Synthesis and characterization of SnO-containing phosphorous oxynitride glasses

SnO-containing oxynitride phosphate glasses have been obtained by ammonolysis and their structure studied by nuclear magnetic resonance. The nitrided glasses are characterized by tetrahedral units P(O,N)₄ in which nitrogen atoms have substituted both bridging and non-bridging oxygen atoms. The N/O substitution in the anionic network induces important changes in the glass properties such as an increase in the glass transition temperature and a decrease in the coefficient of thermal expansion. ³¹P MAS NMR shows that PO₄, PO₃N and PO₂N₂ units coexist within the vitreous network and their relative proportions are a function of the nitrogen content as well as of the base glass composition. The influence of the different modifiers on the nitridation process is explained through a comparative study of the LiNaSnPON and LiNaPbPON systems. Unlike lead in oxynitride glasses, tin affects the nitridation mechanism by limiting the nitrogen/oxygen substitution in the anionic network, so that the substitution model is assumed to be closer to the one taking place in alkali phosphate glasses LiNaPON.     

Structural analysis of bioactive glasses

In this study four series of single and mixed alkali glass systems were made and investigated using MAS NMR. Additionally the densities of the glasses were measured experimentally, as well as calculated theoretically using Doweidar’s model. MAS NMR was used to obtain a quantitative structural understanding of glasses by calculating the concentrations of bridging and non-bridging oxygens per silicon oxygen tetrahedron as a function of the alkali oxide concentration expressed as Qⁿ. ²⁹Si MAS NMR spectra exhibited a single resonance corresponding closely with Si in a Q² state. The chemical shift of the ³¹P MAS NMR peak was attributed to phosphate in an orthophosphate environment. The ²⁹Si NMR spectra are in agreement with the density data. Using Doweidar’s model the proportions of Q² and Q³ were calculated, showing that all glasses studied are predominantly Q² in structure, i.e. silica chains which readily dissolve. The changes in the chemical shifts of the Q² and Q³ species with composition have been interpreted as resulting from the preferential association of Na⁺ with Q³ and Ca²⁺ with Q².     

Synthesis and characterization of tin containing molybdophosphate and tungstophosphate glasses

Two series of tin containing molybdophosphate and tungstophosphate glasses and glass-ceramics were achieved by means of a domestic microwave oven under air. During melting, a redox reaction takes place between Sn²⁺ and Mo⁶⁺ generating the crystallization of a Na(Sn^IV,Mo^IV)(PO₄)₃ solid solution with a NZP (NaZr₂P₃O₁₂) type structure. Such reactivity was not underlined in the case of the W-series. All the samples were characterized from a thermal and mechanical point of view as a function of the RO₃ (R = Mo, W) for SnO substitution. Two types of behaviors were identified. For the Mo-series, all the characteristics, except density, present an extremum value for the chemical composition with a 1:1 SnO-MoO₃ molar ratio. This is strongly correlated to the amount of NZP crystals present in the glass ceramic, the different behavior observed for the density being due to the low compactness of the NZP phase. For the W-series, all these different characteristics varies monotonously according to a progressive strengthening of the network by replacement of a low field strength ion (Sn²⁺) by a higher field strength ion (W⁶⁺). In addition, the solid state reactivity of a 1:1 SnO-RO₃ mixture was examined confirming the absence of any redox process between SnO and WO₃ during the glass synthesis.     

Synthesis and structural characterization of potato starch sponges

Materials with hierarchical porous structures have attracted great attention over the past years since they have been widely used in many industrial applications. Starch stands out among the materials commonly used as sacrificial templates in environmentally friendly applications. In addition, starch is inexpensive, easy to process, and readily available. In this work we present a structural characterization of sponges prepared by freezing and thawing of a starch gel. Samples obtained in this study were examined by scanning electron microscopy (SEM) and X-ray microtomography (μ-CT). SEM tests revealed that these samples show an open macroporous framework with continuous walls. μ-CT tests revealed that it is possible to tailor the pore structure of these materials by changing the starch concentration in gels used in their processing. We noticed that increasing starch concentration from 15 wt.% to 60 wt.% leads to sponges with porosities ranging from about 28% to over 65%. It was also observed that the higher the starch concentration, the greater the mean pore size of the prepared sponge.     

Synthesis and characterization of potassium, rubidium, and cesium thiogermanate glasses

Glass-forming regions were investigated for the binary xM₂S + (1 − x)GeS₂ (M=K, Rb, Cs) systems. Glasses were prepared from 0?x?0.20 mole fraction alkali sulfide using a novel preparation route involving the decomposition of the alkali hydrosulfides in situ. At higher alkali concentrations near x=0.33, the glass-forming regions are limited by the readily formed adamantane-like M₄Ge₄S₁₀ crystals. Structural characterization of the glasses and polycrystals for x?0.33 were performed using Raman scattering and IR absorption. Terminal Ge-S⁻ vibrational modes, observed between 473 and 479 cm⁻¹, increased in intensity and decreased in frequency with increasing alkali modifier content. Glass transition temperatures decreased with increasing alkali modifier, ranging from 250 to 215 °C. Corresponding crystallization onset temperatures were between 340 and 385 °C. DC conductivity values of the glasses ranged from 10⁻¹⁰ to 10⁻⁷ (Ω cm)⁻¹ with activation energies between 0.54 and 0.93 eV for the temperature range of ∼100-250 °C. Higher ionic conductivities were observed with increasing alkali concentration and decreasing alkali radii. Additionally, an increase in the activation energy was observed above the glass transition temperature.     

Functionalization and bioactivity in vitro of mesoporous bioactive glasses

Amino and carboxylic groups functionalized mesoporous bioactive glasses (denoted as N-MBGs and C-MBGs, respectively) were successfully synthesized through a post-grafting process and characterized by XRD, N₂ sorption, TEM, FT-IR and TG techniques. Their in vitro bioactivity and degradation behavior were investigated in simulated body fluid and examined by various techniques. The results demonstrate that the bioactivity of all the samples and the morphology of carbonated hydroxyapatite were affected remarkably by the introduction of functional groups. Spherical carbonated hydroxyapatite particles were observed grown on the N-MBGs surfaces after soaking in simulated body fluid for 8 h, which is different from the rod-like carbonated hydroxyapatite grown on conventional mesoporous bioactive glasses. While for C-MBGs, the nucleation and growth rate of carbonated hydroxyapatite was decreased at increased contents of carboxylic groups.     

Synthesis and structural characterization of 2,5-dihalo-3,4-dinitrothiophenes

Using new nitration protocols, we have been able to efficiently dinitrate 2,5-dihalothiophenes with yields of ～80–95%. The resulting products 2,5-dibromo-3,4-dinitrothiophene (1), 2,5-dichloro-3,4-dinitrothiophene (2), 2-bromo-5-chloro-3,4-dinitrothiophene (3), as well as the analogous 2-bromo-3,4-dinitrothiophene (4), all crystallize easily allowing their characterization via X-ray crystallography. Crystallization of 1 occurs in the monoclinic space group C2/c with a = 14.547(3) Å, b = 7.3534(15) Å, c = 10.775(2) Å, β = 128.89(3)°, and Z = 4. Crystallization of 2 occurs in the tetragonal space group I-42d with a = 9.9398(14) Å, b = 9.9398(14) Å, c = 16.866(3) Å, and Z = 8. Crystallization of 3 occurs as a pseudo-merohedral twin in the triclinic space group P-1 with a = 7.340(5) Å, b = 8.094(5) Å, c = 9.112(5) Å, α = 82.059(5)°, β = 66.232(5)°, γ = 63.021(5)°, and Z = 2. Crystallization of 4 occurs in the triclinic space group P-1 with a = 7.1787(14) Å, b = 7.4092(15) Å, c = 8.3151(17) Å, α = 101.67(3)°, β = 96.00(3)°, γ = 116.13(3)°, and Z = 2. The structures of all compounds exhibit the formation of interesting solid-state assemblies due to halogen-bonding interactions between the halogen and nitro groups.     

Raman spectroscopic study of bioactive silica based glasses

A study of the structure and bonding configuration of the bioactive glasses in the system Na₂O–CaO–P₂O₅–SiO₂ by Fourier transform Raman spectroscopy is presented. The assignment of the Raman lines, the changes in the Si–O–Si bond environment and the identification of the non-bridging silicon–oxygen groups (Si–O–NBO) for a wide range of silicate glasses are discussed. The frequency shifting and intensity variations of the Raman lines as a function of the bioactive glass composition are attributed to a decrease of the local symmetry originated by the addition of alkali and alkali earth oxides to the vitreous silica network. Correlation plots for the quantification of the Si–O–NBO groups as a function of the glass composition are also presented. These Raman analyses contribute to a better knowledge of the structural role of the network modifiers in the bioactive glasses and, as a consequence, improve the understanding of the bioactive process and the chemical routes of the CaP layer formation when exposed body fluids.     

Synthesis and characterization of calcium phosphate based bioactive quaternary P2O5-CaO-Na2O-K2O glasses

Calcium phosphate based bioactive quaternary glass systems P₂O₅-CaO-Na₂O-K₂O were prepared by melt growth technique. Glasses were prepared in five different compositions by fixing P₂O₅ at 47 mol% and CaO at 30.5 mol% and by varying the K₂O and Na₂O concentrations. The structural properties of the glasses are analyzed using X-ray diffraction (XRD) studies and scanning electron microscopy (SEM) studies; and the composition of the glasses are studied using energy dispersive X-ray spectrum (EDS). The microhardness of the glass systems are studied by Vickers hardness measurements and the bioactivity of the glasses are studied using in vitro study. The thermal properties have been examined by means of thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The ultrasonic velocity measurements show that the addition of K₂O contents produces non-bridging oxygen ion and hence weaken of the glass structure. The weakening of the glass structure reduces the ultrasonic velocity and hence an increase in attenuation.     

Optical and structural properties of Sr-Nb-phosphate glasses

This research studied optical and structural properties of SrO-Nb₂O₅-P₂O₅ glasses containing 0 ~ 25 mol% Nb₂O₅ and 35 ~ 60 mol% SrO using spectra of UV-Vis, FTIR and XPS. Our aim was to work new moldable glasses which are colorless with high refractive index and transmittance, and their correlation with glass structure. Nb₂O₅ plays the role as an intermediate of glass formation, and transforms the role to network-former or glass-modifier depending on composition. Refractive index increases monotonically with Nb₂O₅ content at the expense of transmittance, and specific coloring which occurs in ternary compositions with the ratio P₂O₅/SrO > 1. This effect arises from much increased [Nb³⁺ and Nb⁴⁺] fraction, as quantitatively deconvoluted in Nb3d XPS spectra, in the ligand [NbO₆]_octahedral which is supported by FTIR and O1s XPS spectra. As the ratio P₂O₅/SrO ≤ 1, Nb₂O₅ is more of a network former and [NbO₆]_octahedral structure turns into [NbO₄]_tetrahedron with partial Nb-O…(Sr) bonding turns into (Nb-O-Nb)_tetrahedron, coloring disappears.     

Preparation and characterization of telluride glasses

Chalcogenide bulk glasses Ge₂₀Se_80?xTe_x for x ∈ (0, 10) have been prepared by systematic replacement of Se by Te. Selected glasses have been doped with Er and Pr, and all systems have been characterized by transmission spectroscopy, measurements of dc electrical conductivity and low-temperature photoluminescence. Absorption coefficient has been derived from measured transmittance and estimated reflectance. Both absorption and low-temperature photoluminescence spectra reveal shifts of absorption edge and/or dominant luminescence band to longer wavelength due to Te → Se substitution. Arrhenius plots of dc electrical conductivity, in the temperature range 300–450 K, are characterized by activation energies roughly equal to the half of the optical gap. Arrhenius plots for temperatures below 300 K yield much lower activation energies. The dominant low-temperature luminescence band centered at about half the band gap energy starts to quench above 200 K and a new band appears at 900 nm. The band at 900 nm, due to band to band transitions, overwhelms the spectra at room temperature. Systems doped with Er exhibit a strong luminescence due to ⁴I_13/2 → I_15/2 transition of Er³⁺ ion at 1539 nm, and Pr doped samples exhibit a relatively weak luminescence peak at 1590 nm, which we tentatively assign to ³F₃ → ³H₄ transition of Pr³⁺ ion.     

Synthesis and X-ray structural characterization of NiO nanoparticles obtained through gelatin

Nanoparticles of fcc-NiO phase were obtained by heating the dried resin resultant of a mixture of gelatin and NiCl₂ · 6H₂O in aqueous solution. The average particle size and microstrain were calculated from the line broadening of X-ray powder diffraction peaks, and these values were between 15 nm and 78 nm, and 0.056% and 0.172%, respectively. The Rietveld refinement method was applied to all diffraction patterns. The particle size, obtained from this procedure, changes as a function of temperature, heating time and the remarkable reduction due to the addition of NaOH to the solution, which can be attributed to the presence of NaCl crystals and carbon encapsulating NiO nanoparticles during the heating. The heating temperature was in the range of 350–700 °C. Thermo-gravimetric analysis showed that the majority of organic fraction starts to disappear after 300 °C.     

Tetracycline and/or hydrocortisone incorporation and release by bioactive glasses compounds

The delivery of the tetracycline and hydrocortisone drugs that have been incorporated into bioactive glasses was studied in this work. The potentiality of these systems in direct pulp capping is also discussed. A bioactive glass with a composition of (SiO₂)_0.80(P₂O₅)_0.04(CaO)_0.16, was prepared by sol-gel. Sols were prepared with the addition of approximately 2 wt% of tetracycline or hydrocortisone separately for the delivery studies. A third set of samples of bioglass sols containing 2 wt% of each drug were prepared with the same purpose. The amounts of drugs delivered were monitored by ultraviolet spectrophotometry in the tetracycline and hydrocortisone wavelengths. The drug release behavior was strongly dependent on the system. The glass-tetracycline samples showed a rapid drug release kinetics, while glass-hydrocortisone samples show much slow release profiles. The different drug release behaviors have been explained by faster gel formation reaction between hydrocortisone and TEOS due to a stronger interaction between these reagents. On the samples with both drugs, the release was simultaneous and for each drug, the amounts delivered followed a profile similar to the samples with only this specific drug.     

Influence of morphology on in vitro compatibility of bioactive glasses

In vitro bioactivity and biocompatibility of fiber and bulk bioactive glasses were studied. After synthesis with tetraethoxysilane, individual bulk and fiber samples were soaked in a simulated body fluid solution and removed at intervals of 5 and 30 days, respectively. Fourier transform infrared spectroscopic analysis showed hydroxyapatite characteristic P–O vibrational bands for simulated body fluid soaked fibers and bulk samples. Osteoblast viability and alkaline phosphatase production were evaluated by cell incubation in the presence of samples and compared to controls. Fiber glass-incubated osteoblasts showed lower viability but the same alkaline phosphatase production when compared to bulk sample and controls.     

Elastic properties and structural studies on lead-boro-vanadate glasses

This paper describes elastic properties and spectroscopic studies on the xPbO-50B₂O₃-(50 - x)V₂O₅ (where x = 20, 25, 30, 35, 40, 45 and 49 mol%) glass system. Elastic moduli and spectroscopic parameters exhibit compositional dependent trends and the existence of characteristic borovanadate groups in these glasses. The bulk modulus and shear modulus increase with the concentration of [BO_4/2]⁻ and [B₂V₂O₉]²⁻ groups, which increases the dimensionality of the network. The scheme of modification of borate and vanadate groups has been explained by considering the Sanderson’s electronegativity principle. Analysis of infrared(IR) and magic angle spinning-nuclear magnetic resonance (MAS-NMR) spectra suggests the presence of characteristic diborovanadate groups also in these glasses. The results are examined in view of the structural groups formed due to the presence of PbO as a modifier.     

Optical and structural properties of calcium silicate glasses

A detailed analysis of the reflectance and transmittance spectra of a set of glasses allowed retrieval, besides the optical functions, of quantitative information on the structural changes occurring in the calcium silicate glass system. The occurrence of a threshold around 46% of CaO content is confirmed and is connected to the appearance in the glass structure of a new configuration of calcium cations. It was also shown that the calcium cations that exceeds the compositional threshold does not act as modifiers of the silicate network since they form Ca–O–Ca bonds in the glass structure. Obvious changes occurring at the threshold in the physical or chemical properties can be understood in the light of the structural changes observed in the system.     

Optical and structural properties of new chalcohalide glasses

New class of chalcohalide glasses has been prepared in the GeS₂–In₂S₃–CsI system with regard to their potential non-linear properties. The study of glass-forming region was undertaken to select glassy compositions, which present high non-linear (NL) optical properties with a low two-photon absorption. Thermal analyses, structural examination by Raman spectroscopy, non-linear optical measurements were investigated as a function of CsI contents. Introduction of CsI has shifted the band-gap edge towards the blue region of the absorption optical spectrum and therefore has limited the two-photon absorption. Their NL refractive index n₂ are 60 times higher than silica glasses without any NL absorption. Moreover, second harmonic signal was observed in thermally poled samples similar to silica glass. However, this second order non-linearity is not temporally stable.     

Morphological control and in vitro bioactivity of nanoscale bioactive glasses

In this study, nanoscale bioactive glasses with different morphologies were prepared through sol-gel process using lactic acid as hydrolysis promoter. The effect of lactic acid concentration on the morphology of bioactive glass was characterized. The influence of the morphology on the in vitro bioactivity of samples was investigated in simulated body fluid and examined by various methods. The results showed that nanoscale surface morphologies with high roughness, created by addition of lactic acid, greatly enhanced the in vitro bioactivity of as-prepared samples. It was found that the morphology with nanoscale surface feature and pore size distribution, in addition to specific surface area and pore volume, plays an important role in accelerating the formation of carbonated hydroxyapatite. According to our results, bioactive glasses possessing surface morphology with significant numbers of nanoscale bioactive glass particles and a narrow unimodal or bimodal mesopore structure, exhibit the best in vitro bioactivity.