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.     

Characteristics of poly(alkyl silsesquioxane) thin films prepared from chemically linked alkyl units

Poly(alkyl silsesquioxane), PASSQ, copolymers containing the different alkyl components were synthesized by sol–gel polymerization with a bridged alkoxysilane as a matrix component, and the potential applications of low-k films were verified using TGA, FT-IR, ¹³C and ²⁹Si solid state NMR after pore forming process by the thermal decomposition. As the higher alkyl groups in PASSQ were decomposed, the lower refractive indices were achieved from 1.45 to 1.27 due to the formation of nanoporous in the film. In particular, the modulus for the three different PASSQ films were significantly higher than 3.8 GPa of the typical thin film of poly(methyl silsesquioxane). The enhanced moduli for the films are ascribed to the formation of rigid film structure by the introduction of bridged ethylene of BTMSE in spite of the porous structure. In addition, the partial decomposition of bridge ethylene groups was accompanied with the dominant occurrence of methyl silicon groups, which reduced the mechanical properties with microporous structure.     

Immobilization and catalytic activity of lipase on mesoporous silica prepared from biocompatible gelatin organic template

Mesoporous silica (MPS) with high surface area (518.8 m²/g), tunable pore size (3.6-13.7 nm) was synthesized using inexpensive sodium silicate as the source of silica and the biodegradable gelatin as the structure directing agent. The amorphous mesostructures of the materials were characterized by N₂ adsorption-desorption isotherms, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The synthesized MPS was then utilized as supports for immobilization of Porcine pancreatic lipase (PPL) by physical adsorption. The measurements of Fourier transform infrared spectroscopy (FT-IR), N₂ adsorption-desorption isotherms and energy-dispersive spectroscopy (EDS) demonstrated that PPL had been adsorbed into the channels of the MPS. The immobilized PPL was used for catalyzing hydrolysis reaction of triacetin, and its correlative catalytic activity was studied. Compared with free PPL, the immobilized PPL possessed superior adaptability in alkaline range (pH = 7.0-9.0), good thermal stability and excellent reusability in phosphate buffer solution in hydrolysis reactions of triacetin. The results also indicated that the immobilized PPL maintained 45% of its initial activity even after being reused six times.     

Evaluation of glass ionomer cements properties obtained from niobium silicate glasses prepared by chemical process

Glass ionomer cements (GICs) are glass and polymer composite materials. These materials currently find use in the dental field. The purpose of this work is to obtain systems based on composition 4.5SiO₂–3Al₂O₃–XNb₂O₅–2CaO to be used in Dentistry. The systems were prepared by chemical route at 700 °C. The results obtained by XRD and DTA showed that all systems prepared are glasses. The structures of the obtained glasses were compared to commercial material using ²⁷Al and ²⁹Si MAS NMR. The analysis of MAS NMR spectra indicated that the systems developed and commercial material are formed by SiO₄ and AlO₄ linked tetrahedra. The properties of glass ionomer cements based on the glasses prepared with several niobium contents were studied. Setting and working times of the cement pastes, microhardness and diametral tensile strength were evaluated for the experimental GICs and commercial luting cements. It was concluded that setting time of the cement pastes increased with increasing niobium content of the glasses (X). The properties to the GICs such as setting time and microhardness were influenced by niobium content.     

Effect of Ni-addition on the crystallization behavior and the oxidation resistance of Zr-based metallic glasses below the crystallization temperature

The crystallization behavior of Zr_65.0Al_7.5Ni_10.0Cu_17.5 metallic glasses by addition of Ni with 753 K annealing treatment and its effect on the oxidation resistance around the supercooled liquid region at 663 K were studied. By annealing at 753 K, the nanocrystalline phase of bct-Zr₂Cu precipitates was observed in the Zr_65.0Al_7.5Cu_27.5 specimen, while microstructures consisting of finer nanocrystalline bct-Zr₂Cu, fcc-Zr₂Ni and Zr₆Al₂Ni formed in the Zr_65.0Al_7.5Ni_10.0Cu_17.5 specimen. The oxidation resistance of the melt-spun Zr_65.0Al_7.5Ni_10.0Cu_17.5 specimen was improved by addition of Ni, which is evidenced by less mass gain and thin oxide scale. The microstructural refinement by the formation of numerous nanocrystalline phases of bct-Zr₂Cu, fcc-Zr₂Ni and Zr₆Al₂Ni from the matrix resulted in an improvement of the oxidation resistance, whereas a relative coarse nanocrystalline phase consisting of bct-Zr₂Cu exhibited fast oxidation along grain boundaries. Although the oxide species for both specimens were composed of a large amount of CuO/Cu₂O, some tetragonal and monoclinic-ZrO₂ as well as a minor amount of the oxide state of Cu³⁺, the amount of oxides especially for ZrO₂ in the Zr_65.0Al_7.5Ni_10.0Cu_17.5 specimen was lower, which was probably due to suppressed oxygen diffusion in ZrO₂.     

Low temperature specific heat of doped and undoped glasses

In this work we have measured the specific heat, c_p, of several glasses between 2 and 160 K. The experiments were performed in low silica calcium aluminosilicate (prepared under vacuum and room atmosphere conditions), in silicate and in fluoride glasses. The influence of neodymium, iron and cobalt in c_p values at low temperature was also investigated. The scaling proposed by Liu and Löhneysen was used to analyze the experimental data. The temperatures in which the maxima in c_p/T³, the so called boson peak, occur are discussed in terms of the Hrubý coefficient, which provides information about the glass forming ability.     

Mössbauer and EPR spectra for glasses and glass-ceramics prepared from simulated compositions of Lunar and Martian soils

In situ resource processing and utilization on planetary bodies is an important and integral part of NASA’s space exploration program. Within this scope and context, our general effort is primarily aimed at developing glass and glass-ceramic type materials using Lunar and Martian soils, and exploring various application potentials of these materials for planetary surface operations. This paper reports the successful preparation of glasses from the melts of simulated composition of Lunar and Martian soils, and thermal and structural characterization using differential thermal analysis (DTA), Mössbauer and electron paramagnetic resonance (EPR) spectroscopy. Glass-ceramic materials were developed from these glasses using selective heat treatment, and were also analyzed by Mössbauer and EPR spectroscopy. The crystalline phases formed at different stages of heat treatment were analyzed and identified by X-ray diffraction (XRD). Potential applications envisaged up to this time of these glasses/glass-ceramics on the surface of Moon or Mars are discussed.     

Growth habit of crystals of refractory compounds prepared from high temperature solutions

The growth habit of single crystal refractory compounds (borides, carbides and silicides) obtained using a solution-melt method involving various growth conditions is reviewed. The effect of external and internal factors on the growth habit is analyzed. The influence of such external factors as the cooling mode, the cooling rate, the effect of variation of solute concentration, the stoichiometry of the initial components, the presence of additives in the system, the change of the maximum soaking temperature, the nature of the initial components and the solvent metal and microgravity on the growth habit are described. Examples of various anisotrophic properties in crystals of refractory compounds as well as data on crystal michrohardness anisotropy, obtained by the authors, are given. In conclusion the comparative evaluation of the effect of external factors on growth habit is provided.     

Structure and dynamics of oxide melts and glasses: A view from multinuclear and high temperature NMR

From a presentation of the various nuclear magnetic resonance (NMR) experiments that allows to characterize the local structure and dynamics of oxide glasses and melts, we show that it becomes possible to evidence not only the details of the coordination state of the constituting atoms but also the nature of polyatomic molecular motifs extending over several chemical bonds.     

Dielectric behavior and impedance spectroscopy of bismuth iron phosphate glasses

The electrical and dielectrical properties of Bi₂O₃–Fe₂O₃–P₂O₅ glasses were measured by impedance spectroscopy in the frequency range from 0.01 Hz to 4 MHz and over the temperature range from 303 to 473 K. It was shown that the dc conductivity strongly depends on the Fe₂O₃ content and Fe(II)/Fe_tot ratio. With increasing Fe(II) ion content from 17% to 34% in the bismuth-free 39.4Fe₂O₃–59.6P₂O₅ and 9.8Bi₂O₃–31.7Fe₂O₃–58.5P₂O₅ glasses, the dc conductivity increases. On the other hand, the decrease in dc conductivity for the glasses with 18.9 mol% Bi₂O₃ is attributed to the decrease in Fe₂O₃ content from 31.7 to 23.5 mol%, which indicates that the conductivity for these glasses depends on Fe₂O₃ content. The conductivity for these glasses is independent of the Bi₂O₃ content and arises mainly from polaron hopping between Fe(II) and Fe(III) ions suggesting an electronic conduction. The evolution of the complex permittivity as a function of frequency and temperature was investigated. At low frequency the dispersion was investigated in terms of dielectric loss. The thermal activated relaxation mechanism dominates the observed relaxation behavior. The relationship between relaxation parameters and electrical conductivity indicates the electronic conductivity controlled by polaron hopping between iron ions. The Raman spectra show that the addition of up to 18.9 mol% of Bi₂O₃ does not produce any changes in the glass structure which consists predominantly of pyrophosphate units.     

Distributions of copper and CuBr in CuBr nanocrystallite-dispersed glasses prepared by copper staining

CuBr nanocrystallite-dispersed glasses were prepared by incorporation of copper into bromide ion-containing borosilicate glass using the technique of copper staining. The copper ion incorporation process was mainly controlled by ionic diffusion from the surface to the interior of the glass. The depth profiles of Cu and CuBr concentration were examined by energy dispersive X-ray analysis and by reference to the change in absorption intensity assigned to the CuBr exciton band along the depth. While the Cu concentration was found to decrease monotonically, the CuBr concentration profile showed a maximum at a distance of 10-50 μm from the glass surface. Although the depth reached by the copper ions became greater with increasing heat-treatment time, the depth at which CuBr was precipitated was found to be saturated. This means that regions were found in the glasses in which no CuBr crystallites precipitated, although migration of Cu ions to these regions had taken place.     

Influence of the polymer architecture on the high temperature behavior of SiCO glasses: A comparison between linear- and cyclic-derived precursors

Two series of cross-linked polysiloxanes, precursors for silicon oxycarbide glasses, have been synthesized from a linear and a cyclic Si-H-containing siloxane having the same chemical formula (SiCOH₄). The crosslinking has been achieved by hydrosilylation reaction with various amounts of divinylbenzene (DVB). A detailed structural characterization has been performed by ²⁹Si and ¹³C MAS NMR, FT-IR and chemical analysis. As a result, two different structural models have been proposed for the two series of resins. The two resins have been pyrolyzed at 1400 °C and the resulting SiCO ceramics characterized by X-ray diffraction. It has been shown that the stability of the amorphous silica phase present in the SiCO ceramics is strongly influenced by the molecular organization of the starting precursors. The presence of siloxane rings in the cyclic-derived polysiloxane decreases the stability of the amorphous SiO₂ and promotes the crystallization of cristobalite.     

Crystallization behaviour of Al-based metallic glasses below and above the glass-transition temperature

The present paper aims to report an effect of a supercooled liquid region on crystallization behaviour of the Al₈₅Y_8−xNd_xNi₅Co₂ metallic glasses produced by rapid solidification of the melt. The paper describes the crystallization process at different regimes of heat treatment. It is found that crystallization behaviour of the above-mentioned Al-based metallic glasses above the glass-transition temperature and below it follows different transformation mechanisms. Formation of the primary nanoscale α-Al particles was observed during continuous heating or after isothermal annealing above the glass-transition temperature. During isothermal annealing below the glass-transition temperature an unknown metastable phase is formed conjointly with α-Al. The metastable phase formed in the Nd-free alloy varies from that in the Nd-bearing alloys. Al₈₅Nd₈Ni₅Co₂ amorphous alloy exhibiting no glass transition crystallizes equally during isothermal calorimetry at different temperatures and during continuous heating.     

High temperature x‐ray diffraction studies of zirconia thin films prepared by reactive pulsed laser deposition

Zirconium oxide thin films have been deposited on Si (100) substrates at room temperature at an optimized oxygen partial pressure of 3x10^‐2 mbar by reactive pulsed laser deposition. High temperature x‐ray diffraction (HTXRD) studies of the film in the temperature range room temperature‐1473 K revealed that the film contained only monoclinic phase at temperatures ≤ 673 K and both monoclinic and tetragonal phases were present at temperatures ≥ 773 K. The tetragonal phase content was significantly dominating over monoclinic phase with the increase of temperature. The phase evolution was accompanied with the increase in the crystallite size from 20 to 40 nm for the tetragonal phase. The mean thermal expansion coefficients for the tetragonal phase have been found to be 10.58x10^‐6 K^‐1 and 20.92x10^‐6K^‐1 along a and c‐axes, respectively. The mean volume thermal expansion coefficient is 42.34x10^‐6 K^‐1 in the temperature range 773‐1473 K. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Discrepancy of structural stability against temperature between metallic liquids and their glasses

The stability of the disordered structure in liquid or glass states could be characterized by the glass-forming ability (GFA) and thermal stability (TS), respectively. The two quantities are often, but not always, positively correlated. Here we show that the discrepancy between GFA and TS originates from the competition between entropy and enthalpy which fairly much relies on local structural characteristics. This inherent interaction and competition determines hierarchy of phase stability against temperature. As a result, the time susceptibility of GFA and temperature susceptibility of TS were derived from the time-temperature-transformation diagram, which are coincided with the above mentioned entropy-enthalpy competition perspective. Thus, the interrelationship among entropy, enthalpy and local cluster feature provides a potential resolution to design and optimize glass formers, and have implications for better understanding the nature of glass transition.     

Copper redox behavior, structure and properties of copper lead borate glasses

Copper oxidation states, structure and properties of xCuO · (50-x)PbO · 50B₂O₃ glasses were investigated. Both infrared (IR) and ¹¹B magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopies were employed to determine the tetrahedral BO₄ fraction in the glasses as a function of CuO content. IR study indicates that the replacement of Pb²⁺ by Cu²⁺ ions increases the BO₃ units by converting BO₄- containing groups into ring type metaborate groups. The oxidation states of copper ions in the glasses have been studied using both X-ray photoelectron spectroscopy (XPS) and the wet chemical method. For high CuO containing (?30 mol%) glasses, high Cu⁺ ion concentrations (Cu⁺/Cu_tot.>0.3) result in a relatively slow disproportionation of B⁴-containing groups because of the small coordination number of Cu⁺ compared to Cu²⁺ ions. Effects of both glass structure and redox states of copper ions on glass properties including density, Vickers’ hardness, coefficient of thermal expansion, and chemical durability have been discussed.     

Electron paramagnetic resonance and thermal behavior of vanadyl-doped mixed alkali bismuth borate glasses

Glasses with composition 15 Li₂O15K₂O10Bi₂O₃(60 ? x) B₂O₃: xV₂O₅ where x = 1, 3, 5, 7, and 9 mol% are prepared by normal melt-quench technique. Characterization of the prepared samples is done using X-ray diffraction, density and differential scanning calorimetry. The density and molar volume are found to increase with increasing x whereas the glass transition temperature decreases. Electron paramagnetic resonance spectra of the prepared samples are recorded using EPR-spectrometer operating in the X-band frequency. The resonance spectra are well resolved for x ≥ 5 mol% and the intensity of the resonance peak is found to increase with increasing x. The values of spin-Hamiltonian parameters (SHP) and molecular orbital coefficients are evaluated. From the values of SHPs it is concluded that V⁴⁺ ions in the present glass system exist as vanadyl ions in octahedral co-ordination with tetragonal compression. It is observed that the SPHs depend slightly on the relative concentration of V₂O₅. Further, the theoretical optical basicity of the glasses has also been evaluated and it is observed that the changes in optical basicity values are in accordance with the changes in SHPs.     

Molar volume,glass-transition temperature,and ionic conductivity of Na- and Rb-borate glasses in comparison with mixed Na–Rb borate glasses

Mass densities, molar volumes, glass-transition temperatures, and ionic conductivities are measured in series of YNa₂O · (1 − Y)B₂O₃ glasses, with Y = 0.00, 0.04, 0.08, 0.12, 0.16, 0.20, 0.25, 0.30 and YRb₂O · (1 − Y)B₂O₃ glasses, with Y = 0.00, 0.12, 0.16, 0.20, 0.25, 0.30. Measurements of the molar volumes indicate that the incorporation of rubidium ions leads to a considerable expansion of the network, which is not observed for sodium ions. The glass-transition temperature increases with increasing alkali content and reaches a maximum near Y = 0.25 for both glass systems. These trends are attributed to changes in the glass network. For each glass composition an Arrhenius-activated increase of the product of dc conductivity and temperature is observed. The activation enthalpy decreases with increasing number density of ions. A comparison between the binary sodium- and rubidium-borate glasses from this work, with the ternary sodium–rubidium borate glasses studied earlier in our laboratory, provides interesting insights in the influence of the glass structure on ionic transport processes and the mixed-alkali effect.     

Effect of antimony addition on the thermal and electrical-switching behavior of bulk Se-Te glasses

The thermal properties and electrical-switching behavior of semiconducting chalcogenide Sb_xSe_55−xTe₄₅ (2 ? x ? 9) glasses have been investigated by alternating differential scanning calorimetry and electrical-switching experiments, respectively. The addition of Sb is found to enhance the glass forming tendency and stability as revealed by the decrease in non-reversing enthalpy ΔH_nr, and an increase in the glass-transition width ΔT_g. Further, the glass-transition temperature of Sb_xSe_55−xTe₄₅ glasses, which is a measure of network connectivity, exhibits a subtle increase, suggesting a meager network growth with the addition of Sb. The crystallization temperature is also observed to increase with Sb content. The Sb_xSe_55−xTe₄₅ glasses (2 ? x ? 9) are found to exhibit memory type of electrical switching, which can be attributed to the polymeric nature of network and high devitrifying ability. The metallicity factor has been found to dominate over the network connectivity and rigidity in the compositional dependence of switching voltage, which shows a profound decrease with the addition of Sb.