glass, revealed two crystallisation peaks at about 1150 and 1193 K, corresponding to the crystallisation of oxyapatite and β-wollastonite phases, respectively. The two corresponding activation energies, calculated with the Kissinger equation, were also reported.The microstructure and the crystallinity of the A/W glass–ceramics were evaluated depending on the thermal treatment. The morphology and the microstructure were observed by SEM and the crystalline phases were detected by X-ray diffraction. Finally the porosity was determined via image analysis.     

Effect of P2O5 on the Nonisothermal Sinter‐Crystallization Process of a Lithium Aluminum Silicate Glass

Dense (~98.5%), lithium aluminum silicate glass‐ceramics were obtained via the sinter‐crystallization of glass particle compacts at relatively low temperatures, that is, 790–875°C. The effect of P₂O₅ on the glass‐ceramics' sinter‐crystallization behavior was evaluated. We found that P₂O₅ does not modify the surface crystallization mechanism but instead delays the crystallization kinetics, which facilitates viscous flow sintering. Our glass‐ceramics had virgilite (Li_xAl_xSi_3‐xO₆; 0.5 < x < 1), a crystal size <1 μm, and a linear thermal expansion coefficient of 2.1 × 10^?6°C^?1 in the temperature range 40–500°C. The overall heat treatment to obtain these GCs was quite short, at ~25 min.     

Sealing Glass‐Ceramics with Near Linear Thermal Strain,Part I: Process Development and Phase Identification

A widely adopted approach to form matched seals in metals having high coefficient of thermal expansion (CTE), e.g. stainless steel, is the use of high CTE glass‐ceramics. With the nucleation and growth of Cristobalite as the main high‐expansion crystalline phase, the CTE of recrystallizable lithium silicate Li₂O–SiO₂–Al₂O₃–K₂O–B₂O₃–P₂O₅–ZnO glass‐ceramic can approach 18 ppm/°C, matching closely to the 18 ppm/°C–20 ppm/°C CTE of 304L stainless steel. However, a large volume change induced by the α‐β inversion between the low‐ and high‐ Cristobalite, a 1^st order displacive phase transition, results in a nonlinear step‐like change in the thermal strain of glass‐ceramics. The sudden change in the thermal strain causes a substantial transient mismatch between the glass‐ceramic and stainless steel. In this study, we developed new thermal profiles based on the SiO₂ phase diagram to crystallize both Quartz and Cristobalite as high expansion crystalline phases in the glass‐ceramics. A key step in the thermal profile is the rapid cooling of glass‐ceramic from the peak sealing temperature to suppress crystallization of Cristobalite. The rapid cooling of the glass‐ceramic to an initial lower hold temperature is conducive to Quartz crystallization. After Quartz formation, a subsequent crystallization of Cristobalite is performed at a higher hold temperature. Quantitative X‐ray diffraction analysis of a series of quenched glass‐ceramic samples clearly revealed the sequence of crystallization in the new thermal profile. The coexistence of two significantly reduced volume changes, one at ~220°C from Cristobalite inversion and the other at ~470°C from Quartz inversion, greatly improves the linearity of the thermal strains of the glass‐ceramics, and is expected to improve the thermal strain match between glass‐ceramics and stainless steel over the sealing cycle.     

Synthesis, characterization and in vitro bioactivity of magnesium-doped sol-gel glass and glass-ceramics

Bioactive glass and glass-ceramics in the system CaO-MgO-SiO₂-P₂O₅ have been prepared by the sol-gel and high temperature sintering techniques. The obtained samples were characterized by thermogravimetric and differential thermal analysis (TG/DTA), N₂-adsorption measurement, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). In vitro bioactivity tests were also conducted in simulated body fluid (SBF). The studies of crystallization kinetics under non-isothermal conditions showed the activation energy for crystallization to be 381 kJ/mol and the crystallization mechanism gradually changed from three-dimension growth to two-dimension crystallization with the increase of heating rate. Sintering temperature had great influence on the samples texture and structure. In addition, the apatite-formation on glass and glass-ceramics was confirmed by in vitro tests, and crystallization decreased the samples bioactivity.     

Infrared to Visible Up‐Conversion Emission in Er3+/Yb3+ Codoped Fluoro–Phosphate Glass–Ceramics

Erbium Er³⁺ and ytterbium Yb³⁺ codoped fluoro‐phosphate glasses belonging to the system NaPO₃–YF₃–BaF₂–CaF₂ have been prepared by the classical melt‐quenching technique. Glasses containing up to 10 wt% of erbium and ytterbium fluorides have been obtained and characterized using differential scanning calorimetry (DSC) and UV–visible and near‐infrared spectroscopy. Transparent and homogeneous glass–ceramics have been then reproducibly synthetized by appropriate heat treatment above glass transition temperature of a selected parent glass. Structural investigations of the crystallization performed through X‐ray diffractometry (XRD) and scanning electron microscopy (SEM) have evidenced the formation of fluorite‐type cubic crystals based during the devitrification process. Finally, infrared to visible up‐conversion emission upon excitation at 975 nm has been studied on the Er³⁺ and Yb³⁺ codoped glass–ceramics as a function of thermal treatment time. A large enhancement of intensity of the up‐conversion emissions–about 150 times‐ has been observed in the glass–ceramics if compared to the parent glass one, suggesting an incorporation of the rare‐earth ions (REI) into the crystalline phase.     

Growth behavior,morphology and properties of lithium aluminosilicate glass ceramics with different amount of CaO,MgO and TiO2 additive

Li₂O–Al₂O₃–SiO₂ glass with CaO, MgO and TiO₂ additive were investigated. With more CaO + MgO addition, the crystallization temperature (T_p) and the value of Avrami constant (n) decreased, the activation energy (E) increased. The mechanism of crystallization of the glass ceramics changed from bulk crystallization to surface crystallization. With more TiO₂ addition, the crystallization temperature decreased, E and n had a little change. The crystallization of the glass ceramics changed from surface crystallization to two-dimensional crystallization. Plate-like, high mechanical properties spodumene-diopside glass ceramics were obtained. The mechanical properties related with crystallization and morphology of glass ceramics.     

Influence of Al2O3 and B2O3 on Sintering and Crystallization of Lithium Silicate Glass System

This article reports on the effect of Al₂O₃ and B₂O₃ added as dopants on the preparation of glass‐ceramics (GCs) belonging to the lithium silicate glass system. The GCs are prepared by sintering route using glass powders. The reasons for the crystallization of the metastable crystalline phase lithium metasilicate (LS) are discussed and the impact of the dopants on the thermodynamics and kinetics of crystallization is investigated. The addition of dopants modifies the thermodynamic equilibrium of the system and this change is mainly entropy driven and also slowdown the kinetics of crystallization. Differential thermal analysis and hot‐stage microscopy are employed to investigate the glass‐forming ability, sintering, and crystallization behavior of the studied glasses. The crystalline phase assemblage studied under nonisothermal heating conditions in the temperature range of 800°C–900°C in air. Well sintered and dense glass‐ceramics are obtained after sintering of glass powders at 850°C–900°C for 1 h featuring crystalline phase assemblage dominated by lithium disilicate (LS₂).     

Crystallization Behavior of Lithium–Iron-Phosphate Glasses with Additions of ZrO<Subscript>2</Subscript>

Lithium–iron-phosphate (LIP) glasses with different amounts of zirconia were prepared by conventional melting and annealing process. The influence of the nucleation agent, zirconia, on the crystallization behavior of LIP glasses has been studied using differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electronic microscopy (SEM) techniques. The results show that addition of 2 wt% of zirconia results in increases in the glass transition and crystallization temperatures and a decrease in the activation energy of crystallization. However, both temperatures decrease with increased addition of zirconia while the activation energy increases. The zirconia-free LIP glass only shows surface crystallization with crystals of LiFeP₂O₇. The glass containing 2 wt% of zirconia also has surface crystallization; however, mixed ZrP₂O₇ and LiFeP₂O₇ are crystallized. The addition of 5 and 8 wt% of zirconia leads to bulk crystallization and increasing formation of ZrP₂O₇ crystals besides the LiFeP₂O₇ phase.     

SiO2–Al2O3–CaO glass-ceramics: Effects of CaF2 on crystallization,microstructure and properties

The effects of fluorine content on the nucleation and crystallization behavior of SiO₂–Al₂O₃–CaO glass ceramics system have been investigated. The crystalline phases were determined by X-ray diffraction (XRD). The crystallization kinetics was determined by differential thermal analysis (DTA). The microstructures were examined by using scanning electron microscope (SEM). Fourier transformed infrared spectra (FTIR) analysis was used to study the glass structure. The results showed that by increasing the fluorine content, both the crystallization peak temperature (T_p) and activation energy (E) decreased. Wollastonite, anorthite and gehlenite are the main crystalline phases that exist in the glass ceramics system. The study shows that fluorine promoted initial crystallization of glass and can be used as an effective nucleating agent in the SiO₂–Al₂O₃–CaO system.