Bioactivity of SiO2-CaO-P2O5-Na2O glasses containing zinc-iron oxide

Glasses with composition x(ZnO,Fe₂O₃)(65 − x)SiO₂20(CaO,P₂O₅)15Na₂O (6 ≤ x ≤ 21 mol%) were prepared by melt-quenching technique. Bioactivity of the glasses was investigated in vitro by examining apatite formation on the surface of glasses treated in acellular simulated body fluid (SBF) with ion concentrations nearly equal to those in human blood plasma. Formation of bioactive apatite layer on the samples treated in SBF was confirmed by using Fourier transform infrared reflection (FTIR) spectroscopy, grazing incidence X-ray diffraction (GI-XRD) and scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer. Development of an apatite structure on the surface of the SBF treated glass samples as functions of composition and time could be established using the GI-XRD data. FTIR spectra of the glasses treated in SBF show features at characteristic vibration frequencies of apatite after 1-day of immersion in SBF. SEM observations revealed that the spherical particles formed on the glass surface were made of calcium and phosphorus with the Ca/P molar ratio being close to 1.67, corresponding to the value in crystalline apatite. Increase in bioactivity with increasing zinc-iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of glass composition and immersion time in SBF.     

In vitro evaluation of bioactivity of CaO-SiO2-P2O5-Na2O-Fe2O3 glasses

Glasses with compositions 41CaO(52 − x)SiO₂4P₂O₅·xFe₂O₃3Na₂O (2 ≤ x ≤ 10 mol.%) were prepared by melt quenching method. Bioactivity of the different glass compositions was studied in vitro by treating them with simulated body fluid (SBF). The glasses treated for various time periods in SBF were evaluated by examining apatite formation on their surface using grazing incidence X-ray diffraction, Fourier transform infrared reflection spectroscopy, scanning electron microscopy and energy dispersive spectroscopy techniques. Increase in bioactivity with increasing iron oxide content was observed. The results have been used to understand the evolution of the apatite surface layer as a function of immersion time in SBF and glass composition.     

Study on the surface bioactivity of novel magnetic A-W glass ceramic in vitro

Novel magnetic A-W glass ceramic (M GC) in the system MgO-CaO-SiO₂-P₂O₅-CaF₂-MnO-ZnO-Fe₂O₃ was synthesized by doping Mn-Zn ferrite to apatite-wollastonite glass ceramic. The phase composition was investigated by XRD. The magnetic property was measured by VSM. The in vitro bioactivity was tested by immersion in simulated body fluid. The result shows apatite, wollastonite, fluorapatite and Zn_0.75Mn_0.75Fe_1.5O₄ are the main phases of M GC. Under a magnetic field of 10,000 Oe, the saturation magnetization and coercive force of the material are 6 emu g⁻ and 180 Oe, respectively. After soaking in SBF for 14 days, the surface of M GC is coated by a hydroxycarbonate apatite layer.     

Effects of Mg and Zn on the surface of doped melt-derived glass for biomaterials applications

Bioactive glasses in the system SiO₂-CaO-Na₂O-P₂O₅ were synthesized pure and doped with magnesium or zinc by melt-derived method. The bioactivity was studied during in vitro assays: the ability of hydroxycarbonate apatite (HCA) layer to form on the glass surface was examined after contact with simulated body fluid (SBF). The X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) studies were performed before and after immersion in vitro assays. The SBF solutions were also analyzed using inductively coupled plasma-optical emission spectroscopy (ICP-OES).Introduction of magnesium and zinc as trace element induces several modifications on the observed phenomena at the glass surface and in SBF solution after immersion of the samples. The chemical durability of the glasses, the formation of the silica-rich layer and the crystallization of the HCA layer were affected, but not present the same modifications as the introduced doping element.     

Compositional dependence of in-vitro bioactivity in sodium calcium borate glasses

Borate glasses with composition xCaO (100−x) B₂O₃ (20≤x≤50), where x is in mole percent) and 50CaO·45B₂O₃·5Na₂O have been prepared using conventional melt quench technique. Samples were submerged in simulating body fluid solution (SBF) at 37 °C for various periods of time. After storage the samples were analyzed in order to investigate if a surface layer of hydroxyl carbonate apatite layer (HCA layer/Ca-P layer) had formed. The analysis technique used included Fourier-Transform Infrared Spectroscopy (FTIR). The rate of HCA layer formation on the surface of exposed glass samples is determined by FTIR, percentage weight loss measurements of glass samples in SBF and variation of pH of SBF as a function of time. Increase in calcium content in the glass matrix has shown to decrease the rate of HCA formation on glass surfaces. The borate glass with x=20 has shown HCA layer formation on glass surface within two days of dipping. The bone like apatite formation of glass surface demonstrates the potential of glass for integration with bone.     

Biomineralization of electrospun poly(l-lactic acid)/gelatin composite fibrous scaffold by using a supersaturated simulated body fluid with continuous CO2 bubbling

To promote the biomineralization, supersaturated simulated body fluids (SBFs), e.g. five times SBF (5 × SBF), were usually applied. In these SBFs, however, homogeneous nucleation of Ca-P mineralites and deposition unavoidably took place owing to the HCO₃⁻ decomposition and the pH value increment, which made the prediction of bone bioactivity of substrates controversial. In this study, the classically prepared 5 × SBF was continuously bubbled with CO₂ to keep the pH value stable at 6.4 and the solution transparent, and a kind of electrospun poly(l-lactic acid)/gelatin composite fibers was used for the biomineralization study. In such a modified 5 × SBF, heterogenenous nucleation occurred dominantly and thermodynamical unstable brushites (dicalcium phosphate dihydrate, DCPD) were detected shortly on both electrospun PLLA fibers and PLLA/gelatin (1:1 in weight) composite fibers. In comparison with electrospun PLLA fibers, the sheet-like DCPD mineralites transformed into flaky carbonated calcium-deficient hydroxyapatite (CDHA) within 24 h on the PLLA/gelatin composite fibers due to the accelerating effect of gelatin component. The formed apatite coating contained much less Mg²⁺ ions than that deposited in the classical 5 × SBF. The results of this study showed that supersaturated SBFs buffered with gassy CO₂ were expected good choices for the accelerated biomineralization, and for the prediction of the bone bonding bioactivity of substrates.     

Effect of annealing temperature on the decomposition of reactively sputtered Ag2Cu2O3 films

Ag₂Cu₂O₃ films were deposited on glass substrates by reactive sputtering of a composite silver-copper target. The deposited films were annealed in air at 100, 200 and 300 °C. The structure of the films was studied using X-ray diffraction (XRD), their surface morphology was characterised using scanning electron microscopy (SEM) and their electrical resistivity at room temperature was measured using the four point probe method. The 100 °C annealing did not modify either the film structure or the film morphology. On the other hand, Ag₂Cu₂O₃ films were partially decomposed into Ag and CuO after a 200 °C annealing. The decomposition was complete for a 300 °C annealing. The evolution of the film surface morphology as a function of the annealing temperature was discussed in connection to the evolution of the molar volume of the phases constituting the films.     

Magnetic and bioactivity evaluation of ferrimagnetic ZnFe2O4 containing glass ceramics for the hyperthermia treatment of cancer

Glass ceramics of the composition xZnO·25Fe₂O₃·(40−x)SiO₂·25CaO·7P₂O₅·3Na₂O were prepared by the melt-quench method using oxy-acetylene flame. Glass-powder compacts were sintered at 1100 °C for 3 h and then rapidly cooled at −10 °C. X-ray diffraction (XRD) revealed 3 prominent crystalline phases: ZnFe₂O₄, CaSiO₃ and Ca₁₀(PO₄)₆(OH)₂. Vibrating sample magnetometer (VSM) data at 10 KOe and 500 Oe showed that saturation magnetization, coercivity and hence hysteresis area increased with the increase in ZnO content. Nano-sized ZnFe₂O₄ crystallites were of pseudo-single domain structure and thus coercivity increased with the increase in crystallite size. ZnFe₂O₄ exhibited ferrimagnetism due to the random distribution of Zn²⁺ and Fe³⁺ cations at tetrahedral A sites and octahedral B sites. This inversion/random distribution of cations was probably due to the surface effects of nano-ZnFe₂O₄ and rapid cooling of the material from 1100 °C (thus preserving the high temperature state of the random distribution of cations). Calorimetric measurements were carried out using magnetic induction furnace at 500 Oe magnetic field and 400 KHz frequency. The data showed that maximum specific power loss and temperature increase after 2 min were 26 W/g and 37 °C, respectively for the sample containing 10% ZnO. The samples were immersed in simulated body fluid (SBF) for 3 weeks. Scanning electron microscope (SEM), energy dispersive spectroscopy (EDX) and XRD results confirmed the growth of precipitated hydroxyapatite phase after immersion in SBF, suggesting that the ferrimagnetic glass ceramics were bioactive and could bond to the living tissues in physiological environment.     

The influence of the sintering temperature on the structural and the magnetic properties of doped manganites: La0.95Ag0.05MnO3 and La0.75Ag0.25MnO3

La_1−xAg_xMnO₃ samples were synthesized by standard sol-gel method with Ag concentrations of x=0.05 and 0.25. The samples from each concentration were pressed and sintered at 1000, 1200 and 1400 °C for 24 h in air for a systematic study. They were examined structurally by Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) with Energy Dispersive Spectroscopy (EDS) and X-ray Diffraction (XRD) and magnetically by Magnetic Properties Measurements System (MPMS). AFM and SEM analyses show that surface morphology changes with Ag concentration and sintering temperature (T_S). It was observed that high temperature sintering leads Ag to leave material as determined from EDS analyses. XRD spectra exhibited that the crystal structure changes with Ag concentration while showing pronounced change with the sintering temperature. From the magnetic measurements, the Curie temperatures (T_C) and the isothermal magnetic entropy changes (−ΔSM) were calculated. It was observed that T_C increases with Ag concentration and decreases with T_S. The maximum −ΔSM was calculated to be 7.2 J/kg K under the field change of 5 T for the sample sintered at 1000 °C with x=0.25.     

Excellent stability of plasma-sprayed bioactive Ca3ZrSi2O9 ceramic coating on Ti-6Al-4V

In this work, novel zirconium incorporated Ca-Si based ceramic powder Ca₃ZrSi₂O₉ was synthesized. The aim of this study was to fabricate Ca₃ZrSi₂O₉ coating onto Ti-6Al-4V substrate using atmospheric plasma-spraying technology and to evaluate its potential applications in the fields of orthopedics and dentistry. The phase composition, surface morphologies of the coating were examined by XRD and SEM, which revealed that the Ca₃ZrSi₂O₉ coating was composed of grains around 100 nm and amorphous phases. The bonding strength between the coating and the substrate was 28 ± 4 MPa, which is higher than that of traditional HA coating. The dissolution rate of the coating was assessed by monitoring the ions release and mass loss after immersion in the Tris-HCl buffer solution. The in vitro bioactivity of the coating was determined by observing the formation of apatite on its surface in simulated body fluids. It was found that the Ca₃ZrSi₂O₉ coating possessed both excellent chemical stability and good apatite-formation ability, suggesting its potential use as bone implants.     

MAO-synthesized Al2O3-supported V2O5 nano-porous catalysts: Growth, characterization, and photoactivity

V₂O₅-loaded Al₂O₃ layers were successfully grown via micro-arc oxidation (MAO) process for the first time. Surface morphology and topography of the layers were investigated by scanning electron microscope (SEM) and atomic force microscope (AFM). It was found that the composite layers had a porous structure with a rough surface which is suitable for catalytic applications. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDS) techniques were also employed to study phase structure and chemical composition of the composite layers. The layers consisted of γ-alumina, α-alumina, and vanadium pentoxide phases in which their relative contents varied with the applied voltage. Meanwhile, optical properties of the composite layers were investigated using UV-vis spectrophotometry technique, and the band gap energy was calculated as 3.15 eV. Furthermore, photocatalytic performance of the synthesized composite layers was determined by measuring the decomposition rate of methylene blue solution, as a model compound, on the surface of the layers under ultra violet photo-irradiation. It was found that more than 91% of the methylene blue was degraded after 120 min with a rate constant of k = 0.0192 min⁻¹.     

Improving the bioactivity of NiTi shape memory alloy by heat and alkali treatment

TiO₂ films were formed on an NiTi alloy surface by heat treatment in air at 600 °C. Heat treated NiTi shape memory alloys were subsequently alkali treated with 1 M, 3 M and 5 M NaOH solutions respectively, to improve their bioactivity. Then treated NiTi samples were soaked in 1.5SBF to evaluate their in vitro performance. The results showed that the 3 M NaOH treatment is the most appropriate method. A large amount of apatite formed within 1 day's soaking in 1.5SBF, after 7 day's soaking TiO₂/HA composite layer formed on the NiTi surface. SEM, XRD, FT-IR and TEM results showed that the morphology and microstructure are similar to the human bone apatite.     

Synthesis and bioactivity of highly ordered TiO2 nanotube arrays

The highly ordered TiO₂ nanotube arrays were fabricated by potentiostatic anodization of Ti foils in fluorinated dimethyl sulfoxide (DMSO). TiO₂ nanotube arrays are formed using a 40 V anodization potential for 24 h, with a length of 12 μm, diameter of 170 nm and aspect ration of about 70. The as-prepared nanotubes are amorphous, but can be crystallized as the heat treatment temperature increases. Anatase phase appears at a temperature of about 300 °C, then transforms to rutile phase at about 600 °C. After heat treatment at 500 °C and soaking in SBF for 14d, a thick apatite layer of about 13 μm covers the whole surface of TiO₂ nanotube arrays, indicating their excellent in vitro bioactivity, which is mainly attributed to their high specific surface area and the anatase phase.     

Hollow glass microspheres coated with CoFe2O4 and its microwave absorption property

Spinel CoFe₂O₄ coating on the surface of hollow glass microspheres of low density was synthesized by co-precipitation method. The phase structures, morphologies, particle size, shell thickness, chemical compositions of the composites have been characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and energy dispersive X-ray spectroscopy (EDS). The results show that CoFe₂O₄ coating on hollow glass microspheres can be achieved, and the coating layers are constituted by CoFe₂O₄ nanoparticles of mean size ca. 10 nm. The as-synthesized powder materials were uniformly dispersed into the phenolic cement, then the mixture was pasted on metal plate with the area of 200 mm×200 mm as the test plate. The test of microwave absorption was carried out by the radar-absorbing materials (RAM) reflectivity far field radar cross-section (RCS) method. The results indicate that the coated CoFe₂O₄/hollow glass microspheres composites can be applied in lightweight and strong absorption microwave absorbers.     

Study of the synthesis and Cl2 gas-sensing properties of nanometer HNO3-doped SnO2

We focused on the effects of the inorganic acid HNO₃ on the gas-sensing properties of nanometer SnO₂ and prepared the powders via a dissolution-pyrolysis method. Furthermore, the powders were characterized by means of X-ray diffraction (XRD), scanning electron microscope (SEM), field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray spectra (EDS). Several aspects were surveyed, including the calcining temperature, concentration of nitric acid and the working temperature. The results showed that the gas response of 3 wt% HNO₃-doped SnO₂ powders (calcined at 500 °C) to 10 ppm Cl₂ reached 316.5, at the working temperature 175 °C. Compared with pure SnO₂, appropriate HNO₃ could increase the gas sensitivity to Cl₂ gas more significantly.     

Effect of ZnO on phase emergence, microstructure and surface modifications of calcium phosphosilicate glass/glass-ceramics having iron oxide

The effect of ZnO on phase emergence and microstructure properties of glass and glass-ceramics with composition 25SiO₂-50CaO-15P₂O₅-(10 − x)Fe₂O₃-xZnO (where x = 0, 2, 5, 7 mol%) has been studied. They have been characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Surface modifications of these glass-ceramics in simulated body fluid have been studied using Fourier transform infrared reflection spectroscopy (FTIR), XPS and SEM. Results have shown a decrease in the fraction of non-bridging oxygen with increase in zinc oxide content. Emergence of crystalline phases in glass-ceramics at different heat treatment temperatures was studied using XRD. When glass is heat treated at 800 °C calcium phosphate, hematite and magnetite are developed as major phases in the glass-ceramics samples with ZnO up to 5 mol%. In addition to these, calcium silicate (Ca₃Si₂O₇) phase is also observed when glass is heat treated at 1000 °C. The microstructure of the glass-ceramics heat treated at 800 °C exhibits the formation of nano-size (40-50 nm) grains. On heat treatment at 1000 °C crystallites grow to above 50 nm size and more than one phase are observed in the microstructure. The formation of thin flake-like structure with coarse particles is observed at high zinc oxide concentration (x = 7 mol%). In vitro studies have shown the surface modifications and formation of Ca-P-rich layer on the glass-ceramics when immersed in simulated body fluids (SBF) for different durations. The bioactive response was found to depend on ZnO content.     

Structural transformations of Fe81B13Si4C2 amorphous alloy induced by heating

Thermal stability and crystallization of the Fe₈₁B₁₂Si₄C₂ alloy were investigated in the temperature range 25-700 °C by the XRD and Mössbauer analysis. It was shown that on heating the as-prepared amorphous Fe₈₁B₁₂Si₄C₂ alloy undergoes thermal stabilization through a series of structural transformations involving the process of stress-relieving (temperature range 200-400 °C), followed by a loss of ferromagnetic properties (Curie temperature at 420 °C) and finally crystallization (temperature range 450-530 °C). The process of crystallization begins by formation of two crystal phases: Fe₃B and subsequently Fe₂B, as well as a solid solution α-Fe(Si). With increase in annealing temperature, the completely crystallized alloy involved only two phases, Fe₂B and solid solution α-Fe(Si).XRD patterns established a difference in phase composition and size of the formed crystallites during crystallization depending on the side (fishy or shiny) of the ribbon. The first nuclei of the phase α-Fe₃Si were found on the shiny side by XRD after heat treatment even at 200 °C but the same phase on the fishy side of ribbon was noticed after heat treatment at 450 °C. The largest difference between the contact and free surface was found for the Fe₂B phase crystallized by heating at 700 °C, showing the largest size of crystallites of about 130 nm at 700 °C on the free (shiny) surface.     

Investigation on bio-mineralization of melt and sol-gel derived bioactive glasses

The bio-mineralization properties of the melt-derived bioactive glass 45S5 and the sol-gel derived bioactive glasses 58S and 77S were investigated and compared using in vitro test combined with BET, XRD, FTIR and SEM techniques. It was found that the surfaces of the three bioactive glasses could be mineralized by immersion in a simulated body fluid (SBF) at 37 °C for several hours. The bio-mineralized products on the surfaces of the bioactive glasses were apatite microcrystals with a low crystallinity, but the composition and morphologies of the apatite microcrystals on three glasses were different.     

Growth and characterization of Mg(OH)2 film on magnesium alloy AZ31

Magnesium-based biomaterials have been proposed as potential candidates for biodegradable implant materials, such as bone screws, bone plates, intraluminal stents and so on. However, the poor corrosion resistance inhibits their applications in surgery. They collapse before the injured tissues are healed. In this paper, Mg(OH)₂ nonstructural film was synthesized on the substrate of AZ31 magnesium alloy by hydrothermal method with NaOH solution as mineralizer to reduce the corrosion rate of magnesium-based materials. The obtained films were characterized by XRD, SEM, and XPS. The results showed that a Mg(OH)₂ film with nanostructure surface can be synthesized by hydrothermal method. It was observed that the thickness of film increased with the holding time. Corrosion rates of the films were studied by immersing the samples in Hank's solution (37 °C). Surface deposits of samples with films soaked in Hank's solution for 31 days were investigated by XRD, SEM, EDS, XPS, and FTIR. It verified that the corrosion rate of the magnesium alloy with grown film was slowed down in the Hank's solution and the behavior of corrosion was inhibited effectively. Amorphous calcium apatite precursor was observed to deposit on the surface of the film during corrosion experiments in Hank's solution. And the tape test revealed a strong adhesion between the film and the substrate.     

Synthesis and characterization of thermoluminescent glass-ceramics Li2O-Al2O3-SiO2:CeO2

Vitroceramic powders of Li₂O-Al₂O₃-SiO₂ systems (LAS), doped with 1% (LAS:1Ce) and 10% (LAS:10Ce) molar of cerianite (CeO₂) were synthesized by means of the gelification technique of metal formates of aluminum and lithium, in the presence of tetraethoxy silane and CeO₂. The gels obtained were dried (120 °C, 2.5 h), calcined (480 °C, 5 h) and sinterized (1250 °C, 30 min). The sinterized samples were characterized by X-ray difraction (XRD), scanning electron microscopy (SEM) and microchemical analysis (EDS). There is evidence for a mixture of two phases of 64% β-spodumene (Li₂O-Al₂O₃-4SiO₂) and 36% β-eucryptite (Li₂O-Al₂O₃-2SiO₂). The LAS:1Ce system was enriched in aluminum, the LAS:10Ce system showed areas of heterogeneous composition; some regions with a shortage of CeO₂, while others zones with cerium cumulus. From the microscopy images it was found that CeO₂ acts as a densificant agent in LAS system, favoring the sintering in the host. The chemical route and the sintering processes utilized allow the production of samples exhibiting an acceptable linear correlation between total thermoluminescent emission intensity and the irradiation dose when the CeO₂ concentration is low (less than 1%), opening the possibility of using this kind of glass-ceramic in dosimetry.